upgrading of basrah-kirkuk blend crude.pdf

Upgrading of Basrah-Kirkuk Blend Crude Oil Using Mechanical-Acoustical Effect

A Thesis Submitted to the Chemical Engineering Department University of

Technology in Partial Fulfillment of the Requirement for the Degree of Master of Science in Chemical Engineering

By

Ghufran Raheem Hmood

(B.Sc. Chemical Engineering, 2008)

Supervised by

Dr. Adel Sharif Hamadi

2011

Ministry of Higher Education and Scientific Research University of Technology

Chemical Engineering Department

Linguistic Certification

This is to certify that I have read the thesis titled "Upgrading(Basrah-

Kirkuk blend) Crudes Oil Using Mechanical-Acoustical Effect"

and corrected any grammatical mistake I found. The thesis is therefore

qualified for debate.

Signature:

Assist. Prof. Dr. Mumtaz A. Zablouk

University of technology

Date: / /2011

I

First and foremost, praise is to Allah. Best prayer

and peace be unto, the prophet Mohammed messenger of

Allah. Then, I would like to express my sincere gratitude

to my supervisor Dr. Adel Sharif Hamadi for their helpful

suggestions during this work.

I would like to thank sincerely the University of

Technology and the department of Chemical Engineering

for their cooperation.

I also express my sincere thanks to Mr. Salam,

friends and all others who have helped me directly or

indirectly whenever I needed help.

Last but not the least; heartfelt thanks are due to my

family specially my father, my mother (may Allah have

mercy upon her soul), sisters and brothers.

Ghufran R. Hmood

Acknowledgements

II

Some crude oils are almost certain to be less convenient to handle,

more costly, and less stable than the often already difficult substances in

use today. As viscosity increases, so do handling problems and capital

requirement for equipment necessary to handle these materials. System

reliability due to the severity of the handling conditions may become a

problem, heating requirements and the costs become important factors, and

the difficulty of maintaining these materials under the required conditions

for storage and use frequently becomes significant at high viscosities.

These materials are normally very high in caloric value content, but are

extremely difficult to handle, therefore, it is important to find methods to

handle these cruds to make it more stable and easily to use.

Non-Convential method for upgrading crude oil characterization

(mixed of Basrah-Kirkuk crudes oil) using hydrodynamical coaxial turbo

machine type rotary pulsation apparatus (RPA) implement ultra-high

reliability in shearing rotor-stator operation and constructed from high

toughness steel of the type (30CrMoV9). Both directions of the rotor are

designed to have a number of teeth uniformly distributed over the

circumference of the rotor disc as well as the stator disc.

The analysis of the crude oil after acoustic-mechanical effect in RPA

showed that increasing of recirculation time between 5 - 10 min with

higher rotor speed (7610 rpm), leaded to increases the total productivity of

light and intermediate petroleum fraction cuts from (30%) to (39%),

increase in API gravity from (29) to (40), reduce flash point from (75 P

◦PC) to

(54P

◦PC) and reduce pour point from (-10 P

◦PC) to (-32P

◦PC), thus providing better

handling properties and then additional possibilities of being transported in

pipe lines. Also, the addition of linear alkyl benzene sodium sulfonate

Abstract

III

(LABS) as surfactant has been investigated, it improves the treatment of

crude oil properties, decreases the shear stress of crude oil. The results

show that the API increased to (45), flash point reduced to (50◦C), pour

point reduced to (-36 ◦C) and the yield of light and intermediate fraction

increased to (40 vol. %) within (10min) and (7610rpm).

Contents

IV

Pages

Subject

I Acknowledgments

II Abstract

IV Content

VII Nomenclature

CHAPTER ONE : INTRODUCTION

1 1. 1 Introduction

3 1. 2 Aims of the Present Work

CHAPTER TWO: LITERATURE SURVEY

4 2. 1 Introduction

4 2. 2 Methods for Upgrading Heavy Crude Oil

6 2.3 The Convential Methods for Upgrading Heavy Crude Oil

6 2. 3.1 Cracking

6 2. 3. 1.a Thermal Cracking

7 2. 3.1.b Catalytic Cracking

8 2.3.1.c Hydrocracking

10 2.4 Non-Convential Methods for Upgrading Heavy Crude Oil

10 2. 4.1 Electromagnetic Heating

12 2.4.2 Acoustical-Mechanical Method by Using Rotor-Stator-

Apparatus(RPA)

Contents

Contents

V

16 2. 4.2.1 Mechanical Effect for (RPA)

22 2. 4.2.1.a The Classic Single-Stage (Rotor/Stator Mixer)

23 2.4.2.1.b Multi-Stage (Rotor/Stator Mixer)

28

28

2. 4.2.2 Thermal Effect

2.4.2.3 Acoustical Effect for (RPA)

33 2.4.2.4 Ultrasonic Cavitation

39 2. 5 An Upgrading Process through Cavitation and Surfactant

41 2. 5.1 The Mechanism of Surfactant

44

46

2. 5.2 Anionic Surfactant(Linear Alkyl Benzene Sodium

Sulfonate)

2.6 Previous Work

CHAPTER THREE: EXPERIMENTAL WORK

48 3. 1 Introduction

48 3. 2 Apparatus

48 3. 3 Materials

48 3. 3. 1 Crude Oil

49 3. 3. 2 Surfactant

50 3. 4 Experimental Procedure

51 3. 4. 1 Rotary- Pulsation-Apparatus (RPA)

54

55

3. 4. 2 Photo/Contact Tachometer

3. 5 Tests and Analysis

55 3.5.1 Rotational Viscometer

Contents

VI

56 4. 5.3 Boiling Point and (ASTM) Distillation Curve

57 4. 5.4 Density, Specific Gravity and API Gravity

CHAPTER FOUR: RESULTS AND DISCUSSION

58 4.1 Introduction

58 4.2 Characterization of Crude Oil

60 4.3 Characterization of Crude Oil after Upgrading with (RPA)

60 4.3.1 API Gravity

63 4.3.2 Viscosity

67 4.3.3 (ASTM) Distillation Curve

75 4.3.4 Flash Point

78 4.3.5 Pour Point

CHAPTER FIVE:CONCLUSION AND

RECOMMENDATION FOR FUTUR WORK

81 5.1 Conclusions

82 5.2 Recommendation for Future Work

83 REFRENCES

APPENDICES

Appendix (A)

Appendix (B)

Appendix (C)

Appendix (D)

Contents

VII

Contents

VIII

Contents

IX

Nomenclature

VII

Symbols

Greek Symbols

Symbol Definition Unit μ Viscosity mPa.sec μ Viscosity for crude oil before treatment ◦ mPa.sec μ Viscosity for crude oil after treatment

(sample1) 1 mPa.sec μ Viscosity for crude oil after treatment

(sample2) 2 mPa.sec μ Viscosity for crude oil after treatment

(sample3) 3 mPa.sec

μ Viscosity for crude oil after treatment (sample4) 4 mPa.sec

ρ Density of liquid gm/cm3

Symbol Definition Unit

a Indicated by indicator in viscometer [-] a Indicated by indicator for crude oil before treatment ◦ [-]

a Indicated by indicator for crude oil after treatment (sample1)

1 [-]


2 [-]


3 [-]


4 [-]

k Coefficient for viscometer [-]

Nomenclature

Nomenclature

VIII

Abbreviations

Symbol Definition Unit API American Petroleum Institution [-]

ASTM American society for testing Material [-]

BP Boiling point oC

H High speed viscometer rpm IBP Initial Boiling point oC

L Low speed viscometer rpm LABS Liner Alkyl Benzene Sodium Sulfonate [-] RPA Rotary-Pulsation-Apparatus [-] SG Specific Gravity [-] V Volume of liquid cm3

Wt weight gm

Chapter One Introduction

1

Chapter One

Introduction

1.1 Introduction

Upgrading crude oil involves processing (usually conversion) into a

more salable, higher-valued product. Improved characterization methods

are necessary for process design, crude oil evaluation, and operational

control [1].

Worldwide trends in crude oil supply have been indicating the

declining availability of conventional crude. This trend has been offset by

the increasing production of heavy crude. For heavy crude, the yield of

distillate fractions can be increased by upgrading distillation residues. A

number of thermal processes (e.g., visbreaking, delayed-, fluid and flexi-

coking) and asphaltenes and metals separation processes (e.g.,

deasphalting), the so-called carbon rejecting processes, have been used on a

commercial scale for several decades. Heating often requires considerable

amounts of energy and there are some logistic problems in using diluents

[2]. Catalytic cracking the most effective procedure for upgrading heavy oil

in industrial practices, but high temperatures and high pressures are still

necessary. They place constraints and limitation on the reactor material and

on safety considerations. Asphaltenes, contained in heavy oil, are not only

refractory for cracking but can also deactivate the catalyst [3]. Heavy feeds

can also be upgraded by hydroprocessing, the so called hydrogen addition

option. This requires the presence of hydrogen and an active catalyst.

Compared with thermal processes, hydroprocessing operations are more

flexible, giving higher yields of liquid fractions. However, the costs of

high-pressure equipment, catalysts and hydrogen required for

hydroprocessing have to be offset by the increased yields and quality of

liquid products [4].


2

The primary and secondary oil recovery processes currently being

practiced have been successful in recovering only about a third of the

original oil in place leaving behind nearly two-thirds as residual oil. This

points out the need to study and implement new and innovative methods to

recover the remaining oil or heavy oil [5]. There is an address process to

convert asphaltenes in to gas oil and resins at room temperature and

atmospheric pressure [3]. Rather unusual approach used for upgrading

heavy petroleum feeds involves the use of ultrasonic energy, electric field

and magnetic field [4].

The (RPA) turbomachine proven rotor-stator design which

incorporates ultrasonic and mechanical energy to enhancement the

processing and usefulness in many of chemical, food, pharmaceutical and

cosmetics and microbiological industries for improved dispersion,

homogenization, pasteurization, sterilization and sonochemical reaction

using controlled ultrasonic vibration of the rotor and stator[6]. This

technical assistance project dealt with improving fuel in the petroleum

industries by modification of heavy crude properties and then allowing for

use a low cost heavy residue previously discarded by refineries and or

crude oil producers, leading to reduce greenhouse gases and achieving

clean air objectives, as well as, improving maintenances resulting in low

emissions. The technology of RPA suspected an effect in either from an

economic or environmental position or a combination of both. Key

advantages of RPA are many for the refiner, the distributor, the utility or

other customer.


