combustion i s

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7/27/2019 Combustion I S http://slidepdf.com/reader/full/combustion-i-s 1/96 Schlumberger - NTNU Ambassador Lecture Series In-Situ Combustion Simulation with ECLIPSE By Chuck Kossack Schlumberger Advisor Denver, Colorado NTNU - In-Situ Combustion SIS Training April 10 S c h l u m b e r g e r P r i v a t e 2 Outline of the Lecture Where does In-situ Combustion Simulation fit in? Review of Thermal Reservoir Simulation Basic theory of chemical reactions In-situ combustion – overview ECLIPSE Thermal treatment of chemical reactions Simulation of in-situ combustion with ECLIPSE Thermal – Example Simulation – Wet Forward Combustion – Sensitivity to Water Air Ratio

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Page 1: Combustion I S

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Schlumberger - NTNU Ambassador Lecture Series

In-Situ Combustion Simulation withECLIPSE

By

Chuck Kossack Schlumberger Advisor

Denver Colorado

NTNU - In-Situ Combustion

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Outline of the Lecture

Where does In-situ Combustion Simulation fit inReview of Thermal Reservoir SimulationBasic theory of chemical reactionsIn-situ combustion ndash overviewECLIPSE Thermal treatment of chemical reactionsSimulation of in-situ combustion with ECLIPSE Thermal ndash

Example Simulation ndash Wet Forward Combustion ndashSensitivity to Water Air Ratio

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Where does In-situ Combustion Simulation fi t in

simple rarr complex rarr more complex rarr most complex

Black oil rarr Compositional rarr Thermal rarr In-situ Combustion

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Black Oil - Simple

Unknowns P o Sw Sg

Oil

Water

Gas

Oil

Water

Gas

grid block

PVT ndash B o B g R s R v table look up on pressure

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Compositional - Complex

Unknowns P o Sw zi (i=12hellipn c)

Liquid andvaporphasescontaining

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Flash with Equation of State

Liquid andvaporphasescontaining

Methane

Ethane

Propane

hellip

Decane

hellip

and water

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Thermal ndash More Complex

Unknowns P o Sw zi (i=12hellipn c) e

Enthalpy eLiquid and vaporphases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vaporphases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

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In-situ Combustion ndash Most Complex

Unknowns P o SH2O zi (i = N 2 O 2 CO 2 C6 C 10 C 20 C 30) e

Enthalpy eLiquid and vaporphases containing

Methane

Hexane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vaporphases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

Reactions

C6H8 + 8O2 rarr 6CO2 + 4H20 + HEAT

C10H12 + 13O2 rarr 10CO2 + 6H20 + HEAT

C20H22 +255O2 rarr 20CO2 +11H20 + HEAT

C30H32 + 38O2 rarr 30CO2 + 16H20 + HEAT

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Review of Thermal Reservoir Simulation

Key Points From Last Yearrsquos Lecture

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ECLIPSE Thermal Simulator - Energy

In principle there are 2 methods of energy transfer

Convection ndash with fluid flow

Conduction ndash in fluid phases and in rock

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Comparison of Black Oil Compositional and ThermalModels

Unknowns(Nc+3) variables per grid block

ECLIPSE Thermal Live Oil

⎟⎟

⎜⎜

e z z

P

i

w

i = 1 N c (molar density)

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Conservation Equations - Energy

( ) e HLeebe QQC F eV dt d

R ++++=

The energy conservation equation solved in each grid block ateach timestep

blocksgridgneighborininto

rateflowenthalpyconvective

e bulk volum

residuallinear -non

===

e

b

e

F

V

R

where

timesteptheduring

wellsintorateflowenthalpynetthe

loss)(heatrocksgsurroundintheto

rateflowenergyconductive

blocksgridgneighborininto

rateflowenergyconductive

=

=

=

e

HL

e

Q

Q

C

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determinedby K=values

ww

wwg

co

ccg

xT PK y

xT PK y

sdot=

sdot=

)(

)(

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In-Situ Combustion Simulation

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14

Overview of the Lecture and Basic ChemicalReaction Theory

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Pre-requisites

Most chemical engineers - 1 or more courses in ChemicalReactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash cansimulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a

third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction types ndash Reaction mechanisms ndash Activation energy ndash Stoichiometry ndash Reaction Rate Rate Equation Rate Law ndash Heat of reaction ndash Order of reaction ndash Products and Rates

ndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breakingof chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NH H N rarr+

Chemical decomposition - analysis

222 22 O H O H +rarr

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Reaction Types

Single displacement - substitution

2222 H NaCl HCl Na +rarr+

Double displacement

AgCl NaNO AgNO NaCl +rarr+33

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Reaction types

Combustion - any combustible substance combines with anoxidizing element usually oxygen to generate heat and formoxidized products

O H COO H C 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementaryreactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformation ndash Transition state ndash where bonds are broken ndash What order bonds are broken and formed ndash Relative rates of each step ndash Function of catalyst ndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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148

RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 2: Combustion I S

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Where does In-situ Combustion Simulation fi t in

simple rarr complex rarr more complex rarr most complex

Black oil rarr Compositional rarr Thermal rarr In-situ Combustion

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Black Oil - Simple

Unknowns P o Sw Sg

Oil

Water

Gas

Oil

Water

Gas

grid block

PVT ndash B o B g R s R v table look up on pressure

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Compositional - Complex

Unknowns P o Sw zi (i=12hellipn c)

Liquid andvaporphasescontaining

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Flash with Equation of State

Liquid andvaporphasescontaining

Methane

Ethane

Propane

hellip

Decane

hellip

and water

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Thermal ndash More Complex

Unknowns P o Sw zi (i=12hellipn c) e

Enthalpy eLiquid and vaporphases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vaporphases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

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In-situ Combustion ndash Most Complex

Unknowns P o SH2O zi (i = N 2 O 2 CO 2 C6 C 10 C 20 C 30) e

Enthalpy eLiquid and vaporphases containing

Methane

Hexane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vaporphases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

Reactions

C6H8 + 8O2 rarr 6CO2 + 4H20 + HEAT

C10H12 + 13O2 rarr 10CO2 + 6H20 + HEAT

C20H22 +255O2 rarr 20CO2 +11H20 + HEAT

C30H32 + 38O2 rarr 30CO2 + 16H20 + HEAT

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Review of Thermal Reservoir Simulation

Key Points From Last Yearrsquos Lecture

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ECLIPSE Thermal Simulator - Energy

In principle there are 2 methods of energy transfer

Convection ndash with fluid flow

Conduction ndash in fluid phases and in rock

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Comparison of Black Oil Compositional and ThermalModels

Unknowns(Nc+3) variables per grid block

ECLIPSE Thermal Live Oil

⎟⎟

⎜⎜

e z z

P

i

w

i = 1 N c (molar density)

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Conservation Equations - Energy

( ) e HLeebe QQC F eV dt d

R ++++=

The energy conservation equation solved in each grid block ateach timestep

blocksgridgneighborininto

rateflowenthalpyconvective

e bulk volum

residuallinear -non

===

e

b

e

F

V

R

where

timesteptheduring

wellsintorateflowenthalpynetthe

loss)(heatrocksgsurroundintheto

rateflowenergyconductive

blocksgridgneighborininto

rateflowenergyconductive

=

=

=

e

HL

e

Q

Q

C

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determinedby K=values

ww

wwg

co

ccg

xT PK y

xT PK y

sdot=

sdot=

)(

)(

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In-Situ Combustion Simulation

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14

Overview of the Lecture and Basic ChemicalReaction Theory

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15

Pre-requisites

Most chemical engineers - 1 or more courses in ChemicalReactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash cansimulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a

third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction types ndash Reaction mechanisms ndash Activation energy ndash Stoichiometry ndash Reaction Rate Rate Equation Rate Law ndash Heat of reaction ndash Order of reaction ndash Products and Rates

ndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breakingof chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NH H N rarr+

