fuel specs
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Cr ea t i ng f u t u r e f ue l s
Refinery Technologies MeetingFuture Fuel Specifications
Catalytic Technologies for Petroleum Refining
Dr G Murali Dhar
Indian Institute of Petroleum
Dehradun2
Cr ea t i ng f u t u r e f ue l s
Petroleum Refining Industry has been Processing
Crude oil and upgrading quality of Petroleum Products
to meet the Energy Requirement of Mankind
Transportation Sector Accounts for 40% of Oil Consumption in
USA
Crude Oil reserves could come to an end by middle of 21st Century
Consumption continue to grow (0.2 Btoe/ annum)
Realization that crude oil reserves are limited
Attention focused on raw materials which were considered less
important in the past for converting to transportation fuel
Natural Gas
Heavy Oil
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Cr ea t i ng f u t u r e f ue l s
Last Decade: Natural Gas Reserves Increased considerably
Enormous Methane Reserves
Gas Hydrates Bottom of Ocean
Coal Bed Methane
Gradual Take over to Gas Era from Oil Era by Middle of the 21st
century
Renewable Energy Sources
Solar (Photovoltaic)
Bio Mass : Substitute for Transportation Fuel (Diesel)
Hydrogen: Fuel Cells
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Cr ea t i ng f u t u r e f ue l s
Developments in Refining Quality Trends /
Environmental Concern
World Oil Crisis in 1970s
Search for substitute for fossil fuels Alternative fuels
Refining Heavier Fractions Resid Catalytic Cracking
End 1970 Protect Environment from Noxious Emissions -
Strong Impact on Refining
Gasoline - Lead Phase Out: Complete ban since Jan 2000 in
Europe
Sulfur (
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Evolution of Motor Fuel Specifications in Europe
Since 1994
< 340360-
340
360-370Distillation, 95% TC
max
< 211-311--PolyNuclear Aromatics
PNA (wt%) max
< 1050/10350-2000Sulfur (ppm) max
> 5551-5351-49Cetane number, min
0.84-0.820.845-
0.840
0.845--Density (g/ ml) max
Diesel Oil
20102005200019951994Fuel
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Cr ea t i ng f u t u r e f ue l s
5050Particulate mg/ Nm3
450450NOx mg/Nm3
1700400SO2 mg/ Nm3
Power < 300 MWPower > 500 MWPollutant
Emission Limits Europe 2007
Exhaust Emissions: Gaseous Streams main
concern NOx, SOx, VOC
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Cr ea t i ng f u t u r e f ue l s
0.0
1.0
2.0
3.0
4.0
Gasoline LPG Gasoil Jet/ Kerosene
Liquid Fuels: Main transportation fuel demand increase, 2000 - 2010
%
Demand Shifting from Gasoline to Middle Distillates: JET/ Kerosene/ Diesel
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Catalysis play a vital role in petroleumindustry
More than 90% of finished refineryproducts come through a catalytic process
Importance of Purely Thermal Processesdeclined in past 40 years due to high
performance and cost effectiveness ofcatalytic processes.
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Cr ea t i ng f u t u r e f ue l s Petroleum Refining
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Cr ea t i ng f u t u r e f ue l s
Hydrocracking
Hydrocracking : High Pressure: 100 200 bar ,Temp : 300- 450C
Bifunctional Catalyst: Metal Hydrogenation Function
Acid Sites Support - Acid function for cracking
Flexible Products :Gasoline, Diesel -By changing reaction
parameters.
Catalysts:Sulfides NiMo, NiW on SiO2/ Al2O3NiW > NiMo > Co Mo Hydrogenation Activity
Conventional Amorphous SiO2/ Al2O3 has been replaced by
USY Ultra Stable Zeolite
Pt/Pd also added in some catalyst as Additives
Perfect Balance between hydrogenation / Acid Function
- A weak Acid / Strong hydrogenation combination Suit Middle
Distillates (Diesel)
- A Strong Acid / Weak Hydrogenation Suit Gasoline Production.