3

1.2 The aim of present study was to upgrade crude oil by using

acoustical-mechanical effect of (RPA) by; Upgrading the flow

characterization for (Basrah-Kirkuk blend) crudes oil as (reducing

viscosity, reducing pour point and flash point, increasing the yield of

light and intermediate fraction and increase API) and Studying the

effect of adding (linear alkyl benzene sodium sulfonate) as surfactant

on the flow characterization of this cruds.

Aims of the present work

Chapter Two Literature Survey

4

Chapter Two

Literature Survey

2.1 UIntroduction Large quantities of crude oil are consumed throughout the world for

purposes as diverse as propulsion, chemical processing and electric power

generation. Consequently, the trend in the modern hydrocarbon processing

is toward more complete recovery of high value light and middle distillate,

and to reduce the wasted energy and disposal costs [7].

2.2 UMethods For Upgrading Heavy Crude Oil There are other types of petroleum that are different from

conventional petroleum in that they are much more difficult to recover

from the subsurface reservoir. These materials have a much higher

viscosity (and lower API gravity) than conventional petroleum. Heavy oils

are more difficult to recover from the subsurface reservoir than light oils.

The definition of heavy oils is usually based on the API gravity or

viscosity, and the definition is quite arbitrary although there have been

attempts to rationalize the definition based on viscosity, API gravity, and

density [8]. Oil transportation has become a complex and highly technical

operation. One of the major difficulties in the pipe line transportation is the

high viscous fluids that require efficient and economical ways to transfer

the heavy crude [9].

Most of the world refineries are equipped with alloys capable of

handling sweet light crude, which is most suitable for refining into

gasoline, gas oil and heating oil. On the other hand, refining of heavy crude

is difficult and is associated with operational problems. The problems arise


5

from the increased risk of corrosion, equipment failures, and downtime of

process units. .To make matters worse, many of the compounds are

unstable during refining operations and they break into smaller components

or combine with other constituents. These current events are facing the oil

industry with many decisions and technological challenges not only

regarding the methodologies of producing heavy oil, transportation and

refining of heavy oil, but also evaluating the value and optimum utilization

of this produced oil, including crude oil segregation, up-grading and

blending approaches [10].

Various method and procedures that make it possible to vary the

physicochemical parameters of petroleum fuels, and increase the yield of

light petroleum derivatives during the refining of crude are currently under

development. The kinetics of processes of crude and petroleum-derivative

refining can be influenced by chemical substances (catalyst, surface-active

substances-SAS, additives, etc.) and physical fields (thermal, cavitation,

electromagnetic, etc.)[11].


6

2.3 UThe Convential Methods For Upgrading Heavy Crude Oil

2.3.1 U Cracking Cracking is a petroleum refining process in which heavy molecular

weight hydrocarbons are broken up into light hydrocarbon molecules by

the application of heat and pressure, with or without the use of catalysts, to

derive a variety of fuel products. Cracking is one of the principal ways in

which crude oil is converted into useful fuels such as motor gasoline, jet

fuel, and home heating oil [12].

2.3.1.a. UThermal Cracking In 1913, the thermal cracking process was developed. In this process,

heavy fuels containing large molecules are broken into smaller ones to

produce additional gasoline and distillate fuels by application of both

pressure and intense heat. Thermal cracking is a radical chain process. The

chain process contains three main stages: chain start, chain growth and

chain termination [13].The majority of the thermal cracking processes

temperatures of (455C to 540C) and pressures of (7 to 68) atm. , where use

to break down, rearrange, or combine hydrocarbon molecules. However,

this method produced large amounts of solid, unwanted coke. This early

process has evolved into the following application of thermal cracking:

visbreaking, steam cracking, and coking [12]. Figure (2.1) shows one stage

thermal cracking[14].


7

Figure (2.1) The One Stage Thermal Cracker[14].

2.3.1.b. UCatalytic Cracking Catalytic cracking is the most important and widely used refinery

process for converting heavy oils into more valuable gasoline and lighter

products. Originally cracking was accomplished thermally but the catalytic

process has almost completely replaced thermal cracking because more

gasoline having a higher octane and less heavy fuel oils and light gases are

produced. The light gases produced by catalytic cracking contain more

olefins than those produced by thermal cracking.

The cracking process produces carbon (coke) which remains on the

catalyst particle and rapidly lowers its activity. To maintain the catalyst

activity at a useful level, it is necessary to regenerate the catalyst by

burning off this coke with air. As a result, the catalyst is continuously

moved from reactor to regenerator and back to reactor[14]. Figure (2.2)

shows the two stage catalyst regeneration[14].

The cracking reaction is endothermic and the regeneration reaction

exothermic. Some units are designed to use the regeneration heat to supply

that needed for the reaction and to heat the feed up to reaction temperature.

These are known as ‘‘heat balance’’ units.


8

Average riser reactor temperatures are in the range (480–540°C),

with oil feed temperatures from (260–425°C) and regenerator exit

temperatures for catalyst from (650–815°C). The catalytic-cracking

processes in use today can all be classified as either moving-bed or

fluidized-bed units. There are several modifications under each of the

classes depending upon the designer or builder, but within a class the basic

operation is very similar. Also catalytic cracking relatively cost

process[15].

Figure (2.2) The Two Stage Catalyst Regeneration[14].

2.3.1.c UHydrocracking Hydrocracking is a two-stage process combining catalytic cracking

and hydrogenation, wherein heavier feedstocks are cracked in the presence

of hydrogen to produce more desirable products. The process employs high

pressure, high temperature, a catalyst, and hydrogen. Hydrocracking is used

for feedstock that are difficult to process by either catalytic cracking or

reforming, since these feedstocks are characterized usually by a high

polycyclic aromatic content and/or high concentrations of the two principal

catalyst poisons, sulfur and nitrogen compounds [16].


9

The hydrocracking process largely depends on the nature of the

feedstock and the relative rates of the two competing reactions,

hydrogenation and cracking. When the feedstock has a high paraffinic

content, the primary function of hydrogen is to prevent the formation of

polycyclic aromatic compounds. Another important role of hydrogen in the

hydrocracking process is to reduce tar formation and prevent buildup of

coke on the catalyst. Hydrocracking produces relatively large amounts of

isobutane for alkylation feedstock. Hydrocracking also performs

isomerization for pour-point control and smoke-point control, both of

which are important in high-quality jet fuel [16].

Hydrocracking reactions are normally carried out at average catalyst

temperatures between (290 to 400°C) and at reactor pressures between (83

and 138 atm.). The circulation of large quantities of hydrogen with the

feedstock prevents excessive catalyst fouling and permits long runs without

catalyst regeneration. Careful preparation of the feed is also necessary in

order to remove catalyst poisons and to give long catalyst life [15]. This

processes less coke formation from catalytic cracking but costly process.

It was shown in thermal and catalyst cracking that it is impossible to

convert a hundred percent of the crude oil residue to light fractions. The

main reason for this is that cracking reactions need to be accompanied by

hydrogen transfer reactions in order to stabilize the product. It is obvious

that light fractions such as gasoline or diesel fractions are more hydrogen

rich than coke and residue by-products of thermal or catalytic cracking

processes. This means that hydrogen transfer proceeds from heavy

fractions to light cracking products during the cracking processes.

However, the complete conversion of cracking feed to light fractions is

impossible because of the shortage of hydrogen in the feed. Also,

heteroatom compounds present in the feed tend to form coke on the


10

catalysts. [13]. Figure (2.3) shows 5Tschematic of a two-stage hydrocraking

unit5T[16].

5T Figure (2.3) Schematic of a Two-Stage Hydrocraking Unit 5T[16].5T

2.4 UNon-Convential Methods for Upgrading Heavy Crude Oil Rather unusual approach used for upgrading heavy petroleum feeds

involves the use of ultrasonic energy, electric field and magnetic field.

However, their brief account may be useful because they differ markedly

from the catalytic and non-catalytic methods which have been either under

investigation or used for upgrading heavy petroleum feeds on a commercial

scale [4].

There are many types of non convential methods for upgrading heavy crude

oil some of them are:-

2.4.1 UElectromagnetic Heating U Electromagnetic heating has been considered to be an effective

technique for improving oil recovery for the cases of high heat loss in the

formation and the production pipe [8]. Alternative methods discusses of

transferring heat to heavy oil reservoirs, based on electromagnetic energy.

It has been detailed analysis of low frequency electric resistive (ohmic)

heating and higher frequency electromagnetic heating (microwave


11

frequency) alternative methods for heating heavy oil reservoirs, which may

be economically viable alternatives to steam in certain situations. For tar-

sands or extremely high viscosity reservoirs, where the temperature effect

on viscosity is significant, electromagnetic heating could be used as a pre-

heating tool to create preferential pathways for steam injection. This would

minimize the heat losses during steam injection, and improves steam

injection performance [17]. Past investigations have mainly focused on the

reservoir aspect of the applications, mostly in the areas of heavy oil or tar.

It was demonstrated that the recovery technique can be useful for heavy oil

reservoirs that are marginal due to their low thickness. It was also indicated

that the injection of gas in conjunction with electromagnetic heating can

have the benefit of adding a driving force while lowering the heavy oil

viscosity. It was also reported that the best results are obtained when a

medium-range wavelength of 20 MHz is applied, demonstrated through a

series of scaled model studies that electromagnetic heating can be

considered as a recovery scheme when combined with gas injection or

other enhanced oil recovery methods [8]. The viscosity reduction of crude oil was achieved by applying either an

electric or magnetic field [3]. Paraffinic and intermediate crudes, as well as

a heavy crude oil, were investigated. The method had little effect on the

temperature of crude oil. However, the viscosity reduction was not

permanent, although the reduced viscosity was maintained for several

hours. Among the crude oil tested, the most pronounced effect was

observed for the paraffinic crude oil [4].