Chemical decomposition - analysis

222 22 O H O H +rarr

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Reaction Types

Single displacement - substitution

2222 H NaCl HCl Na +rarr+

Double displacement

AgCl NaNO AgNO NaCl +rarr+33

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Reaction types

Combustion - any combustible substance combines with anoxidizing element usually oxygen to generate heat and formoxidized products

O H COO H C 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementaryreactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformation ndash Transition state ndash where bonds are broken ndash What order bonds are broken and formed ndash Relative rates of each step ndash Function of catalyst ndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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142

Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 3: Combustion I S

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Compositional - Complex

Unknowns P o Sw zi (i=12hellipn c)

Liquid andvaporphasescontaining

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Flash with Equation of State

Liquid andvaporphasescontaining

Methane

Ethane

Propane

hellip

Decane

hellip

and water

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Thermal ndash More Complex

Unknowns P o Sw zi (i=12hellipn c) e

Enthalpy eLiquid and vaporphases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vaporphases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

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In-situ Combustion ndash Most Complex

Unknowns P o SH2O zi (i = N 2 O 2 CO 2 C6 C 10 C 20 C 30) e

Enthalpy eLiquid and vaporphases containing

Methane

Hexane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vaporphases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

Reactions

C6H8 + 8O2 rarr 6CO2 + 4H20 + HEAT

C10H12 + 13O2 rarr 10CO2 + 6H20 + HEAT

C20H22 +255O2 rarr 20CO2 +11H20 + HEAT

C30H32 + 38O2 rarr 30CO2 + 16H20 + HEAT

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Review of Thermal Reservoir Simulation

Key Points From Last Yearrsquos Lecture

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ECLIPSE Thermal Simulator - Energy

In principle there are 2 methods of energy transfer

Convection ndash with fluid flow

Conduction ndash in fluid phases and in rock

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Comparison of Black Oil Compositional and ThermalModels

Unknowns(Nc+3) variables per grid block

ECLIPSE Thermal Live Oil

⎟⎟

⎜⎜

e z z

P

i

w

i = 1 N c (molar density)

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Conservation Equations - Energy

( ) e HLeebe QQC F eV dt d

R ++++=

The energy conservation equation solved in each grid block ateach timestep

blocksgridgneighborininto

rateflowenthalpyconvective

e bulk volum

residuallinear -non

===

e

b

e

F

V

R

where

timesteptheduring

wellsintorateflowenthalpynetthe

loss)(heatrocksgsurroundintheto

rateflowenergyconductive

blocksgridgneighborininto

rateflowenergyconductive

=

=

=

e

HL

e

Q

Q

C

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determinedby K=values

ww

wwg

co

ccg

xT PK y

xT PK y

sdot=

sdot=

)(

)(

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In-Situ Combustion Simulation

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14

Overview of the Lecture and Basic ChemicalReaction Theory

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Pre-requisites

Most chemical engineers - 1 or more courses in ChemicalReactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash cansimulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a

third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction types ndash Reaction mechanisms ndash Activation energy ndash Stoichiometry ndash Reaction Rate Rate Equation Rate Law ndash Heat of reaction ndash Order of reaction ndash Products and Rates

ndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breakingof chemical bonds

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19

Reaction Types

Direct combination - synthesis

322 23 NH H N rarr+

Chemical decomposition - analysis

222 22 O H O H +rarr

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Reaction Types

Single displacement - substitution

2222 H NaCl HCl Na +rarr+

Double displacement

AgCl NaNO AgNO NaCl +rarr+33

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Reaction types

Combustion - any combustible substance combines with anoxidizing element usually oxygen to generate heat and formoxidized products

O H COO H C 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementaryreactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformation ndash Transition state ndash where bonds are broken ndash What order bonds are broken and formed ndash Relative rates of each step ndash Function of catalyst ndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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24

Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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25

Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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28

Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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29

Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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30

Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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33

Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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34

Activation energy - threshold energy - Ea

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35

Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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36

Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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39

Stoichiometry

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40

Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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53

Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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59

Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 4: Combustion I S

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In-situ Combustion ndash Most Complex

Unknowns P o SH2O zi (i = N 2 O 2 CO 2 C6 C 10 C 20 C 30) e

Enthalpy eLiquid and vaporphases containing

Methane

Hexane

Propane

hellip

Decane

hellip

and water

grid block

PVT ndash Thermal Flash with K(PT)

Enthalpy eLiquid and vaporphases containing

Methane

Ethane

Propane

hellip

Decane

hellip

and water

Reactions

C6H8 + 8O2 rarr 6CO2 + 4H20 + HEAT

C10H12 + 13O2 rarr 10CO2 + 6H20 + HEAT

C20H22 +255O2 rarr 20CO2 +11H20 + HEAT

C30H32 + 38O2 rarr 30CO2 + 16H20 + HEAT

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Review of Thermal Reservoir Simulation

Key Points From Last Yearrsquos Lecture

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ECLIPSE Thermal Simulator - Energy

In principle there are 2 methods of energy transfer

Convection ndash with fluid flow

Conduction ndash in fluid phases and in rock

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Comparison of Black Oil Compositional and ThermalModels

Unknowns(Nc+3) variables per grid block

ECLIPSE Thermal Live Oil

⎟⎟

⎜⎜

e z z

P

i

w

i = 1 N c (molar density)

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Conservation Equations - Energy

( ) e HLeebe QQC F eV dt d

R ++++=

The energy conservation equation solved in each grid block ateach timestep

blocksgridgneighborininto

rateflowenthalpyconvective

e bulk volum

residuallinear -non

===

e

b

e

F

V

R

where

timesteptheduring

wellsintorateflowenthalpynetthe

loss)(heatrocksgsurroundintheto

rateflowenergyconductive

blocksgridgneighborininto

rateflowenergyconductive

=

=

=

e

HL

e

Q

Q

C

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determinedby K=values

ww

wwg

co

ccg

xT PK y

xT PK y

sdot=

sdot=

)(

)(

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In-Situ Combustion Simulation

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14

Overview of the Lecture and Basic ChemicalReaction Theory

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15

Pre-requisites

Most chemical engineers - 1 or more courses in ChemicalReactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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16

Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash cansimulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a

third and give off or consume energy

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17

Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction types ndash Reaction mechanisms ndash Activation energy ndash Stoichiometry ndash Reaction Rate Rate Equation Rate Law ndash Heat of reaction ndash Order of reaction ndash Products and Rates

ndash Thermochemistry

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18

Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breakingof chemical bonds

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19

Reaction Types

Direct combination - synthesis

322 23 NH H N rarr+

Chemical decomposition - analysis

222 22 O H O H +rarr

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Reaction Types

Single displacement - substitution

2222 H NaCl HCl Na +rarr+

Double displacement

AgCl NaNO AgNO NaCl +rarr+33

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Reaction types

Combustion - any combustible substance combines with anoxidizing element usually oxygen to generate heat and formoxidized products

O H COO H C 222810 41012 +rarr+

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22

Reaction Mechanisms

Definition ndash the step by step sequence of elementaryreactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformation ndash Transition state ndash where bonds are broken ndash What order bonds are broken and formed ndash Relative rates of each step ndash Function of catalyst ndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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24

Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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25

Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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27

Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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28

Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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29

Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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30

Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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32

Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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33

Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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34

Activation energy - threshold energy - Ea

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35

Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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36

Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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37

Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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38

Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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39

Stoichiometry

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40

Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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42

Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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44

Reaction Rate Rate Equation Rate Law

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45

Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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46

Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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48

Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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49

Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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50

Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 5: Combustion I S

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ECLIPSE Thermal Simulator - Energy

In principle there are 2 methods of energy transfer

Convection ndash with fluid flow

Conduction ndash in fluid phases and in rock

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Comparison of Black Oil Compositional and ThermalModels