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Cr ea t i ng f u t u r e f ue l s
Hydrocracking a Two Stage Process
Pretreatment: HDS/ HDN
HDN Hydrodenitrogenation NiMo/ Al2O3 important as nitrogen in the
feed forms NH3 and poison acid sites of the cracking catalyst
AKZO Nobel Developed Improved HDN Catalyst NiMo
0
6
1965 1980 1990 2000 2005
Relative volume activities for hydrocrackers pretreater catalysts
Years
Relative activity
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Cr ea t i ng f u t u r e f ue l s
Hydrotreating
Widely used Process in Refinery
Purification of Different Petroleum Fractions
Organo-S-Compound + H2 ! H2S + Hydrocarbons - HDS (Hydrodesulfurization)
Organo-N-Compound + H2 ! NH3 + Hydrocarbons - HDN (Hydrodenitrogenation)
Organo-O-Compound + H2 ! H2O + Hydrocarbons - HDO (Hydrodeoxygenation)
Improve Quality of Products- Desulfurize Naphtha prior to Reforming
- Reduce S & Aromatics in Kerosene & Diesel
- Improve Color & Stability of waxes & Lube Base Oil
- Lower S & Metal Content in Hydrocracker & FCC Feedstock
Catalysts: CoMo > NiMo > NiW / Al2O3 (HDS)
NiMo > CoMo / Al2O3 . (HDN)
Active Metal : Mo, W 15 25% MoO3 / WO3Promoters: Co, Ni 4 8 % CoO, NiO
Used in sulfided form. Very stable: Long Life 5 years
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Reaction Rates of DBT
Relative Rate
40 f
10 f
Intermediate
f(slowest)
S
R1
R2
+ H2 + H2S
S
R+ H2
R+ H2S
+ H2S+ H2
R2
R1
SR3
R1
R2
R2
R1
S
R1
R2
+ H2 + H2S
R4 R3R4 R3
R3
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Cr ea t i ng f u t u r e f ue l s
0
Low Temperature
Reactor Temperature and Catalysts Effects
High Temperature
50
100
150
200
250
Product Sulfur ppm
Co Mo cat
Ni Mo cat
Smart cat system
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Deep HDS: Costly H2 Consumption
Alternative Routes explored:
Bio - Desulphurization: Last decade Much Progress
Technically viable but economic viability to be explored.
Oxidative Desulfurization
Sulfur Compounds! Sulphones / Extracted with solvent
Oxidizing Agents: H2O2, Organic Peroxides
Hydrocarbon Sulphones Adsorbed on Alumina/Adsorbents.
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Fluid Catalytic Cracking ( FCC )
1930 - First Catalytic cracking - Silica- Alumina
1960 - Y- zeolite Containing Rare Earth (REY) Increased Gasoline Yields
1980 - USY ( Dealuminated Y ) + ZSM-5 Octane Booster1990 USY -ZSM-5 regulation to Maximize Olefins ( Propylene )
FCC Gasoline - Represents 35% of Gasoline Pool contributes
- 95% of Sulfur in Gasoline
Process Conditions: Temp. -500 -550 C, Press.15-20 psi, Res. Time 1-10sRegeneration : 650 700C , Res. Time >10s
Feed : VGO, Resid
Moving Bed Operation: Sufficient Attrition Resistance
Catalyst Fines Formed , Make up Fresh Catalyst 0.5 -1 ton /day for plant1000 #ton catalyst
Catalyst : Silica-Alumina Matrix with binder primary cracking ofRecipe heavy molecules
Zeolite Y (USY ) - secondary cracking in pores of zeolite
ZSM -5 Additive ( small % ) - Gasoline, Olefins productionReactions : Acid catalyzed cracking reaction - Carbenium ion mechanism
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Cr ea t i ng f u t u r e f ue l s
Alkylation
MTBE Phase Out -- USA -- California Banned MTBE