12

2.4.2 UAcoustical-Mechanical Method by Using Rotor-Stator-

Apparatus (RPA) Heavy crudes (bitumen) are highly viscous and contain high

concentrations of asphaltene, resins, nitrogen and sulfur containing

heteroaromatics and several metals, particularly nickel and vanadium.

These properties of heavy crude oil present serious operational problems in

heavy oil production and downstream processing. There are vast deposits

of heavy crude oils in many parts of the world. In fact, these reserves are

estimated at more than seven times the known remaining reserves of

conventional crude oils. It has been proven that reserves of conventional

crude oil are being depleted, thus there is a growing interest in the

utilization of these vast resources of unconventional oils to produce refined

fuels and petrochemicals by upgrading. Presently, the method used for

reducing viscosity and upgradation is cost intensive, less selective and

environmentally reactive [18].

The ultrasonic treatment was used to treat heavy crude oil at a near

atmospheric pressure in the absence of additives. The lighter gaseous

hydrocarbons produced were identified as methane, ethylene, ethane and

propylene. The reduction in viscosity, were obtained at the sonochemical

conditions. A radical chain mechanism was proposed to explain mechanism

of the reactions of hydrocarbons which were initiated by ultrasound [4]. At

low temperatures, many petroleum products become very thick,

transforming, by nature, into a gel. High adhesion of the gel to the inner

surface of the production pipeline is observed here. Available pump

equipment cannot develop the static pressure necessary to displace from the

site the gel column that has “frozen onto” the pipeline over a length ranging

from several tens of meters to several kilometers. Until now, this problem

has been resolved by heating the entire pipeline, or a portion of it, using

special electric heating elements in the form of strips (bands). Moreover,


13

portable steam generators are used for gradual warming of the pipe from

the outside. After rapid softening, the oil, as a thixotropic (non-Newtonian)

fluid, will return to its initial gel-like state over a period of several hours.

These methods are extremely energy- and time-consuming [19].

The acoustic method of lowering the low-temperature viscosity of

petroleum products in pipelines has a number of advantages, among which

are low energy capacity and labor outlays, and a shorter exposure time for

the pipeline. The method in question is based on excitation of vibrations

having a tangential component, for example, torsional or longitudinal

oscillations with sufficient amplitude in the walls of the pipeline. These

oscillations create intersecting forces that act on the adhesive bonds

between the “congealed” gel-like petroleum product and the walls of the

pipeline, and their rupturing forces. As a result, a thin, by nature, liquid

layer of oil is formed near the wall of the pipeline over a considerable

length (several tens, and even hundreds of meters), which also effectively

lowers the viscosity of the oil in the pipeline. Accordingly, the start-up

pressure is reduced by several times, and the entire gel-like column within

the tube will be displaced after 20–100 sec of the acoustic effect – will

begin to slide at first in the form of a single column, and then even in the

form of a liquid medium, i.e., pumping of the petroleum product will begin.

Significant acoustic power is not required here, since formation of a thin

liquid layer occurs without heating of the pipe itself, and the acoustic effect

will take place over a rather large length virtually instantaneously owing to

the high spread velocity of the acoustic oscillations (2500–5500 m/sec).

Moreover, an increase in the transfer speed of the oil is observed, under the

acoustic effect. Here, vibrations of the pipe wall create large deformations

and high strain rates in the near-wall region of the medium, as a result of

which the latter is transformed from a solid to a liquid medium in this

region; this provides for the possibility of moving the basic volume of oil


14

under a static pressure created by a pump. The basic volume of the medium

is moved, like a solid, by “sliding” over a thin liquid interlayer. On

continuation, the thickness of the liquid interlayer may increase under the

action of vibrations, and also static shear stress. The influence of acoustic-

mechanical effect suspected an effective operation on flowing liquid

passing exposed to hydrodynamical power; shearing and fractional forces,

acceleration power and high frequency ultrasonic waves[19].

To counteract the problems associated with today's heavy crude oil,

especially asphaltenes and fuel sludgem, improved engine performance

resulting from heavy oil homogenization has been reintroduced. However,

the high crude oil prices and short supply eventually disappeared, and so

did the need for onsite heavy crude oil blending and homogenization.

Today's performance-effective fuel homogenizer is essentially a milling

machine that physically grinds the fuel at it is pumped through the modern

homogenizers often consists of a stationary stator housing with a motor

driven rotor, which is concentrically mounted inside the stator. The mating

surfaces of the rotor and stator have special channeled grinding surface.

During the operation, the fuel passing through the homogenizer is exposed

to hydrodynamic power:

• Shearing and frictional forces

• Acceleration power

• High frequency ultrasonic waves [20].

Figure (2.4) shows homogenizer rotor-stator[20].


15

Figure (2.4) homogenizer rotor-stator[20].

In combination, these forces act together to shear the asphalten particles

down to 3 to 5 microns. Smaller particles size introduces. Figure (2.5)

shows the fuel droplet combustion stages[21].

Figure (2.5) The Fuel Droplet Combustion Stages[21].


16

The fundamentals dispersion along rotor-stator occurs into two stages:

2.4.2.1 UMechanical Effect for (RPA) Rotary - Pulsation-Apparatus (RPA) has been reintroduced as an

efficient answer dealing heavy oil handling as well as many other

applications such as food, pharmaceutical, and microbiological industries for

improved dispersion, homogenization, pasteurization, sterilization and

sonochemical reaction using controlled ultrasonic vibration of the rotor and

stator. The hydroacoustic effect in the stator channel is a combination of

two effects, namely, the effect of the macroturbulent pulses of the liquid

velocity and the effect of cumulative microjets, which result from the

collapse of cavitation bubbles [21].

The design construction of RPA is relatively simple, extremely reliable in

operation, economical to manufacture, and requires a minimum time of

maintenance and servicing, and can be handled in equipment without

necessary of heating, transportation vessels, and containers. The in-Line

design of RPA is designed to withstand the most demanding applications,

and provide ultimate flexibility. The RPA can be deliver flow and ultra

high shear throughput, improved process control, and superior end product

consistency [22]. The application of rotary-pulsed apparatus (RPA) in the

petroleum industry has recently appreciably increased. With RPA it is

possible to improve the technological processes in heterogeneous liquid

media. This method for treating the dispersed systems advantageously

differs from other known methods by the fact that the operational principles

of mixing and displacement apparatus are simultaneously combined in it,

and a frequency of treatment of the entire medium in guaranteed in the

RPA[23]. The action of a mechanical agitation, which occurs in the

clearance between the rotor and stator. Ahydrodynamical coaxial

turbomachine type Rotary-Pulsation-Apparatus (RPA) has been

experimentally designed implement ultra-high reliability in shearing rotor-


17

stator operation and constructed from high toughness steel of the type

(30CrMoV9). Both directions of the rotor are designed to have a number of

teeth uniformly distributed over the circumference of the rotor disc as well

as the stator disc [22]. Mixing apparatus includes a rotor having at least one rotor surface

comprising a cylindrical surface of revolution about the rotor shaft axis and

a stator having at least one stator surface which is substantially reciprocal

in shape to the rotor surface. Rotors have been designed in cylindrical

configuration with teeth extending radially outwardly from the cylindrical

surface. The stator of such a mixing head is a hollow cylinder with

inwardly extending teeth which are arranged to interdigitate with the

outwardly extending rotor teeth. Such a mixing head has advantages from

the standpoint of reduced stator weight and improved heat dissipation. In

general, since it is advantageous to have as many mixing teeth as possible,

the cylindrical head must be made undesirably long to provide adequate

surface area for teeth[24].

The teeth of prior art mixing heads were substantially rectangular in

configuration and were substantially identical in shape at all points on both

the rotor and stator surfaces. Material entering the mixing head of a mixer

utilizing such prior art teeth tended to remain axially stratified as it passed

between the rotor and the stator because insufficient mixing occurred in an

axial direction which is the direction extending along the projecting teeth.

It is necessary to provide teeth having an adequate cross sectional area in

order to make them strong enough to withstand periodic impact forces

which are generated during disassembly of the head for cleaning and

maintenance and which can result when hard pieces of foreign material are

within the material to be mixed. As indicated above it is advantageous to

provide a maximum number of teeth per unit area on these surfaces to

insure the beast mixing characteristics of the resulting mixing head. In the


18

processing industries, it is customary to blend fluid under pressure by

passing them through a continuous mixer which includes a mixing head.

This mixing head includes a rotor member having a plurality of teeth

extending outwardly from its outer surface. A stator member is disposed

rows of teeth which are arranged to interdigitate with the rotor teeth.

Material is inserted into the mixer under pressure and passes between the

interdigitated teeth of the rotor and stator causing it to be beaten and mixed

[24].

A method and apparatus (RPA) is provided for conjoint or

simultaneous adjustment of the gap spaces of the inner and outer grinding

zones. The inner grinding zones are generally radially oriented, and merge

into an outer inclined grinding zone. feeds to be ground is introduced in to

a central inlet position and is accelerated through the inner and outer zones

by centrifugal forces generated by a pair of grinding members which rotate

relative to one and other [25].

The opposed surfaces of the relatively rotating members each carry a

plurality of concentric rows of teeth, and the gap spacing of the inner

grinding zone is defined between adjacent surfaces of the teeth. The

adjacent teeth defining the inner grinding zone are arranged so that

adjustment of the gap space of the outer grinding zone simultaneously

controls the gap spacing of the inner grinding zone without the need for

separate adjustment [25]. Between the stationary guide vanes and the

rotating runner, the so called rotor-stator interactions—the flow in turbo-

machines is unsteady and highly turbulent. [26].