Unknowns(Nc+3) variables per grid block

ECLIPSE Thermal Live Oil

⎟⎟

⎜⎜

e z z

P

i

w

i = 1 N c (molar density)

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Conservation Equations - Energy

( ) e HLeebe QQC F eV dt d

R ++++=

The energy conservation equation solved in each grid block ateach timestep

blocksgridgneighborininto

rateflowenthalpyconvective

e bulk volum

residuallinear -non

===

e

b

e

F

V

R

where

timesteptheduring

wellsintorateflowenthalpynetthe

loss)(heatrocksgsurroundintheto

rateflowenergyconductive

blocksgridgneighborininto

rateflowenergyconductive

=

=

=

e

HL

e

Q

Q

C

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determinedby K=values

ww

wwg

co

ccg

xT PK y

xT PK y

sdot=

sdot=

)(

)(

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In-Situ Combustion Simulation

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Overview of the Lecture and Basic ChemicalReaction Theory

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Pre-requisites

Most chemical engineers - 1 or more courses in ChemicalReactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash cansimulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a

third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction types ndash Reaction mechanisms ndash Activation energy ndash Stoichiometry ndash Reaction Rate Rate Equation Rate Law ndash Heat of reaction ndash Order of reaction ndash Products and Rates

ndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breakingof chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NH H N rarr+

Chemical decomposition - analysis

222 22 O H O H +rarr

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Reaction Types

Single displacement - substitution

2222 H NaCl HCl Na +rarr+

Double displacement

AgCl NaNO AgNO NaCl +rarr+33

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Reaction types

Combustion - any combustible substance combines with anoxidizing element usually oxygen to generate heat and formoxidized products

O H COO H C 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementaryreactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformation ndash Transition state ndash where bonds are broken ndash What order bonds are broken and formed ndash Relative rates of each step ndash Function of catalyst ndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 6: Combustion I S

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Conservation Equations - Energy

( ) e HLeebe QQC F eV dt d

R ++++=

The energy conservation equation solved in each grid block ateach timestep

blocksgridgneighborininto

rateflowenthalpyconvective

e bulk volum

residuallinear -non

===

e

b

e

F

V

R

where

timesteptheduring

wellsintorateflowenthalpynetthe

loss)(heatrocksgsurroundintheto

rateflowenergyconductive

blocksgridgneighborininto

rateflowenergyconductive

=

=

=

e

HL

e

Q

Q

C

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Thermodynamic Equilibrium Flash

Three phases in thermodynamic equilibrium ndash determinedby K=values

ww

wwg

co

ccg

xT PK y

xT PK y

sdot=

sdot=

)(

)(

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In-Situ Combustion Simulation

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14

Overview of the Lecture and Basic ChemicalReaction Theory

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Pre-requisites

Most chemical engineers - 1 or more courses in ChemicalReactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash cansimulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a

third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction types ndash Reaction mechanisms ndash Activation energy ndash Stoichiometry ndash Reaction Rate Rate Equation Rate Law ndash Heat of reaction ndash Order of reaction ndash Products and Rates

ndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breakingof chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NH H N rarr+

Chemical decomposition - analysis

222 22 O H O H +rarr

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Reaction Types

Single displacement - substitution

2222 H NaCl HCl Na +rarr+

Double displacement

AgCl NaNO AgNO NaCl +rarr+33

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Reaction types

Combustion - any combustible substance combines with anoxidizing element usually oxygen to generate heat and formoxidized products

O H COO H C 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementaryreactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformation ndash Transition state ndash where bonds are broken ndash What order bonds are broken and formed ndash Relative rates of each step ndash Function of catalyst ndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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39

Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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62

Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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In-Situ Combustion Simulation

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Overview of the Lecture and Basic ChemicalReaction Theory

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Pre-requisites

Most chemical engineers - 1 or more courses in ChemicalReactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash cansimulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a

third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction types ndash Reaction mechanisms ndash Activation energy ndash Stoichiometry ndash Reaction Rate Rate Equation Rate Law ndash Heat of reaction ndash Order of reaction ndash Products and Rates

ndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breakingof chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NH H N rarr+

Chemical decomposition - analysis

222 22 O H O H +rarr

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Reaction Types

Single displacement - substitution

2222 H NaCl HCl Na +rarr+

Double displacement

AgCl NaNO AgNO NaCl +rarr+33

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Reaction types

Combustion - any combustible substance combines with anoxidizing element usually oxygen to generate heat and formoxidized products

O H COO H C 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementaryreactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformation ndash Transition state ndash where bonds are broken ndash What order bonds are broken and formed ndash Relative rates of each step ndash Function of catalyst ndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 8: Combustion I S

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Pre-requisites

Most chemical engineers - 1 or more courses in ChemicalReactions and Chemical Kinetics ndash so this is a reviewMost petroleum engineers mechanical engineers

mathematicians - not had such a courseThe following lecture gives a brief overview of Chemical

Reactions and Chemical KineticsWith this knowledge one will be able to understand

ECLIPSE Chemical Reactions theory and applications

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Overview of the lecture

Chemical reactions exist in ECLIPSE Thermal ndash cansimulate

bull Combustionbull Biodegradationbull Decay of radioactive tracersbull Non-equilibrium reactions

Allows one component to react with another and create a

third and give off or consume energy

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction types ndash Reaction mechanisms ndash Activation energy ndash Stoichiometry ndash Reaction Rate Rate Equation Rate Law ndash Heat of reaction ndash Order of reaction ndash Products and Rates

ndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breakingof chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NH H N rarr+

Chemical decomposition - analysis

222 22 O H O H +rarr

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Reaction Types

Single displacement - substitution

2222 H NaCl HCl Na +rarr+

Double displacement

AgCl NaNO AgNO NaCl +rarr+33

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Reaction types

Combustion - any combustible substance combines with anoxidizing element usually oxygen to generate heat and formoxidized products

O H COO H C 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementaryreactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformation ndash Transition state ndash where bonds are broken ndash What order bonds are broken and formed ndash Relative rates of each step ndash Function of catalyst ndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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62

Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Outline ndash Section 1

IntroductionKeys To Understanding Chemical Reactions

ndash Reaction types ndash Reaction mechanisms ndash Activation energy ndash Stoichiometry ndash Reaction Rate Rate Equation Rate Law ndash Heat of reaction ndash Order of reaction ndash Products and Rates

ndash Thermochemistry

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Chemical Reaction

A chemical reaction is a process that results in the inter-conversion of chemical substancesChemical reactions encompass changes that strictly

involve the motion of electrons in the forming and breakingof chemical bonds

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Reaction Types

Direct combination - synthesis

322 23 NH H N rarr+

Chemical decomposition - analysis

222 22 O H O H +rarr

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Reaction Types

Single displacement - substitution

2222 H NaCl HCl Na +rarr+

Double displacement

AgCl NaNO AgNO NaCl +rarr+33

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Reaction types

Combustion - any combustible substance combines with anoxidizing element usually oxygen to generate heat and formoxidized products

O H COO H C 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementaryreactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformation ndash Transition state ndash where bonds are broken ndash What order bonds are broken and formed ndash Relative rates of each step ndash Function of catalyst ndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Reaction Types

Direct combination - synthesis

322 23 NH H N rarr+

Chemical decomposition - analysis

222 22 O H O H +rarr

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Reaction Types

Single displacement - substitution

2222 H NaCl HCl Na +rarr+

Double displacement

AgCl NaNO AgNO NaCl +rarr+33

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Reaction types

Combustion - any combustible substance combines with anoxidizing element usually oxygen to generate heat and formoxidized products

O H COO H C 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementaryreactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformation ndash Transition state ndash where bonds are broken ndash What order bonds are broken and formed ndash Relative rates of each step ndash Function of catalyst ndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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142

Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 11: Combustion I S

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Reaction types

Combustion - any combustible substance combines with anoxidizing element usually oxygen to generate heat and formoxidized products

O H COO H C 222810 41012 +rarr+

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Reaction Mechanisms

Definition ndash the step by step sequence of elementaryreactions by which overall chemical change occursMechanism describes in detail exactly what takes place

at each stage of a chemical transformation ndash Transition state ndash where bonds are broken ndash What order bonds are broken and formed ndash Relative rates of each step ndash Function of catalyst ndash All products formed and their amount

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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48

Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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50

Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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52

Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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53

Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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54

Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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55

Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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59

Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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62

Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Intermediate Reactions

Overall Reaction3H 2(g)+N 2(g)rarr 2NH 3(g)

Intermediate steps N2(g) rarr N2(adsorbed- on iron catalyst (Fe 3+)

N2(adsorbed) rarr 2N(adsorbed) Rate Limiting StepH2(g) rarr H2(adsorbed)H2(adsorbed) rarr 2H(adsorbed)

N(adsorbed) + 3H(adsorbed) rarr NH 3(adsorbed) NH

3(adsorbed) rarr NH

3(g)

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Products and Rates

Thermodynamicsbull Controls specifies whether a specific chemical reaction

can occur bull Determines initial and final states of the reaction mixture

(products)

Chemical kineticsbull Determines rates of the reactions

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Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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142

Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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161

Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 13: Combustion I S

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Chemical Kinetics

Rate of a chemical reaction - measure of how theconcentration or pressure of the involved substanceschanges with time

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Chemical Kinetics

Rates of reaction depends basically onbull Reactant concentrationsbull Surface Areabull Pressurebull Activation energy ndash Ea (some time Er or E)bull Temperaturebull The presence or absence of a catalyst

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Chemical Kinetics

Some reactions occur in gas phase ndash Combustion of liquid fuel ndash As fuel heats up some components vaporize ndash Oxygen and vapor components react in gas phase

Some reaction occur on a solid surface ndash If reactants are in different phases (one in gas other

solid) ndash Surface area interface between reactants is the key to

the rate

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Order of Reaction

A detailed discuss of Order of Reaction will follow later A short summary isMost reactions are either ndash Zero Order ndash reaction rate is independent of reactants

concentration ndash First Order ndash reaction rate is dependent on a

concentration to 1st power ndash Second Order - reaction rate is dependent on a

concentration to 2nd power or product of 2 concentrations

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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48

Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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50

Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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52

Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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53

Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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54

Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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55

Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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56

Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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59

Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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62

Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Activation energy - threshold energy - Ea

Svante Arrhenius (1859-1927Sweden Nobel Prize in 1903)studied the dependence of thereaction rate versus temperatureand proposed aphenomenological law

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Activation energy - threshold energy - Ea

Introduced in 1889 by Svante Arrhenius that is defined asthe energy that must be overcome in order for a chemicalreaction to occur As previously stated reaction proceed from

ndash Reactants rarr transition staterarr products ndash Activation energy is energy required to produce the

transition state ndash transition states exist for 10-15 seconds

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 16: Combustion I S

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Activation energy with and without catalyst

biological catalyst is termed an enzyme

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Activation energy - threshold energy - Ea

Activation energy is the height of the potential barrier (sometimes called the energy barrier) separating twominima of potential energy (of the reactants and of theproducts of reaction)For chemical reaction to have noticeable rate there

should be noticeable number of molecules with the energyequal or greater than the activation energy

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Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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36

Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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39

Stoichiometry

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40

Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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44

Reaction Rate Rate Equation Rate Law

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45

Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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142

Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 17: Combustion I S

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33

Activation energy - threshold energy - Ea

3 necessary requirements for a reaction to take place ndash molecules must collide to react ndash must be enough energy (energy of activation) for the two

molecules to react ndash molecules must be orientated with respect to each other

correctly

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Activation energy - threshold energy - Ea

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 18: Combustion I S

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Activation energy - threshold energy - Ea

Energy comes from ndash Heat of the system ndash From translational vibrational and rotational energy of

each molecule ndash Higher the temperature pressure ndash higher the energy

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Activation energy - threshold energy - Ea

Arrhenius Equation - quantitative - relationship between theactivation energy and the reaction rate

⎟ ⎠ ⎞

⎜⎝ ⎛ minus=

Ak

RT E a ln

Where k = reaction rate or rate constant or reactionrate constant (units depend on order of reaction)

A = frequency factor (units same as k) sometime alsocalled reaction rate constant

R = gas constant

T = absolute temperature

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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59

Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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62

Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 19: Combustion I S

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Arrhenius Equation

To give the reaction rate (or rate constant)

RT E a Aek minus=A is pre-exponential factor (sometime called reaction rateconstant) ndash units same as rate constant ndash varies ndash depends onorder of reaction (discuss later)

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Reaction Rate Constant ndash A or Ar

Units depend of order of reactionValues determined from experimentsFinding values in hand books references and internet is

difficultValues can be 1 to 1010 depending on the size of your

system

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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47

Some Reaction are Fast ndash oxidation of wood

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48

Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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50

Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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51

Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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52

Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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53

Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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54

Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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55

Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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56

Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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59

Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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62

Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 20: Combustion I S

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Stoichiometry

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Stoichiometry

Stoichiometry derives from the Greek words stoikheion(element) and metriā (measure from metron)Stoichiometry ndash based on ndash law of conservation of mass ndash the law of definite proportions (ie the law of constant

composition) ndash the law of multiple proportions

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Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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50

Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 21: Combustion I S

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41

Stoichiometry

Chemical reactions combine in definite ratios of chemicalsChemical reactions ndash neither create nor destroy matter ndash nor transmute one element into another ndash the amount of each element must be the same

throughout the overall reactionbull For example the amount of element X on the reactant side

must equal the amount of element X on the product side

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Stoichiometry

Example combustion of Hydrogen

O H O H 222 22 rarr+

4 Hydrogen atoms on reactants side ndash 4 Hydrogen atomson products side

2 Oxygen atoms on the reactants side - 2 Oxygen atomson the products side

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Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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44

Reaction Rate Rate Equation Rate Law

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45

Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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49

Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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50

Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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53

Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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55

Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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59

Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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62

Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 22: Combustion I S

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43

Stoichiometry

Example thermite reaction

FeO Al AlOFe 22 3232+rarr+

2 Iron atoms on reactants side ndash 2 Iron atoms on productsside

3 Oxygen atoms on the reactants side - 3 Oxygen atomson the products side

2 Aluminum atoms on the reactants side - 2 Aluminum

atoms on the products sideA thermite reaction is a type of aluminothermic reaction in which aluminum metal is oxidized by the oxide of another metal most commonly iron oxide

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Reaction Rate Rate Equation Rate Law

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Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 23: Combustion I S

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45

Reaction Rate Rate Equation Rate Law

Questions we would like answeredHow fast does the reaction proceedWhat factors effect the reaction rateCan we calculate the amount of products creates as a

function of time

Studying the Reaction Rate will answer these questions

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Some Reactions are Slow ndash oxidation of Iron

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Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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49

Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 24: Combustion I S

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47

Some Reaction are Fast ndash oxidation of wood

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Reaction Rate

Reaction rate = v = r = R

Closed system ndash constant volume conditions ndash without appreciable build-up of reactionintermediates

qQ pPbBaA +rarr+

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49

Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 25: Combustion I S

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49

Reaction Rate

[ ] [ ] [ ] [ ]dt Qd

qdt Pd

pdt Bd

bdt Ad

av

1111 ==minus=minus=

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Factors Influencing Rate of Reaction

Concentration

Reaction rate increases with concentration asdescribed by the rate law and explained bycollision theory

As reactant concentration increases the

frequency of collision increases

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Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 26: Combustion I S

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51

Factors Influencing Rate of Reaction

The nature of the reaction

(1)The number of reacting species

(2)Their physical state (the particles that formsolids move much more slowly than those of gases or those in solution)