Refineries have To Manage : -
Loss in Octane in gasoline pool
Demand of Gasoline with Lower Aromatics < 35% , Lower Benzene (
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Cr ea t i ng f u t u r e f ue l s Gasoline Blend
Light Naphtha Alkylation / Isomerization
Heavy Naphtha Cat. Reforming
Reformulated
Gasoline (RFG )
Light Olefins MTBE
FCC Gasoline DHDS/ Isomerization
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Cr ea t i ng f u t u r e f ue l s
Hydrogen Economy -- Enormous Impact on Energy Industry/ Existing Infrastructure
Hydrogen Generation/ Consumption : Technology Emerging
Link between H2 Generation & Distribution No Convincing Technology
H2 Distribution : Storage / Transportation / Release on Demand ----- Barriers
Transportation Gas State Pipelines Risky
Liquefication Cryogenic Technology --- Expensive
Chemical Storage : Metal Hydrides / Carbon Nano tubes --- Small Scale Only
Production of Hydrogen Based on Hydrocarbon Feed Stock ---- CO2 as a Byproduct
Chemical Sequestration of CO2 ------- Additional Technology Required
Two Ways Producing Mechanical Energy From Hydrogen: Direct Use in IC Engine
Through a Fuel Cell
Options: 1. H2 in Fuel Cell in-situ on board car or 2. From Residential units
Sulfur Should be very Low- Poison Every stage of Processing Chain of Fuel Cell
Future Catalytic Technologies
Alternative Fuels : Hydrogen
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Cr ea t i ng f u t u r e f ue l s
Alternative Fuels
Hydrogen Production :
Catalytic Reforming of Naphtha
Steam Reforming of Light Naphtha
Steam Reforming of Natural Gas
Gasification of Coal / Petroleum residues
Syn Gas / WGS Reaction
Bio- Mass
Electrolysis
Fuel processor for small-scale hydrogen production for fuel cell28
Cr ea t i ng f u t u r e f ue l s
Natural Gas
Transformation of Natural Gas ( > 95% Methane) to Syn Gas Followed by
Fischer- Tropsch Synthesis ! Hydrocarbons ---- GTL (Gas to Liquid ) Technology
Steam Reforming : CH4 + H2O --( Ni Cat./ 800oC,20 bar) -! 3H2+ CO
Partial Oxidation : 2CH4 + O2 ( 1200-1500oC),>140 bar ) ----! 2CO + 4 H2
Potential FT Catalyst : Carbon Rich Source ( Coal) -- Ni /Fe / Alumina or Silica
Hydrogen Rich Source ( Natl. Gas ) Co / Alumina
FT Process Since 1920 : Catalyst & Process Development Still in Progress
Production of Syn Gas itself Accounts for 60% of the Capital Cost
FT Synthesis : Temp. 200 300 oC , Press. 10 40 bar
n CO + ( 2n+1) H2 ----! Cn H2n+2 + n H2O ("H = - 39.4 Kcal/ mol)
FT Diesel Quality : S < 5ppm, Aromatics < 1%, Cetane >70, Density
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Catalysis in 21st Century Would be Centered around
A Shift from Oil to Gas Era
Environmentally Benign Technologies
Sulfur Reduction : Deep HDS : Diesel
FCC Gasoline
Aromatics / Benzene : Gasoline -- Alkylation / Isomerization
Alternative Fuels : Natural Gas
GTL SynGas -- FT HC ( Diesel/ Gasoline )DME ( Diesel)
Bio-mass Jatropha Seeds Diesel
Methane Activation
C1 C4 Alkane Oligomerization ( Aromatics)
Hydrogen Fuel Cell
Catalytic Combustion : DeNOx Catalyst Pollution Abatement -- Diesel Fuel
Petrochemicals : Propylene ---- FCC ( DCC)
BTX
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Thank You