One of the basic designs a feature of RPA is the use of a rotor and

stator in the form of cylinders (radial type of RPA), there are located in the

cylindrical walls of the rotor and stator, and the flow of liquid takes place

in the radial direction. The development of centrifugal force acting on the

liquid within the recess of the rotor is an advantage for the RPA. The liquid


19

to be treated is delivered under pressure, or gravity flow through an inlet

pipe in to the rotor recess, proceeds through the channels of the rotor and

stator, and effective chamber formed by the housing and cover, and exits

from the apparatus via a discharge pipe. During rotation, the rotor channels

become periodically aligned with the stator channels. If the rotor channels

are covered by the stator wall, the pressure increases in the rotor. When a

rotor channel is aligned with a stator channel, the pressure is reducing for a

short time interval, as a result of which a pulse of excess pressure develops

in the stator channel. A short-lived pulse of reduced ("negative") pressure

develops behind it, since alignment of the rotor and stator channels has

been conclude, and the feed of liquid into the stator channel is

accomplished only by a "transit" flow from the radial gap between the rotor

and stator. The volume of liquid in the stator channel tends to exit from the

latter, and tensile stresses are created in the liquid under inertial forces; this

will result in cavitation. Cavitation bubbles will grow as the pressure drops

to that of the saturated vapors of the liquid being treated at a given

temperature, and collapse or surge into the stator channel as the pressure

increases [27].

Figure (2.6) represents two types of flow in the channels between the

rotor and stator. The directions of flowing liquid are shown by pointers. In

the Fig (2.6a) the channel between the stator teeth is closed with the rotor

teeth. Flow in this case occurs directly in the clearance between the coaxial

cylinders of rotor and stator. While, in Fig (2.6 b) channel between the

teeth of stator is opened, and then worked liquid flows on it to the similar

next stages[21].


20

Figure (2.6) two types of flow in the channels between the rotor and

stator[21].

This combination of teeth position and channels on the rotor and

stator creates effective mechanical agitation dispersion on the medium

liquid. Most important factors effect in the shear forces, depend upon the

contraction details of the rotor and stator, which are circumferential speed,

outer diameter of the rotor, and the number of teeth, and the gap between

rotor and stator[21].

The rotor and a stationary stator typically operate at considerably high

rotational speeds and as result, differential speed between rotor and stator

imparts extremely high shear and turbulent energy which produces an

intense friction on the material being processed in the gap between the

rotor and stator. Fig (2.7) and Fig (2.8) show the flow, and velocity profile

in the gap between a toothed Rotor-Stator[21].


21

Figure (2.7) flow profile in a toothed Rotor-Stator[21].

Figure (2.8) Velocity profile in a toothed Rotor-Stator[21].

The very effective mechanical breakdown of the native fluid velocity and

of the internal fluid velocity profile is carried out by dynamics forces

between rotor and stator i.e. impact and shock wave, stress caused by

turbulent flow and stress caused by surrounding fluid. The non uniform,

accelerated flow of the liquid in the stator channels brings about developed

turbulence, intensive cavitations and liquid pressure, and viscosity pulses. If

gap between rotor and stator is narrow (0.1-0.5 mm) the main effect exerted

on the heterogeneous liquid system is a hydro-acoustic nature [21].


22

There are two types of rotor-stator:

2.4.2.1.a. UThe Classic Single-Stage (Rotor/Stator Mixer) All rotor/stator mixers are comprised of a rotor that turns at high

speed within a stationary stator. In a “single-stage” unit, the rotor includes

a single set of four blades. As the rotating blades pass each opening in the

stator, they mechanically shear particles and droplets, and expel material at

high velocity into the surrounding mix, creating intense hydraulic shear. As

fast as material is expelled, more is drawn into the bottom of the

rotor/stator generator, which promotes continuous flow and fast mixing.

The Ross Rotor/Stator Mixer easily replaces other high speed mixers in

many applications. With the rotor turning at 3,000 - 4,000 feet per minute

(fpm), the generator applies intense mechanical and hydraulic shear, and

produces vigorous flow in a low-viscosity batch[30].

Applications

Homogenization, solubilization, emulsification, powder wet-out,

grinding and particle size reduction, in batch and in-line configurations.

The single stage rotor/stator mixer is ideal for applications that require fast

particle/droplet size reduction[30]. Figure (2.9) shows images for several

type of Single-Stage rotor-stator[30].


23

Figure (2.9) A Single-Stage Rotor-Stator[30].

2.4.2.1.b. UMulti-Stage Rotor/Stator MixersU Multi-stage rotor/stator generators include two or four rows of

rotating blades that nest inside a matching stator. The mixed material

enters the center of the generator through an inlet connection and is

accelerated outward by centrifugal force. During each transit through the

rotor/stator generator, the material is subjected to a quick succession of

increasingly intense shearing events – until it finally exits the generator and

is either piped downstream or recirculated for another pass through the

mixer. By applying a series of shearing events with every pass through the

generator, the multi-stage mixer accelerates the mixing process

dramatically. This action also produces particles and droplets that are quite

small – usually well below 1 micron in diameter – and extremely uniform.

These rotors are of high-energy, high-shear mixer. For equipment users, it

means that rotor/stator mixing technology now provides a cost-efficient

answer for even more processing challenges. And now, with an inline

design that can deliver both high flow and ultra-high shear in a single pass,

it addresses other critical needs in production, as well – by providing higher


24

throughput, improved process control, and superior end-product

consistency[30]. Figure (2.10) shows the multistage rotor-stator[30].

Figure (2.10) The Multistage Rotor-Stator[30].

A process and apparatus for the mixing of material by means of the

combination of sheer-dispersion and/or extensional-dispersion and

distributive mixing action, in which the mixing occurs in one or more

stages within stress inducing flow channels between movable members

whereby the material is essentially propelled through the flow channels of

such stages by pumping action provided by the relative movement between

the members within the mixer itself [31]. Figure (2.11) shows an axial

section view of the rotor


25

Figure (2.11) is an axial section view of the rotor

The disruption with the rotor-stator homogenizer involves hydraulic and

mechanical shear as well as cavitation. In the homogenizing field also

claim that there is to a lesser extent high-energy sonic and ultrasonic

pressure gradients involved [32]. The only thing that ultrasonic and

mechanical (rotor-stator) homogenizing have in common is that both

methods generate and use to some degree cavitation. Cavitation is

generated as you move a solid object through a liquid at a high rate of

speed. In ultrasonics the object being moved is the probe which is being

vibrated at a very high rate of speed generating cavitation. In mechanical

homogenizing (rotor-stator) the blade (rotor) is being moved through the

liquid at a high rate of speed generating cavitation. Appropriately sized

cellular material is drawn up into the apparatus by a rapidly rotating rotor

(blade) positioned within a static head or tube (stator) containing slots or

holes. There the material is centrifugally thrown outward in a pump like

fashion to exit through the slots or holes. Because the rotor (blade) turns at

a very high rpm, the material is rapidly reduced in size by a combination of


26

extreme turbulence, cavitation and scissor like mechanical shearing

occurring within the narrow gap between the rotor and the stator. Since

most rotor-stator homogenizers have an open configuration, the product is

repeatedly recirculated. The variables to be optimized for maximum

efficiency are as follows:

• Design and size of rotor-stator (generator)

• Rotor tip speed

• Initial size of sample

• Viscosity of medium

• Time of processing or flow rate

• Volume of medium and concentration of sample

• Shape of vessel and positioning of rotor-stator [32].

The rotor is the vibrator consisting of a toothed metal ring with

piezoelectric ceramic bonded, which generates ultrasonic vibration. The

rotor is in contact with the shell of motor and is driven by the friction

between the rotor and the stator. This configuration not only removes the

rotor in a conventional type of traveling wave ultrasonic motor but also

changes the interaction between the rotor and the stator of the motor so that

it improves the output performance of the motor. Although an electric

brush is added to the ultrasonic motor, it is easy to be fabricated because of

the low speed of motor. A traveling wave ultrasonic motor consists of a

stator and a rotor [33]. The rotor is in contact with another side of the

stator at the crests of the traveling wave and is pressed against the stator

with a normal force. The movement trajectory of a point on the surface of

the stator is usually elliptical. The tangential displacement of the stator at

the contact interface drives the rotor by means of the friction force. In order

to improved the interaction between the rotor and the stator it has used the


27

motor shell as the stator and the rotor as the vibrator [33]. Figure (2.12)

shows image for the application of (RPA) in industrial work.

Figure (2.12) The Application Of (RPA) In Industrial Work.

Changing the physicochemical parameters of liquids in RPA, breaking

down molecular compounds by multifactorial pulsed action on liquid-

liquid, liquid-solid, and gas-liquid system, including:

1. Mechanical action on particles of a heterogeneous medium (impact,

shear, and pulverizing loads and contacts with working parts of RPA);

2. Hydrodynamic effect (large shear stresses in a liquid, developed

turbulence, and pressure and velocity pulsations in liquid flow); and

3. Hydroacoustic effect on a liquid (small-scale pressure pulsations, heavy

cavitation, shock waves, and nonlinear acoustic effects) [34].


28

U2.4.2.2 Thermal Effect There are thermal effects in rotor-to-stator rub, and influence on the

rotor vibrational response. Based on machinery observations, it is assumed

in the analysis that velocities of transient thermal effects are considerably

lower than that of rotor vibrations, and thermal effects affect only rotor

steady-state vibrational responses. These responses would change due to

thermally induced bow of the rotor, which can be considered slowly

varying in time for the purposes of rotor vibration calculation. The major

consideration is given to the rotor, which experiences intermittent contact

with the stator due to predetermined thermal bow of the rotor, unbalance

force, and radial constant load force. In the case of an inelastic impact, this

causes an on/off step-change in the stiffness of the system [28].

Impacts generated from the surface of a stator rubbing against the

surface of a rotor during its rotation. These impacts lead to an increase of

magnitudes not only at the fundamental rotational frequency and its

harmonics, but also at some high-frequency components. The more severe

the rubbing, the higher and the more components at high frequencies [29].

2.4.2.3 UAcoustical Effect for (RPA) The action of dynamic radial pressure pulsations plays a main role

from elements side of the flowing area in the RPA to the liquid system by

cavitations and ultrasonic emission. The circumferential of the rotation of

the rotor and the vibration of the stator ensures a deeper and effective

treatment of the medium in the apparatus. In this stage, the final dispersion

and size reduction of the dispersed particles occurs [35].