(3)The complexity of the reaction

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Factors Influencing Rate of Reaction

Temperature

Conducting a reaction at a higher temperature

(1) delivers more energy into the system

(2) increases the reaction rate by causing morecollisions between particles

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Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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55

Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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59

Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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62

Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 27: Combustion I S

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53

Factors Influencing Rate of Reaction

Solvent

Reactions that occur in a solution

The properties of the solvent affect thereaction rate

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54

Factors Influencing Rate of Reaction

Pressure

The rate of gaseous reactions increases withpressure which is in fact equivalent to anincrease in concentration of the gas

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55

Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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56

Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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59

Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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62

Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 28: Combustion I S

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55

Factors Influencing Rate of Reaction

Electromagnetic Radiation

Electromagnetic radiation is a form of energy- may speed up the rate or even make areaction spontaneous

Provides the particles of the reactants withmore energy

This energy - may break bonds promote

molecules to electronically or vibrationallyexcited states - creating intermediate speciesthat react easily

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56

Factors Influencing Rate of Reaction

A Catalyst

Catalyst increases the reaction rate byproviding an alternative pathway with a loweractivation energy

Catalyst can increase rate in both the forwardand reverse reactions

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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59

Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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62

Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 29: Combustion I S

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57

Effect of Catalyst on Reaction

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58

Factors Influencing Rate of Reaction

Surface Area

Reactions on surfaces

the rate of reaction increases as the surface areaincreases

Powders react faster than solid blocks - greatersurface area = faster rate

Surface example - heterogeneous catalysis ndash seenext slide ndash Catalyst and surface area

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59

Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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60

Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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61

Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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62

Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (Platinum Palladium andRhodium) in you car

Three main reactions are catalyzed by Catalyticconverters(1) The oxidation of carbon monoxide to carbondioxide

2CO(g) + O 2(g) rarr 2CO 2(g)

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Heterogeneous Catalyst and Surface Area

Catalytic Converters (continued)

Three main reactions are catalyzed by Catalyticconverters

(2) The reduction of nitrogen monoxide back tonitrogen2NO(g) + 2CO(g) rarr N2(g) + 2CO 2(g)

(3) Oxidation of un-combusted hydrocarbonsC 6H 6(g) + 7frac12O 2

rarr 6CO 2(g) +3H 2O(l)

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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64

Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Factors Influencing Rate of Reaction

Order

The order of the reaction controls how thereactant concentration affects reaction rate

See this in the next slides

Detailed discussion or reaction order - later

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Rate Equation

For the chemical reaction

nA + mB rarr C + D

The rate equation or rate law is

[ ] [ ])( mn B AT k r =

Where k(T) is the reaction rate coefficient or rateconstant ndash not constant ndash function of temperatureand other parameters except for concentration

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Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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Reaction Order

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Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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142

Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 32: Combustion I S

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63

Rate Equation

[ ] [ ])( mn B AT k r =[A] and [B] are the concentrations of A and B

Exponents n and m are called reaction orders (tobe discussed) and depend on the reactionmechanism

Sometimes are the same as the stoichiometriccoefficients (n and m) of A and B but notnecessarily

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Rate Equation

[ ] [ ])( mn B AT k r =

Concentration

Higher concentrated = faster rateNote in some cases the rate may be unaffected bythe concentration of a particular reactantprovided it is present at a minimum concentration

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 33: Combustion I S

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65

Reaction Order

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66

Reaction Order

The Order of reaction for a reactant

Defined as the power to which its concentrationterm in the rate equation is raised

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 34: Combustion I S

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67

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Reaction order with respect to A = 1

Reaction order with respect to B = 2

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68

Reaction Order ndash Example

Chemical reaction A + 2B rarr C

Rate equation r = k[A] 1[B] 2

Double the concentration of A for this reaction thenwe would double the rate

But doubling the concentration of B wouldquadruple the rate

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69

Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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70

Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 35: Combustion I S

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Reaction Order

Not necessary that the order of a reaction is a wholenumber

Zero and fractional values of order are possible

But tend to be integers ndash 0 1 2 3 hellip n

Reaction orders can be determined only byexperiment

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Zero Order Reactions

A zero-order reaction - rate - independentof the concentration of the reactant(s)

Increasing the concentration of the reactingspecies will not speed up the rate of thereaction

Zero-order reactions are typically found

when a material required for the reaction toproceed such as a surface or a catalyst issaturated by the reactants

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Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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142

Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 36: Combustion I S

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71

Zero Order Reactions

The rate law for a zero-order reaction is

Where r is the reaction rate and k 0 is the reactionrate coefficient k 0 (reaction rate constant) hasunits of concentrationtime

0k r =

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Zero Order Reactions

Mass Balance ndash Zero Order Reaction

t-k [A]-[A]

yieldsnintegratio

][

00

0

=

=minus= k dt Ad

r

Assumptions ndash closed system no build-up of intermediates

[A] 0 is initial concentration

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 37: Combustion I S

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Excel Calculation of Reaction Rate ndash Zero FirstSecond Orders

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Zero Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 2 4 6 8 10

Time (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 0 Order

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 38: Combustion I S

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75

First Order Reactions

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First Order Reactions

A rarr B

Rate of reaction is proportional to the rates of change in concentrations of the reactants and

products ndash proportional to a derivative of aconcentration

Rate of reaction = r

Rate Law is

dt Ad

r ][minus=

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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142

Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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161

Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 39: Combustion I S

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Derivation of First Order Equations

For a First Order Reaction

1timeof unitsthehasconstant)rate(reactionk

][][

is balancemassthesystemclosedainor

][

1

1

1

Ak dt Ad

r

Ak r

=minus=

=

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Derivation of First Order Equations

For a First Order Reaction

timeistwhere

][

][

sexpressioncombining

][][

havewe

1

1

t k A

Ad

Ak dt Ad

r

minus=

=minus=

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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80

First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 40: Combustion I S

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Derivation of First Order Equations

lawratethegintegratin

[A]isAof ionconcentrat0at t][][

0

1

=

minus= t k A Ad

For a First Order Reaction we have

t k e 10[A][A] minus=

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First Order Reactions

A first-order reaction depends on the concentrationof only one reactant

Other reactants can be present but each will bezero-order

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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142

Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 41: Combustion I S

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First Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 5 10 15 20 25

Time (Days)

R

e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u

b i c

f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 1 Order

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82

Examples of First Order Reactions

2H2O2(l)rarr 2H2O(l) + O2(g) ndash decomposition of HydrogenPeroxideSO2Cl2(l)rarr SO2(g) + Cl2(g) ndash decomposition of Sulfuryl

chloride2N2O5(g) rarr 4NO2(g) + O2(g) ndash decomposition of

Dinitrogen Pentoxide (an important nitrogen reservoir inpolar stratospheric clouds found in Antarctica

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 42: Combustion I S

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83

Second Order Reactions

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Second Order Reactions

A second-order reaction depends on theconcentrations of one second-order reactant or twofirst-order reactants

]][[

or

][

2

22

B Ak r

Ak r

=

=

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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142

Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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158

REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 43: Combustion I S

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Simple Second Order Reactions

2A rarr P

With Rate Law

22 ][

][ Ak

dt Ad

sdot=minus

Second order reaction rate constant k 2 in mol -1 s-1

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Simple Second Order Reactions

dt k A

Ad sdot=minus

22][][

Separation of variables gives

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 44: Combustion I S

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Second Order Reactions (Simple Second Order)

02

0

20

][1][

][

][1

][1

At k A

A

t k A A

+=

=minus

The integrated second-order rate laws

Concentration of the reagent [A] decreasesaccording to a hyperbolic function

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Mixed Second Order Reactions

A + B rarr Products (1) OR

aA + bB rarr Products (2)