Ultrasonics is a form of acoustical energy, generally pitched above the

audible range of frequencies [36].The ultrasonic power generated enhances

chemical and physical changes in the liquid medium through the generation

and subsequent destruction of cavitations bubbles. Like any sound wave


29

ultrasound is propagated via a series of compression and rarefaction waves

induced in the molecules of the medium through which it passes[37].

At sufficiently high power the rarefaction cycle may exceed the

attractive forces of the molecules of the liquid and cavitations bubbles will

form. Such bubbles grow by a process known as rectified diffusion i.e.

small amounts of vapor (or gas) from the medium enters the bubble during

its expansion phase and is not fully expelled during compression[37].

The bubbles grow over the period of a few cycles to an equilibrium

size for the particular frequency applied. It is the fate of these bubbles when

they collapse in succeeding compression cycles which generates the energy

for chemical and mechanical effects (Fig (2.13)). Cavitations bubble collapse

is a remarkable phenomenon induced throughout the liquid by the power of

sound [35]. Sound may be defined as any pressure variation (in air, water

or any other medium) that the human detect [37].

Figure (2.13): Generation of an acoustic bubble[35].

Thermal energy by high temperature heating is not selective and may result

in damage. For example, good (premiere) molecules may undergo

polymerization and become coke. The effects caused by ultrasound can be

attributed to three phenomena. First, there is a rapid movement of fluids

caused by a variation of sonic pressure, which subjects the solvent to


30

compression and rarefaction. The second phenomenon, and by far the most

important, is cavitation. It is generally accepted that the formation and

collapse of microbubbles is responsible for most of the significant chemical

effects that are observed. Actually, this technique can be operated at one

atmospheric and room temperature. This process is called cold cracking.

This violent implosion of the microbubbles also gives rise to luminescence.

Thirdly, there is microstreaming, where a large amount of vibrational

energy is put into small volume with little heating. Under the cavitation

conditions, two events may occur simultaneously, thermal scission of

bonds of heavy oil according to rice mechanism of cracking, and the

generation of hydrogen atom. These are essential for the upgrading of

heavy molecule in heavy oil and other residua. Furthermore, the ultrasound

can be applied in situ for generation of oil by reduction of viscosity using a

drilling wanted with a number of transducers [38]. A rotary pulsation

device having a body, at least one rotor and one or more stators, in which

the increased efficiency of the device is effected through the presence of

ultrasonic vibration generated by the bulk vibration of the rotors, stator, or

both, the generation of the vibrations is a function of a combination of one

or more of the clearance between the rotors and stators which can be

adjusted; turbulizing element on the rotor, stators, or both; incisions on the

rotors; slots in the rotors; and choke channels for controlling and directing

recirculated flow within the device[39]. Sound waves having frequencies

higher than those to which the human ear can respond (about 16 kHz) are

called ultrasound. Ultrasound in the range of 20 to 100 kHz produces high

energy waves sometimes referred to as power ultrasound. Power ultrasound

is used for a variety of purposes including cleaning, welding, rupturing cell

walls in biochemistry studies, and dispersing solids in liquids. Power

ultrasound produces its effect via cavitation bubbles. When power

ultrasound is applied to a liquid in sufficient intensity, the liquid is


31

alternately compressed and expanded forming bubbles [40]. Ultrasonic

energy is mechanical energy. Its transmission is dependent upon the elastic

properties and the densities of the media through which it is propagated.

The stresses associated with the propagation of ultrasonic waves are the

basic cause of the numerous mechanical effects attributable to applying

ultrasonic energy. The stresses may operate directly or may be converted

into thermal energy by absorption or into chemical energy by their effects

upon the molecular conditions of the materials. Examples of the direct

effect of ultrasonic stresses are breaking particles down into smaller

particles, emulsifycation, degassing of liquids, drying and dewatering of

materials, ultrasonic machining, atomization of liquids, and metal forming.

Examples of thermal effects of ultrasonic irradiation are ultrasonic welding

of polymers and metals [36]. When power ultrasound is applied to a

mixture of particles and liquid and the bubbles collapse near a solid

surface, a high-speed jet of liquid is driven into the particles and this jet can

deposit enormous energy densities at the site of impact. Cavitation tends to

occur preferentially along gas-filled crevices in particles, creating the

conditions necessary for a violent cavitation event termed "transient

cavitation" [40]. The propagation of bulk waves in liquids and gases is

much simpler than that of solids; fluids in equilibrium are always isotropic

and only longitudinal (compressional) waves can propagate [41].

Ultrasound has many attributes to offer industry, medicine, and

research. This section discusses some important applications; in many of

these, cavitation plays an important role. Materials undergo physical and

chemical processes under external stress, both physical and chemical.

Stress is often used to change the nature of materials, to give them shape

and size, and to make them useful in different applications. It is therefore

essential to have a basic understanding of physical and chemical processes


32

[40]. Figure (2.14) shows a Classification of the chemical and physical

effects of ultrasound[42] .

Figure (2.14) Classification of the Chemical and Physical Effects Of

Ultrasound[42].

One widely used method to disrupt cells is ultrasonic disruption.

These devices work by generating intense sonic pressure waves in a liquid

media. The pressure waves cause streaming in the liquid and, under the

right conditions, rapid formation of micro-bubbles which grow and

coalesce until they reach their resonant size, vibrate violently, and

eventually collapse. This phenomenon is called cavitation. The implosion

of the vapor phase bubbles generates a shock wave with sufficient energy

to break covalent bonds. Shear from the imploding cavitation bubbles as

well as from eddying induced by the vibrating sonic transducer disrupt cells

[32].The method of pulsed energy effect of acoustic waves and cavitation,

which alter the hydrodynamics and dispersion stability of liquid media, is

the basis of technologies utilizing the cavitation effect on crude and

petroleum derivatives; this will exert different influences on process

mechanisms-markedly intensifying one (destruction) and abruptly slowing

others (coking). An energy effect on the crude and petroleum derivatives


33

makes it possible to increase the yield of highly volatile fraction resulting

from their distillation [43].

2.4.2.4 UUltrasonic Cavitation

•Bubble forms due to compression and expansion by ultrasound

•Bubbles resonate and destabilize

•Bubble implodes generating a pressure wave of up to 10,000 atm. [44].

These bubbles have very short lifetimes and, when they collapse, hot

spots with temperatures of around 4980˚C [40]. The vibrations were due to

the enormous turbulence, heat and pressure of imploding cavities [45].

Figure (2.15) shows photo for the caustic cavitation[45].

Figure (2.15) A caustic cavitation bubble[45].

High-frequency ultrasonic waves are propagated as oscillatory motion

through materials: solid, liquid, or gas. The oscillatory effect is attenuated

by scattering, absorption, and other mechanisms. The high-intensity

oscillations in liquids cause strong bubble formation and collapse

(cavitation), producing a large increase in instantaneous local temperature

and pressure. Increase in temperature leads to phase changes, acceleration

of chemical reactions, and material decomposition. Material decomposition

may result in generation of free radicals capable of initiating chemical


34

reactions, including polymerization. High-frequency ultrasonics has

therefore found many applications in a variety of chemical and physical

processes involving both organic and inorganic materials [40]. Acoustic

cavitation is responsible for sonochemistry. Bubble collapse in liquids

results in an enormous concentration of energy from the conversion of the

kinetic energy of liquid motion into heating of the contents of the bubble

[42]. The basic mechanism of chemical effects of ultrasound can be

explained on the basis of the formation of cavitation bubbles that, during

their vigorous oscillation, are able to produce free radical. This

phenomenon is called cavitation. Oscillating bubbles behave like heat

engines. Therefore, very high temperatures (several thousand ˚C) can be

achieved at the moment of adiabatic compression of bubble content [46].

Cavitation may occur when liquid is forced through certain constrictions or

behind a high-speed propeller. In the present context, cavitation is

produced by the presence of high-intensity ultrasonic waves in a liquid.

When a liquid is subjected to a high-intensity ultrasonic wave, during the

rarefaction portion of the cycle when the pressure in the wave is below

ambient, gas pockets expand with the impressed field until the pockets

collapse violently due to the high stresses developed in the walls. The

source of these gas pockets is generally molecules of gas that are very

finely dispersed throughout the liquid volume. These may be located at

vacant sites of the quasi crystalline structure of the liquid or they may be

contained in invisible bubbles of microscopic dimensions[42].

Cavitation is of two types:

1. Gaseous cavitation: involves gases dissolved or entrapped in the

liquid or existing on surfaces in contact with the liquid.

2. Vaporous cavitation involves gases from the vaporization of the

liquid itself.


35

Most liquids contain nuclei about which cavitation bubbles

originate. These nuclei may consist of dispersed dust particles,

prominences on immersed surfaces, and minute gas bubbles. In fact,

unless especially treated, liquids contain dissolved or entrained gas.

Various factors influence the onset and intensities of the cavitation

bubbles. These factors include the sizes of the nuclei, ambient

pressure, amount of dissolved gases, vapor pressure, viscosity,

surface tension, and the frequency and duration of the ultrasonic

energy. To be able to produce the effects associated with the

expansion and the violent collapse of cavitation bubbles, the bubble

must be capable of expanding with the rarefaction part of the cycle

of the impressed field and of collapsing before the total pressure

reaches its minimum value. That is, the bubble must reach the size

where it will collapse catastrophically in less than one-quarter the

cycle of the impressed wave [42]. Cavitation will accelerate

diffusion of the crude in wax cages and intensity its breakdown.

Acceleration of wax dissolution occurs due to intensification of

agitation of crude on the crude-wax boundary, and the effect of

pressure pulses, which disperse the wax particles. Cavitation rupture

the bonds between individual parts of the molecules, and influences

the change in structural viscosity[47]. To rupture the bonds in the

molecules of the hydrocarbon compounds in such multicomponent

system as crude and petroleum derivatives, it is necessary to provide

a multifactorial energy effect in pulsed form, for which pulsed rotor

units have been, developed [48]. The dissociation energy of the C-H

bond varies from 322 to 435 kJ/mole, depending on the molecular

mass and structure of the molecule, while the dissociation energy of

the C-C bond ranges from 250 to 348 kJ/mole [49]. In rupturing the

C-H bond, the hydrogen is separated from the molecule, while


36

during rupture of C-C bond, the molecule is broken into two unequal

parts. Destruction of molecules, which is caused by their

microcracking and ionization processes, occurs during cavitation

treatment of a raw hydrocarbon material; as a result, "activated"

particles are accumulated in the system: radical and ion-radical

formation [50]. The cavitations bubble has a variety of effects within

the liquid medium depending upon the type of system in which it is

generated. These systems can be broadly divided into homogeneous

liquid, heterogeneous solid/liquid and heterogeneous liquid/liquid.

Within chemical systems these three groupings represent most

processing situations [35].

Group (1)-homogenous liquid phase reactions: (I) - In the bulk liquid

immediately surrounding the bubble where the rapid collapse of the bubble

generates shear forces which can produce mechanical effects and (II) - In the

bubble itself where any species introduced during its formation will be

subjected to extreme conditions of temperature and pressure on collapse

leading to chemical effects as shown in Fig (2.16)[35].

Figure (2.16): Acoustic cavitation in a homogeneous liquid[35].

Collapse of a cavitation bubble on or near to a surface is unsymmetrical

because the surface provides resistance to liquid flow from that side. The

result is an inrush of liquid predominantly from the side of the bubble


37

remote from the surface resulting in a powerful liquid jet being formed,

targeted at the surface (Fig (2.17)). The effect is equivalent to high pressure

jetting and is the reason that ultrasound is used for cleaning. This effect can

also activate solid catalysts and increase mass and heat transfer to the

surface by disruption of the interfacial boundary layers[35].

Figure (2.17): Cavitation bubble collapse at or near a solid surface[35].

Group (2)-heterogeneous solid particles reaction: Acoustic cavitation

can produce dramatic effects on powders suspended in a liquid as shown in

Fig (2.18). Surface imperfections or trapped gas can act as the nuclei for

cavitation bubble formation on the surface of a particle and subsequent

surface collapse can then lead to shock waves which break the particle

apart[35].

Figure (2.18): Acoustic cavitation in a liquid with a suspended powder[35].

Cavitation bubble collapse in the liquid phase near to a particle can force it

into rapid motion. Under these circumstances the general dispersive effect


38

is accompanied by interparticle collisions which can lead to erosion,

surface cleaning and wetting of the particles and particle size reduction.

Group (3) - heterogeneous liquid/liquid: In heterogeneous

liquid/liquid reactions, cavitational collapse at or near the interface will

cause disruption and mixing, resulting in the formation of very fine

emulsions as shown in Fig (2.19) [35].

Figure (2.19): Cavitation effects in a heterogeneous liquid/liquid

system[35].

Cavitation substantially affects and intensify the processes of mixing and

ensures the preparation of stable crudes with fine and homogeneous

dispersion [51, 52]. A substantial intensification of the processes of

dispergation and homogenization of mixtures is based on the cavitation

effects (hydrodynamic and acoustical microflows, sound pressure, and the

capillary effect). Owing to them, the liquid and solid particles disintegrate,

become finer, and homogeneously distribute in the mixture.

The limited layer on the liquid–liquid and liquid– solid interfaces is

modified, its thickness decreases, and this ensures the greater penetration

ability of materials into the internal regions of the porous body; this

intensifies the processes of diffusion and dispergation [52].

Cavitation methods are widely used for the processes of dispergation

and homogenization. The latter are effective and optimal when the


39

following parameters are determined correctly: the static pressure in the

closed technological recirculation system at the cavitation treatment, the

duration of the homogenization, and the ratio between the liquids phases

(the concentration) [53].

2.5 UAn Upgrading Process through Surfactant

The active petroleum reserves have been depleted by 50-80% by

almost all oil companies and the basic feedstock resources are concentrated

in fields with difficult to produce heavy and highly viscous crudes [54].

Extraction of such crudes from in situ seams and transport when the resin

and wax content is 20% and higher are complicated by deposition of n-

paraffins in oil-field equipment and pipelines [55]. The costs of removing

these deposits are up to 30% of the cost of the product produced. The

search for ways of acting on these systems to improve their flow is a

pressing problem. Colloidal properties are regulated by different methods

of acting on the phase transitions in petroleum disperse systems: by

addition of modifying additives [56, 57]. It is generally believed that the

use of chemical reagents – surfactants and pour depressants – is a

technologically effective and efficient method of controlling wax deposits.

The viscosity of the crude is essentially a function of the temperature and

additive content.Exposure to a high-frequency field is thus the most

effective method of reducing wax deposits in pumping and transport of

high-solid-point crudes in pipelines [58].Surfactants are widely used and

find a very large number of applications because of their remarkable ability

to influence the properties of surfaces and interfaces. Some important

applications of surfactants in the petroleum industry are shown in table

(2.1). Surfactants may apply or encountered at all stages in the petroleum

recovery industry, from oil well drilling, reservoir injection, oil well

production, and surface plant processes, to pipeline and seagoing

transportation of petroleum emulsions [59].


40

Table (2.1) Some examples of surfactant applications in the

industry[59].

Gas/liquid systems

Liquid/liquid systems

Liquid/solid systems

Producing oilwall and well-head foams, Oil flotation process forth, Distillation and fractionation tower foams, Fuel oil and jet fuel tank (truck) foams, Foam drilling fluid, Foam fracturing fluid, Foam acidizing fluid, Blocking and diverting foams, Gas mobility control foams

Emulsion drilling fluids, Enhanced oil recovery in situ emulsions, Oil sand flotation process slurry, Oil sand flotation process froths, Well head emulsions, Heavy oil pipeline emulsions, Fuel oil emulsions, Asphalt emulsion, Oil spill emulsions, Tanker bilge emulsions

Reservoir wettability modifiers, Reservoir fines stabilizers, Tank/vessel sludge dispersants, Drilling mud dispersants

Ultrasound provides the high temperature and pressure at localized

cavitation centers. And surfactant prevents the agglomeration of the

asphaltenes. They have applied these two elements for petroleum

upgrading. asphaltenes could form free radicals of lower molecular weight

by bond cleavage under ultrasound . The free radical reactions could be

terminated by recombination or disproportionation. The purpose of

hydrogen radicals is to terminate the free-radical reactions after bond

cleavage as well as to saturate the product. In this system, it has introduced

a solid reducing agent, sodium borohydride, as a hydrogen source. In this

initial investigation, the participation of reducing agent and surfactants

enhances the conversion of petroleum asphaltenes into lighter fractions by


41

about 10 times. Through the effects of cavitation and surfactant, 35% of

asphaltene is converted into gasoil and resin in 10 min under mild

conditions [3].All the petroleum industry's surfactant applications or

problems have in common the same basic principles of colloid and

interface science [59].

2.5.1 UThe Mechanism of Surfactant In English the term surfactant (short for surface-active-agent)

designates a substance which exhibits some superficial or interfacial

activity. It is worth remarking that all amhiphiles do not display such

activity; in effect, only the amphiphiles with more or less equilibrated

hydrophilic and lipophilic tendencies are likely to migrate to the surface or

interface. It does not happen if the amphiphilic molecule is too hydrophilic

or too hydrophobic, in which case it stays in one of the phases. Anionic

Surfactants are dissociated in water in an amphiphilic anion, and a cation,

which is in general an alcaline metal (Na+, K+) or a quaternary

ammonium. They are the most commonly used surfactants. They include

alkylbenzene sulfonates (detergents), (fatty acid) soaps, lauryl sulfate

(foaming agent), di-alkyl sulfosuccinate (wetting agent), lignosulfonates

(dispersants) etc. Anionic surfactants account for about 50 % of the world

production [60].

Some compounds, like short-chain fatty acids, are amphiphilic or

amphipathic [59]. A typical amphiphilic molecule consists of two parts: on

the one hand a polar group which contents heteroatoms such as O, S, P, or

N, included in functional groups such as alcohol, thiol, ether, ester, acid,

sulfate, sulfonate, phosphate, amine, amide etc. On the other hand, an

essentially apolar group which is in general a hydrocarbon chain of the

alkyl or alkylbenzene type, sometimes with halogen atoms and even a few

nonionized oxygen atoms. The polar portion exhibits a strong affinity for

polar solvents, particularly water, and it is often called hydrophilic part or


42

hydrophile. The apolar part is called hydrophobe or lipophile, from Greek

roots phobos (fear) and lipos (grease) [60]. These molecules from oriented

monolayers at interfaces and show surface activity (i.e, they lower the

surface or interfacial tension of the medium) in which they are dissolved. In

some usage surfactants are defined as molecules capable of associating to

form micelles. These compounds are termed surfactants, amphiphiles, and

surface active agents, tensides, or, in the very old literature, paraffin chain

salts [59]. The length of the alkyl chain is a major factor affecting the

properties of a gemini surfactant, and the spacer group is also an important

factor influencing the surfactant properties. The addition of surfactant is

reducing the interfacial tension. Variation in temperature will affect the

dynamic and equilibrium interfacial tension, and increasing the temperature

can shorten the time to reach the equilibrium and decrease the equilibrium

interfacial tension in the range of experimental temperatures [61].

Surfactant was used in reducing viscosity of viscous crude oil. The

application of surfactants in reduce viscosity of viscous crude oil were

introduced in which included anionic surfactant [62].

In two-phase dispersions, a thin intermediate region or boundary,

known as the interface, lies between the two phases. The physical

properties of the interface can be very important in all kinds of petroleum

recovery and processing operations. Whether in a well, a reservoir or a

surface processing operation, one tends to encounter large interfacial areas

exposed to many kinds of chemical reactions. In addition, many petroleum

industry processes involve colloidal dispersions of which contain large

interfacial areas; the properties of these interfaces may also play a large

role in determining the properties of the dispersions themselves. In fact,

even a modest surface energy per unit area can become a considerable total

surface energy. For a constant gas volume fraction the total surface area

produced increases as the bubble size produced decreases. Since there is a


43

free energy associated with surface area, this increases as well with

decreasing bubble size. The energy has to be added to the system to

achieve the dispersion of small bubbles.If this amount of energy cannot be

provided, say through mechanical energy input, then another is to use

surfactant chemistry to lower the interfacial free energy, or interfacial

tension. The origin of surface tension may be visualized by considering the

molecules in a liquid. The attraction van der waals forces between

molecules are felt equally by all molecules except those in the interfacial

region. This imbalance pulls the latter molecules towards the interior of the

liquid. The contracting force at the surface is known as the surface tension.