Rate Law

11

2][][

][ B Ak

dt

Ad sdot=minus

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 45: Combustion I S

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Mixed Second Order Reactions Reaction (1)

kt B Ae B A

B A )][]([

0

0 00

][][

][][ minus=

A + B rarr Products

The integrated second-order rate laws

[A] 0 ne [B] 0

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90

Example of Second Order Reaction

2NO2(g) rarr 2NO(g) + O2(g) destruction of NitrogendioxideThis reddish-brown gas has a characteristic sharp biting

odor NO2 is one of the most prominent air pollutants and apoison by inhalation

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 46: Combustion I S

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Second Order Reactions

0

01

02

03

04

05

06

07

08

09

1

0 20 40 60 80 100 120 140

Tim e (Days)

R e a c

t a n

t C o n c e n

t r a t i o n

( l b m o

l e c u b i c f t )

[A] at Temp 1

[A] at Temp 2

[A] at Temp 3 - 2 Order

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Comparison at High Temp

0

01

02

03

04

05

06

07

08

09

1

0 02 04 06 08 1

Time (Days)

[A] at Temp 3 - 0 Order

[A] at Temp 3 - 1 Order

[A] at Temp 3 - 2 Order

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Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 47: Combustion I S

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93

Third Order Reactions

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94

Third Order Reactions

Third order reactions proceed only when threespecies come into contact simultaneously

A + B + C rarr Products

The Rate Law is

]][][[][][][

3 C B Ak

dt

C d

dt

Bd

dt

Ad minus===

Third order reactions are rare so nofurther analysis will be given

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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96

Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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97

End of Section 1

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98

In-situ Combustion - Overview

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99

In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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106

In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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109

Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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117

Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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130

Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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134

Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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136

End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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142

Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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146

Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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149

REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 48: Combustion I S

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95

Example of Third Order Reaction

In the atmosphere

2NO + O 2 rarr 2NO 2

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Units of k (rate constant)

Zero Order ndash mole V-1 sec -1

First Order ndash sec-1

Second Order ndash V mole-1 sec -1

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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100

History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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102

References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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108

High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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113

The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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126

Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 49: Combustion I S

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End of Section 1

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In-situ Combustion - Overview

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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110

Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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In-situ Combustion(In si tu = Latin for in place)

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History

Start in early 1900rsquos ndash underground combustion ndashaccidentally started from air injection used to drive oiltoward producing wells

ndash Production increased and heat was noted ndash at first notattributed to subsurface fire

ndash Produced oil showed 10 to 15 CO2

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History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 51: Combustion I S

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101

History

Russians ndash first planned work on subsurface combustion ndash Ignited shallow oil with glowing charcoal ndash injected air into

well ndash 1935 ndash English translation of report ndash 1938

US ndash Patent ndash 1923 to Standard Development CompanyFirst US test ndash 1953 ndash Magnolia Petroleum ndash produced 80

barrels ndash demonstrated feasibility

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References on in-situ combustion or Fire Flooding

100rsquos of SPE papersKey References at end of chapters(SPE Monograph) Thermal Recovery Monograph Vol 7

Chapter 8 ndash Author Michael Pratts

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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114

The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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116

Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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118

Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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127

Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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128

Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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131

Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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138

Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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140

Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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141

Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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144

Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 52: Combustion I S

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103

Overview

This section is a short overview of in-situ combustionLater section will discuss the simulation of in-situ

combustionClosely linked to Thermal Simulation ndash instead of injecting

steam ndash we inject air oxygen or air + oxygen mixture ndashstart the oil burning ndash burn oil or coke to create heat steamand gases to displace the oil

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104

API Classifications

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Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 53: Combustion I S

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105

Canada Forecast

In-situ = steam drive HampP in-situ combustion SAGD VAPEX

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In-situ Combust ion or Fire Flooding

Usually applied to heavy oilsVertical wells ndash air oxygen injector and producer Inject air or oxygen or air enriched with oxygen into

reservoir rockLower heater or igniter into injection wellStart reservoir oil burning down holeCombustion front advances into reservoir producing heat

hot gases water vapor (steam)Sometime water is also injected ndash wet combustion

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Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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112

Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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122

Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 54: Combustion I S

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107

Oxidation of Some of the Oil Does

Produces heat that reduces viscosity for the remaining oilCracks some high-molecular weight hydrocarbons into

smaller moleculesVaporizes some of the lighter hydrocarbons to help

miscibility displace oilCreates steam that may steam-distill trapped oil

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High Pressure Air Injection Scheme

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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111

Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 55: Combustion I S

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Overview

Vaporizing zone contains combustion products lighthydrocarbons and steamOil bank is formed containing oil water and combustion

gasesThermal cracking and distillation can occur is temperature

is high enoughIf thermal cracking occurs ndash leaves carbon rich residue ndash

this maybe the primary fuel that burns

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Problems with conventions in-situ combustion

Gravity segregation or gas overriding due to differencebetween gas and oil densitiesChanneling due to unfavorable rock heterogeneityUnfavorable gasoil mobility ratioMust have gas saturation in reservoir between injector

and producer for oil bank and product gases to flow(without gas saturation nothing will move gas injectivitylimited)

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Cross Section of Formation

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Overview

Lots of theory field examples analytical analysisavailable on in-situ combustion

ndash Dry forward combustion ndash Wet combustion ndash Reverse combustion

Will present here a summary of key considerationsMore detail in SPE papers and Monograph

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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The Fuel

Usual way to determine fuel would be burned ndash byexperiments ndash fuel burned determined from the amount of oxygen consumed and the combustion front velocityField user of combustion process ndash interest ndash Amount of air required to burn a unit bulk volume of

reservoir rock ndash Amount of crude available for displacement from the

burned zone

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The Fuel

Less fuel burned as API gravity increasesOxidation of fuel divided into 2 categories dependent on

temperature ndash HTO ndash high temperature oxidation = burning ndash LTO ndash low temperature oxidation = smoldering ndash Separation temperature ~ 650o F (sometimes called

minimum active combustion temperature)

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Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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129

WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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132

Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 58: Combustion I S

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115

Oxygen Fuel Reactions

At high temperatures ndash cracking of heavy hydrocarbonscreates coke (solid) ndash most likely fuel in HTOHTO ndash oxidation products are CO2 CO and H2O ndash Note in simulations ndash will ignore formation of CO ndash Small effect on energy balance fluid flow ndash CO can be easily added ndash just one more component

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Oxygen Fuel Reactions

LTO ndash reaction products = H2O and partially oxidationproducts

ndash Carboxylic acids ndash Aldehydes ndash Keytones ndash Alcohols ndash Hydroperoxides

In our simulations we will assume HTO products

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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123

Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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125

Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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135

THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 59: Combustion I S

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Oxygen Fuel Reactions

HTO ndash found during frontal advanced in dry forwardcombustionLTO ndash found ndash Under bypass conditions ndash fluids bypass the combustion

zone in high permeability layers ndash In wet combustion ndash In dry combustion operations in thin sands or at low air

injections rates

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Gas Produced in Field Operations

Gases Produced ndash Hydrocarbon gases ndash N2

ndash CO2

ndash CO ndash O2

ndash H2

ndash Ar ndash H2S

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Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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120

Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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119

Air Requirements

Dependent on HC ratio = xDependent on CO(CO+CO2) ratio = mrsquo

(1-05mrsquo+025x) moles of O 2 react with 1 mole of fuel

With mrsquo = 0 and x = 2 get 15 moles of O 2

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Heat of Combustion

air Btuscf 250501

231967094 xm

xmha +minus

+minus=Δ

Heat release

When water of combustion condenses

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Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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121

Kinetics

During low temperature oxidation ndash fuel is crude itself At higher temperatures ndash cracking of heavy andintermediate MW crude form coke (solid) ndash combustioninvolves burning of coke

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Kinetics

In Thermal simulations have various approximations ndash React the crude with O2 to produce H2O and CO2

ndash Crack high MW crude to coke + light oil then burn cokeand burn light oil to produce H2O and CO2