Since the surface has a tendency to contract spontaneously in order to

minimize the surface area, bubbles of gas tend to adopt a spherical shape:

this reduces the total surface free energy. As surfactant adsorbs at an

interface the interfacial tension will decrease. Figure(2.20) represent

Surfactant molecules surrounded the liquid particles [59].

Figure(2.20) Surfactant molecules surrounded the liquid particles[59].


44

Also the surfactants significantly improve the efficiency of the distillation.

The improved efficiency was caused by a stabilization of liquid film so

providing an increased interfacial area for mass transfer [63].

2.5.2 UAnionic Surfatant (Linear Alkyl Benzene Sodium

SulfonatUe) various types of additives are used in feed stocks for dewaxing to

increase the fraction rate and the dewaxed oil yield. The introduction of

activating additives is a rather simple method for influencing the balance of

foces of intermolecular interaction in the systems. The addition of

surfactant offers an increasing of the yield of light distilled [64]. The non-

Newtonian flow behavior and the activation energy of the viscous flow

drastically decrease in the presence of anionic surfactants [65]. The first commercially important synthetic surfactants were alkyl

benzene sulfonates which were developed as a result of shortages during

world war. Original versions of these chemicals had branched-chain alkyl

groups which eventually became intolerable of their slow rate of

biodegradation. Linear alkyl benzene sulfonates have proved to biodegrade

at acceptable rates and are still the major surfactant in the word today.

Alkyl benzene sulfonates are good detergents, emulsifiers, and foams and

are used in virtually all surfactant applications [66]. In the preparation of normal paraffins for use in the manufacture of

linear alkyl benzene, one obtains a reduced hydrocarbon which is as high in

straight-chain or normal molecules as possible. The proper carbon chain

length, C10-C14, is insured by boiling range. The linear paraffins are

separated from the branched ones with a continuous MOLEX unit, which

filters a kerosene feedstock through molecular sieves. The linear paraffin

stream is then redistilled to insure the desired chain length [66].


45

The following formula shows an amphiphilic (anionic) molecule

which is commonly used in shampoos (alkyl benzene sodium

sulfate)[67].Figure (2.21) show the molecular structure for surfactant[67].

Alkyl benzene sodium sulfonate *(56%C11, 33%C12, 7%C10, 4% C13)

Figure(2.21) anionic detergents[67].

The characterization of waxy crude oil (heavy crude oil) is measured

by the pour pointed to the temperature at which the oil observed to flow

when cooled under prescribed conditions. A waxy crude oil in contrast, has

a shear rate dependant viscosity. If during transport through the pipeline,

the crude oil will cool down, paraffines will crystallise and non-newtanian

effects will become apparent. At low temperatures, the viscosity of waxy


46

crude oils depends on the shear rate. During flow, a shear force is applied

that in addition to visco-elastics effects, may breakdown the interlocking

crystals making the viscosity time dependent as well. The amount of wax

deposited on the cold finger can be reduced by the utilization of a certain

quantity of chemical additives (surfactant) [67].

2.6 UPrevious Work Following is some of the selected previous works that cover the area

of interest :

Diakovi (1978) used a homogenizer ultraturrax (T-45), with rotor

speed (9200rpm) for crude oil of (55.2cp) viscosity and (0.853g/cmP

3 P)

density, with emulsion homogenization samples were taken after 3,6,12

and 24 minutes, as well as sodium dodeoyle sulphate and sodium

paradodecyle benzene sulphonate were used as surfactant.

Alteration of the number of revolutions of homogenizer changes the

viscous characteristics emulsions.

The results indicate that viscous characteristics of emulsions depend on the

type of emulsifier and its concentration plays a very important role in

viscosity changes during emulsification.[72]

Lin and Yen (1993) used ultrasound and surfactant (sodium

borohydride) at room temperature and atmospheric pressure to upgrading

heavy crude oil by converting asphaltenes in to gas oil and resins.

The results shows that the yield of light and intermediate fraction increased

to approximately 45% gasoline, 5% kerosene, 34% light and heavy

distillates, and 4% asphalt.[71]

Klokova and Glagoleva (1997) used various types of additives as

surfactant such as(progalite, prochiuor and Diproxomin) to improvement

crude oil distillation, the density of crudes oil that used (0.863 and 0.858

g/cmP

3P),where the yield of light and intermediate fractions increase from

(42%) to (50.6%) with using diproxamin as surfactant.[64]


47

Al-Roomi and George (2004) used a newly designed surfactant for

enhancing the flow properties of heavy/viscous crude oils of (0.975 g/cmP

3P)

density has been investigated using a programmable viscometer with speed

of (1000rpm) for (30 minutes), with surfactant alkylamide (AA) molecule

to reducing the viscosity of heavy crude oil. In which this surfactant has

high potential in reducing the viscosity of heavy crude oil emulsions even

though it constitutes a very low concentration in emulsions when compared

withthe commercial non-ionic surfactants. [2]

Boukadi and Amri (2005) upgraded the pipeline transportation of

waxy crude oils of density(0.920 and 0.832 g/cmP

3 P) at temperature below

their natural pour point, with additives of types Cocamidopropyl Betaine

(AC) and Sodium dodecyl Sulfate ( SS) and these retained a very low

dynamic viscosity, up to 70% lower than for crudes before upgrading. The

addition of additives to waxy crude oils improves their fluidity, where pour

point lowered to (-30 P

◦PC).[67]

Shiryaeva and Kudasheva (2005) used a high-frequency

electromagnetic field for crude oils of density(0.8226 and 0.8435 g/cmP

3P ).

The rheological by a rotary viscometer in (20-50 P

◦PC) temperature range,

with oligoisobutylene (OIB) as the modifying additive has been used to

decrease the viscosity and controlling wax deposits of crude oils.[58]

Redha (2006) used ultrasound technique for desulfurization and

upgrading crude oil with demulsification agent type (RP6000), at

temperatures of (30,50 and 60 P

◦PC), under sonication power, for different

periods of time (3,6,9,12 minutes). The results shows that API increased

from 20 to 30, and viscosity decreased from (87 to 54 cp).[6]

Experimental Work Chapter Three

48

Chapter Three Experimental Work

3.1 Introduction The experimental work is divided into three stages: In the first stage,

measuring and characterization of crude oil, the second stage includes

characterization of crude oil after applying the Rotary-Pulsation-Apparatus

(RPA), adding for this work, stage three studies the effect of (LABS)

addition as surfactant on characterization of crude oil with (RPA) process.

3.2 Apparatus 1. RPA elements (Rotor and Stator Apparatus).

2. Rotational viscometer.

3. Cleveland opens cup (Flash point apparatuse).

4. Electronic balance type (Ntrols mod. Mark 2200) with ± 0.05g accuracy.

5. Electric heater (electronic temperature regulated), (Tianjin City Taisite

Instruments).

3.3 Materials

3.3.1 Crude Oil Experimental work was carried out on mixed (Basrah-kirkuk) crudes

from (Daura refinery), with physical properties shown in Table (3.1).


49

Table (3.1) Physical Properties of the mixed (Basrah-kirkuk) crude oil

Properties of heavy crude oil

0.8807 Sp.gr

29 API

Nil Salt content (%wt.)

Nil Water and Sediment content(%vol.)

1.12 Ash content (%wt.)

1.14 Carbon residue(%wt)

75 Viscosity (cp) at 25P

oPC

75 Flash point (˚C)

-10 Pour point (˚C)

3.3.2 Surfactant Anionic Surfactant (alkyl benzene sodium sulfonate),concentration

38% was used .

Molecular Formula: C18H29NaO3S [12]

(LABS) is anionic surfactants with molecules characterized by a

hydrophobic and a hydrophilic group. They are nonvolatile compounds

produced by sulfonation [68]. Table (3.2) shows the Physical and chemical

properties for (LABS).


50

Table (3.2) Physical and chemical properties for (LABS)[68].

Items Index

Appearance (25°C) brown liquid

Sulphate % 1.5

Water content % 1

Molecular Weight (average C11.6 linear alkylchain) g/mol

342.4

Density kg/L 1.06 (relative) 0.55 (bulk)

Solubility g/L 250

Melting Point (Calculated as

C12)C

277

Boiling Point (Calculated as

C12)◦C

637

Vapour Pressure (at 25◦C;

calculated as C12) Pascal

7-10

pH in 1% water solution 7-10

3.4 Experimental Procedure

Characterization of Crude Oil after Upgrading with (RPA) The samples (liter of heavy crude oil at each run) after upgrading

include:

1. Crude oil treated at different (rpm) for (RPA) within (5 min).

2. Crude oil treated at different (rpm) for (RPA) within (10 min).

3. Crude oil treated with (LABS) at different (rpm ) for (RPA) within (5

min).

4.Crude oil treated with (LABS) at different (rpm) for (RPA) within (10

min).


51

3.4.1 Rotary-Pulsation-Apparatus

Figure (3.1) and figure (3.2) represent the schematic diagram for

(RPA).

Figure (3.1) (RPA) equipment

1: RPA elements (rotor and stator), 2: Electric motor of direct current DC, 3: The

instrument board and regulators, 4: Shift to achieve high rotational shift speed, 5:

Gearbox, 6: Tank, 7: U-shape tube, 8: pressure controller, 9: Rotational speed

controller, 10: Thermometer, 11: Flow meter, 12: fan.