End result is the same H2O and CO2 plus heat

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Combustion Processes

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Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Combustion Processes

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124

Dry Forward Combustion with Air

Conceptual model ndash called Frontal Advance (FA) model ndash One dimensional view

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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137

ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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139

Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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151

PROPS Keywords

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152

Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Saturations and Temperature Profiles in DryForward Combustion

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Wet Combustion

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Wet Combustion

Process where water passes through combustion frontwith air Applied to forward combustionWater entering combustion zone ndash liquid or vapor or bothWater injected with air if 2 phase flow resistance lowWhen high resistance ndash water injected intermittently

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Wet Combustion

Addition of water ndash alters performance of in situcombustionNo new mechanismsControl of wet combustion ndash thru injected waterair ratio =

Fwa or WARSignificant steam zone between the combustion front and

the three phase zone (down stream ndash water bank oil bank)

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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WaterAir Ratios Fwa or WAR

Low Fwa ndash injected water turns to steamHigh Fwa ndash water enters reaction zone as liquidHigh Fwa ndash cooling effect reduces the peak temperatureHigher Fwa ndash low temperature reactions will occur ndash

partially quenched combustion ndash increased size of steamzone ndash more rapid displacement of oil ndash reduction in fuelburned

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Saturation and Temperatures during WetCombustion

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 66: Combustion I S

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Reverse Combustion

Combustion front moves opposite to direction of air flowCombustion started at production wellDisplaced crude ndash pass through burning combustion zone

and through hot burned zoneNo oil bank ndash total flow resistance decreases with timeSometimes only a narrow channel is burnedWe will try to simulate this process

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Temperature and Saturation during ReverseCombustion

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Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 67: Combustion I S

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133

Toe-to-Heel Air Injection Process - THAI

Problems with conventional in-situ combustion usingvertical wells

ndash Communication between injector and producer ndash Movement of oil bank and combustion gases thru cold

heavy oil region

Problems overcome with a long horizontal producer

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Toe-to-Heel Air Injection Process - THAI

Vertical air injection well ndash high in the formationHorizontal producer ndash low in the formationCombustion front sweeps oil from toe to the heel of the

horizontal producer High temperatures ndash 400 to 700o C results in partially

upgrading crude oilbitumen in-situ

Coke is deposited at the combustion front ndash fromintensive cracking of the bitumen residue

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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THAI Process Concept

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End of Section 2

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 69: Combustion I S

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ECLIPSE Thermal Treatment of Chemical Reactions

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Outline of this Section

Overview of ECLIPSE Chemical Reaction program usage

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 70: Combustion I S

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Chemical Reaction in ECLIPSE

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Reactants and Products

Need components for ndash Injection gases ndash air oxygen nitrogen ndash Oil components ndash liquid fuel produced oil ndash Coke ndash solid fuel ndash Combustion products ndash gases and sometime coke

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 71: Combustion I S

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Reactants and Products

Reactants ndash need for combustion ndash Oxygen ndash Nitrogen if air is injected

bull N2 is important in the transport of heat down stream of thecombustion front

bull N2 does not react easilybull If it does it form NOx compounds at high temperaturesbull NOx mole fractions are ignored

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Reactants and Products

Products of the oxidation of oil or coke are ndash Water ndash in the vapor phase until it contacts cold rock or oil ndash Oxides of carbon ndash CO2 and CO

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CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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Page 72: Combustion I S

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143

CVTYPE

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Phases corresponding to each volatil ity type

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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153

Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 73: Combustion I S

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CNAMES and CVTYPE - Examples

CNAMESCO2 N2 C1 O2 C10 C20 C36

CVTYPELIVE GAS LIVE GAS LIVE LIVE DEAD

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Chemical Reaction Keywords

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RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 74: Combustion I S

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147

RUNSPEC and PROPS Keywords

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RUNSPEC Keywords

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 75: Combustion I S

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REACTION

Number of chemical reactionsIn RUNSPEC SectionGive total number of reactions

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REACTION Example

REACTION4

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

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End of Lecture

Page 76: Combustion I S

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PROPS Keywords

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Key Reaction Related Parameters

Activation energy in chemical reaction rates ndash REACACTEnthalpy of a chemical reaction ndash REACENTHReaction rate component order ndash REACCORDPhase of component terms in chemical reaction rates ndash REACPHAReaction rate porosity order ndash REACPORDReaction rate constant (lb-molDay) ndash REACRATEReaction rate solid order ndash REACSORD

Stoichiometric coefficients for products ndash STOPRODStoichiometric coefficients for reactants ndash STOREAC

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Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

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End of Lecture

Page 77: Combustion I S

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153

Reaction Rate - ECLIPSE Nomenclature andVariables

Rate of a chemical reaction depends on ndash the rate constant Ar (REACRATE) ndash The porosity order nrp (REACPORD) ndash The component concentrations to the power of the index or order nri

(REACCORD) ndash The component concentration cri in reacting phase (REACPHA) ndash The activation energy Er (REACACT) ndash The gas constant R ndash The temperature T ndash The bulk volume V

b

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Reaction Rate ndash ECLIPSE Nomenclature

rinrir r br c RT E AV R Πsdotminussdotsdot= ))(exp(

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 78: Combustion I S

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155

REACTACT

Activation energy in chemical reaction rates

Er in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole) [FIELD] J(g-mole) [LAB]

Reaction rate is related to Activation Energy by

)exp( RT E

R r r minusprop

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REACTACT - Example

--Activation energy in chemical reaction ratesREACACT--reaction-- 1 2 3 4

70206 32785 32785 32785 reaction 1234 (BTUlb mol)

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REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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REACENTH ndash more typical values

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

7272019 Combustion I S

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

7272019 Combustion I S

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

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SIS Training

April 10

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

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SIS Training

April 10

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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SIS Training

April 10

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 79: Combustion I S

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157

REACENTH

Reaction Enthalpy

Hr in units of kJ(kg-mole) [METRIC PVT-M] BTU(lb-mole)[FIELD] J(g-mole) [LAB]

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REACENTH ndash typical values

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159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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161

Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

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172

Reaction Rate Units in ECLIPSE Thermal

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April 10

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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174

STOPROD

Stoichiometric coefficient for productsExample coming

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175

STOREAC

Stoichiometric coefficient for reactantsExample coming

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176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

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SIS Training

April 10

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

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er P r i v

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

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190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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SIS Training

April 10

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 80: Combustion I S

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159

REACENTH ndash more typical values

NTNU - In-Situ Combustion

SIS Training

April 10

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REACENTH - Example

--Enthalpy of a chemical reactionREACENTH

382400 5142400 4521600 2102400 reaction 1234 (BTUlbmol)

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Exothermic

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162

REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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163

Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

NTNU - In-Situ Combustion

SIS Training

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

7272019 Combustion I S

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

NTNU - In-Situ Combustion

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April 10

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170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

7272019 Combustion I S

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171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

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er P r i v

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172

Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

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End of Lecture

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Exothermic

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REACCORD

Order of component terms in chemical reactionratesGives the order of reaction nc

If R r is the reaction rate

And m c is the concentration of component c in the reacting phase

Then n c (REACCORD) is the index or order of the reactants

cncr m R )(prop

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

NTNU - In-Situ Combustion

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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181

End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

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b er g

er P r i v

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Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

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Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

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FloViz View of the Grid

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Initial Temperature ndash hot at the inlet (500o F)

injection

production

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Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

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189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

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Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

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April 10

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Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

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Example of REACCORD

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2

And the reactions areC12H26 + 185 O2 rarr 12 CO2 +13 H2OC3H8 + 5 O2 rarr 3 CO2 +4 H2O All reactions are first order

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

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REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

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REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

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Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

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REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

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REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

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170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

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Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

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Reaction Rate Units in ECLIPSE Thermal

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REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

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STOPROD

Stoichiometric coefficient for productsExample coming

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STOREAC

Stoichiometric coefficient for reactantsExample coming

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STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

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Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

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STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

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STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

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Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

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End of Section 3

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Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

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Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

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April 10

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a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 83: Combustion I S

7272019 Combustion I S

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SIS Training

April 10

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er P r i v

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165

REACCORD ndash Example

--Order of component terms in chemical reaction ratesREACCORD-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 1 0 0 0 reaction 10 0 0 1 2 0 0 reaction 20 0 0 1 0 2 0 reaction 30 0 0 1 0 0 2 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

166

REACPHA

Phase of component terms in chemical reaction ratesEach component in each reaction is assigned a parameter

ndash ALL ndash if all phase react ndash OIL - if only the oil phase reacts ndash GAS ndash if only the gas phase reacts ndash GPP ndash if only the gas phase reacts and the rate depends on the gas

partial pressure ndash WAT ndash if the component is water in the water phase ndash NONE ndash if the reaction rate is independent of the component ndash Default is ALL ndash Phases are ignored for components with reaction order = 0

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

172

Reaction Rate Units in ECLIPSE Thermal

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8796

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

174

STOPROD

Stoichiometric coefficient for productsExample coming

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8896

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8996

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9096

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

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er P r i v

a t e

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9196

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

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er P r i v

a t e

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9296

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 84: Combustion I S

7272019 Combustion I S

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NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

167

Example of REACPHA

If have four components ndash Heavy = C12H26 and Light = C3H8 ndash O2 and CO2 and water

Have 2 reactions with same StoichiometryC3H8(o) + 5 O2 rarr 3 CO2 +4 H2O o = liquid phaseC3H8(g) + 5 O2 rarr 3 CO2 +4 H2O g = gas phase

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

168

REACPHA - Example

--Phase of component terms in chemical reaction ratesREACPHA-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 1 ALL GAS 1 1 1 1 reaction 11 1 1 GAS ALL 1 1 1 reaction 21 1 1 GAS 1 ALL 1 1 reaction 31 1 1 GAS 1 1 OIL 1 reaction 4

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

172

Reaction Rate Units in ECLIPSE Thermal

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8796

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

174

STOPROD

Stoichiometric coefficient for productsExample coming

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8896

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8996

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9096

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9196

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9296

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 85: Combustion I S

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

169

REACRATE

Reaction rate constant = Ar

Rr prop Ar

Input one constant for each reaction (defined byREACTION keyword)Units of Ar not fixed ndash chosen so that units or Rr are

correct ndash depending on value of component concentrationorder (REACCORD)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

170

Reaction Rate Constant

As previously stated ndash Units depend on order of reaction ndash Values should be determined experimentally ndash Values vary widely ndash Smith and Perkins values vary from

bull 42 x 104

bull 5 x 105

bull 1 x 107

bull 5 x 107

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

172

Reaction Rate Units in ECLIPSE Thermal

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8796

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

174

STOPROD

Stoichiometric coefficient for productsExample coming

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8896

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8996

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9096

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9196

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9296

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 86: Combustion I S

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

171

Reaction Rate Constant

Coats values vary frombull 28 x 1010

bull 34 x 1010

bull 403 x 1010

bull 42 x 106

bull 2 x 106

bull 1 x 106

bull 3 x 106

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

172

Reaction Rate Units in ECLIPSE Thermal

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8796

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

174

STOPROD

Stoichiometric coefficient for productsExample coming

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8896

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8996

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9096

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9196

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9296

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 87: Combustion I S

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8796

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

REACRATE - Example

--Reaction rate constant (lb-molDay)REACRATE--reaction-- 1 2 3 4

10E10 34054E10 028164E10 04035E10 reaction 1234

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

174

STOPROD

Stoichiometric coefficient for productsExample coming

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8896

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8996

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9096

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9196

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9296

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 88: Combustion I S

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8896

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

175

STOREAC

Stoichiometric coefficient for reactantsExample coming

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

176

STOPROD and STOREAC Example

If have seven components + water ndash CO2 ndash N2 ndash C1 ndash O2 ndash C10 ndash C20 ndash C36

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8996

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9096

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9196

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9296

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 89: Combustion I S

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 8996

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Reactions - Examples

-- reactions--No1 CH4 + 2 O2 ----gt CO2 + 2 H2O--No2 C10 + 155 O2 ----gt 10 CO2 + 11 H2O--No3 C20 + 305 O2 ----gt 20 CO2 + 21 H2O--No4 C36 + 545 O2 ----gt 36 CO2 + 37 H2O

All reactions are first order

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

178

STOREAC Example

--Stoichiometric coefficients for reactantsSTOREAC-- CO2 N2 C1 O2 C10 C20 C36 WATER

0 0 1 2 0 0 0 0 reaction 10 0 0 155 1 0 0 0 reaction 20 0 0 305 0 1 0 0 reaction 30 0 0 545 0 0 1 0 reaction 4

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9096

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9196

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9296

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 90: Combustion I S

7272019 Combustion I S

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NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

179

STOPROD - Example

--Stoichiometric coefficients for productsSTOPROD-- CO2 N2 C1 O2 C10 C20 C36 WATER

1 0 0 0 0 0 0 2 reaction 110 0 0 0 0 0 0 11 reaction 220 0 0 0 0 0 0 21 reaction 336 0 0 0 0 0 0 37 reaction 4

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

180

Reaction Summary Keywords

FREAC BREAC ndash reaction rate for field or block ndash FREAC_1 for reaction 1 in LB-MDAY for Field ndash BREAC_2 for reaction 2 in LB-MDAY for block

FREAT ndash reaction total for field ndash FREAT_1 for reaction 1 in LB-MOLES

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9196

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9296

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 91: Combustion I S

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9196

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

181

End of Section 3

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

182

Example ExerciseWet Forward Combustion SimulationSensit ivity Study of Water Air Ratio (WAR)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9296

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 92: Combustion I S

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9296

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Objective

Determine the optimum Water Air Ratio to maximize theoil Recovery Factor (RF)

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details ndash 3 Layer Model ndash Field Units

Simulation Model ndash laboratory field experimental size40 x 2 x 6 feet system20 x 1 x 3 (nx x ny x nz) grid (60 grid blocks)6 component4 reactionsΔx =Δy =Δz = 2 feet

Porosity = 025Permeability = 2000 mD

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 93: Combustion I S

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9396

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Model Details

Connate water saturation = Swcr = 025Initialize with previouslypartially water flooded reservoir ndash

Swat (initial) = 045 ndash give system mobility to injectionInitial oil viscosity = 260 cPInjectionsimulation time = 70 daysInject 600o F air (and) water for 3 daysInject 100o F air (and) water for 67 days

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

FloViz View of the Grid

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 94: Combustion I S

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9496

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Temperature ndash hot at the inlet (500o F)

injection

production

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Initial Mole Fractions of Components in Oil Phase

00097 ndash CO200 ndash N201 ndash C100 ndash O20084 ndash C1002063 ndash C20

06 ndash C3600 ndash H2O

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 95: Combustion I S

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9596

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

189

Sensit ivity Study of Wet Forward Combustion

Air injection rate is 20 Mscfday from gas injection wellHave defined an air injection well and a water injection well at

the same location ndash INJG (gasair) and INJW (water)Water injection rate vary from 0 STBDay to 11 STBDay

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

190

Water Air Ratio

No water ndash Dry combustionLots of water ndash quenches combustion or LTO (Low

Temperature Oxidation)

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture

Page 96: Combustion I S

7272019 Combustion I S

httpslidepdfcomreaderfullcombustion-i-s 9696

NTNU - In-Situ Combustion

SIS Training

April 10

S c h l um

b er g

er P r i v

a t e

Oil Recovery Factor for Various Water Air Ratios

Dry combustion

Increasing WAR

SIS Training

S c h l um

b er ge

End of Lecture