52

Figure (3.2) Schematic diagram for the equipment

The experimental test bench includes the following parts ;(1) RPA

elements (rotor and stator) apparatus,(2) the electric motor of direct

current DC,(3)the instrument board. The control is brought out to the

front panel; ammeter, voltmeter, potentiometer for adjustment of

revolutions, the tumbler of start, the indicator of emergency situation,

general switch.

Electric current from the network falls on the instrument board (3), it is

converted into direct current DC, the block of adjustment is passed and it is

supplied to electric motor (2). The torque generated from the engine is

transmitted to gearbox(5) by shaft (4) to achieve high rotational shaft

speed, where frequency the rotation increases and then the torque is

transmitted directly to the rotor wheel of RPA .

The experimental procedures was:

1.Before starting the experimental run, the working liquid must be

injected into tank (6) with suitable level (in volume of 1 liter

approximately).


53

2.The tank (6) is mechanically connected directly with the (1) entrance

of RPA dispersing system by tubing.

3.The exhaust pipe of RPA dispersing system is connected with U-shape

tube (7) through which the working liquid going out from the RPA. The

number of recirculation of working liquid depends on the time of the

experimental working liquid.

4.The frequency of rotational speed is measured with aid of tachometric

sensor. The temperature in the tank is measured by thermometer.

The important part in this equipment in which most of the effect for

experimental work for crude oil is the (RPA) in which the mechanical

and acoustical effect is illustrated. Figure(3.3) and figure (3.4) show an

axial section view of the rotor and cross section view along the line A-

Aof the rotor-stator resbectivily.


54

Figure (3.3) is an axial section view of the roto

Figure (3.4) cross section view along the line A-Aof the rotor-stator

3.4.2 Photo/Contact Tachometer

Photo/Contact tachometer model DT-2268 has been used to

measure the number of rotation speed in (rpm).


55

3.5 Tests and Analysis

3.5.1 Rotational Viscometer

Model NDJ-4 Rotational viscometer is an instrument was used in

measuring the absolute viscosity. Figure (3.5) shows image for rotational

viscometer.

Figure (3.5) Image of rotational viscometer.

3.5.2 Cleveland opens cup (Flash point apparatus) Flash point, TF, for a hydrocarbon or a fuel is the minimum

temperature at which vapor pressure of the hydrocarbon is sufficient to

produce the vapor needed for spontaneous ignition of the hydrocarbon with

the air in the presence of an external source, i.e., spark or flame. Flash point

is used as an indication of the fire and explosion potential of a petroleum

product [69]. The Cleveland open cup method is one of three main methods

for determining the 0Tflash point0T of 0Tpetroleum0T using a Cleveland open cup

http://en.wikipedia.org/wiki/Flash_point�

http://en.wikipedia.org/wiki/Petroleum�


56

apparatus or Cleveland open cup tester. This apparatus may also be used to

determine the 0Tfire point0T which is considered to have been reached when the

application of the test flame produces at least five continuous seconds of

ignition [70]. Figure (3.5) shows the flash point equipment.

Figure (3.10) Cleveland equipment

3.5.3 Boling Point and (ASTM) Distillation Curve D-86 For a petroleum fraction of unknown composition, the boiling point may

be presented by a curve of temperature versus vol. % (or fraction) of

mixture vaporized. The boiling point of the lightest component in a

petroleum mixture is called initial boiling point (IBP) and the boiling point

of the heaviest compound is called the final boiling point (FBP). In some

references the FBP is also called the end point. The difference between

FBP and IBP is called boiling point range or simply boiling range. For

petroleum fraction derived from a crude oil, those with wider boiling range

contain more compounds than fraction with narrower boiling range. This is

due to the continuity of hydrocarbon compounds in a fraction. Figure (3.6)

shows ASTM distillation equipment [69].

http://en.wikipedia.org/wiki/Fire_point�


57

Figure (3.11) The Distillation Equipment.

3.5.4 Density, Specific Gravity and API Gravity Density is defined as mass per unit volume of a fluid. It is determined by

using a picknometer.

Results and Discussion Chapter Four

58

Chapter Four Results and Discussion

4.1 Introduction In this study experimental results (see appendix C) where carried out

in (RPA) treatment for crude oil, with, without additive surfactant

(LABS) at different homogenizing time and rotation speeds in rpm. The

effect of some of the above parameters on physical properties (i.e. ASTM

distillation curve, viscosity, API gravity, flash point and pour point for

crude oil ) are also studied.

4.2

Property

Characterization of Crude Oil The physical properties ;(API gravity, viscosity, ASTM distillation

curve, flash point and pour point) are used for evaluate crude oil.

Table (4.1) represents the physical properties of mixed (Basrah-kirkuk)

crude oil before treatment with (RPA).

Table (4.1) Physical Properties for mixed (Basrah-Kirkuk) crudes oil

Value

Flash point(˚C) 75

Pour point(˚C) -10

Density (gm/cm3 0.8807 )

API 29

Viscosity (c p) 75


59

(ASTM) runs for fractions before treatment with (RPA) and surfactant

(LABS) is shown in figure (4.1), where the total volume distilled for light

and intermediate fraction were (30 vol.%).

Figure (4.1) ASTM standard method for fraction

From figure (4.1), the yield of light and intermediate fractions for crude oil

before treatment with (RPA) have been measured and these results are

shown in table (4.2).

Table (4.2) Yield of light and intermediate fractions of crude oil before

treatment

Temperature

for fraction (C◦ ) %Yield of fraction

Gasoline (IBP-104)

0.6

Naphtha (104-157)

3.2

Kerosene (157-232)

11.5

Light gas oil (232-350)

14.7

Total 30

100

150

200

250

300

350

400

0 5 10 15 20 25 30 35

Tem

pera

ture

◦C

%Volume Distilled


60

4.3 Characterization of Crude Oil after Upgrading with

(RPA)

4.3.1

API Gravity Figure (4.2) shows the effect of (RPA) in (rpm) and homogenizing

time on API gravity of crude oil with and without adding surfactant

(LABS). Table (4.3) shows the samples of crude oil tested at various

rotation speeds for (RPA) in (rpm) within time of (5 to10 min).

Table (4.3) Samples of crude oil tested at various( rpm)

From the experimental work, API gravity was found equal to (29 API)

initially, then API increased with increasing rotation speed of (RPA) and

homogenizing time. The results show that the light and intermediate

fraction in range of temperature (IBP-104◦C), (104-157◦C), (157-232◦C)

and (232-350 ◦

C) increased as shown in table (4.5) and (4.6), (see p.68,

72). The API for sample (1) ,( tested at 1614 rpm ) in (RPA) equal to (30),

but for sample(7), (tested at 7610 rpm) equal to (38) within time(5min.),

also when increasing homogenizing time , API increases, as observed in

sample ( 1) API equal to (30) within (5 min.), but API became equal to

(32) for sample tested within (10 min) at the same (rpm).Which indicate

upgrading in the properties of crude oil.

Sample Number

Number of Rotation for (RPA) in (rpm)

1 1614 2 2189 3 3925 4 4425 5 5267 6 6225 7 7610


61

It is clear from figure (4.2) that a maximum increase in API of 40

for the samples tested within ( 5 to 10 min. ) without adding (LABS) is

found in sample number (7) at rotation speed (7610 rpm ) and

homogenizing time (10 min.).

The results show a significant increase in API gravity about (40)

with homogenizing time, which agrees with the results obtained by (Redha,

2006 and Yen, 1993) [6, 71] where, API reach to (30).

Figure (4.2) API Gravity for samples

28

32

36

40

44

48

1000 2000 3000 4000 5000 6000 7000 8000

API

gra

vity

Rotation Speed (rpm)

API for samples tested at 5min

API for samples tested at 10min

API for samples tested at 5min with LABS

API for samples tested at 10min with LABS


62

The percentage increase in API is shown in figure (4.3) for the

treated crude oil samples in RPA tested at 5 and 10 min homogenizing

time at different rotation speed of (RPA) as shown in table (4.3).

Figure (4.3) Percentage increase of API for at (5 and 10) min.

From figure (4.3), the maximum increase was 28% for the sample tested

at maximum homogenizing time (10 min), and maximum rotation speed

(7610 rpm) in RPA.

The increase in API gravity was upgraded when adding (2 gm/lit.)

of surfactant (LABS) to (RPA) system. The maximum increase for API

was at maximum homogenizing time and rotation speed (10 min., 7610

rpm), where the effect of (LABS) clear for the increasing the value of API

from (40 without LABS) to (45 with LABS) at the same time and (rpm) of

(10 min. and 7610 rpm ).

Figure (4.4) shows the percentage increasing in API for samples

tested within (5 to 10min.) with (LABS) at different rotation speed, where

the percentage increments increase with increasing homogenizing time and

rotation speed in (rpm) for RPA, where the maximum percentage

increasing in API at maximum homogenizing time and rotation speed for

36

12

1719

2224

912

1519

2224

28

0

10

20

30

1614 2189 3925 4425 5267 6225 7610perc

enta

ge in

crea

sing

in A

PI


percentage increasing in API fo samples tested at 5min

percentage increasing in API fo samples tested at 10min


63

RPA (10 min., 7610 rpm) respectively equal to (28%) without adding

(LABS), but increased to (36% ) after adding (LABS).

Figure (4.4) Percentage increase in API at (5 and 10min.) with (LABS)

4.3.2 Viscosity Viscosity is one of the important parameters to characterize crude

oil, where it is an important in the flow property in pipeline and in handling

processes. Figures (4.5) and (4.6) show the reduction in viscosity for

samples upgrades at homogenizing time (5 and 10min) with varies rotation

speed of (RPA).

In figure (4.5) and (4.6) samples (1, 2, 3, 4) refer to samples tested

at (1614, 3925, 5267, 7610 rpm) respectively at homogenizing time (5 and

10 min) at (30˚C).

1517

1922

26

3134

1922

2426

3133

36

0

10

20

30

40

1614 2189 3925 4425 5267 6225 7610

Perc

enta

ge in

crea

sing

in A

PI


Percentage increasing in API for samples tested at 5min with LABS

percentage increasing in API for samples tested at 10min with LABS


64

Figure (4.5) Viscosity of sample tested at (5min) in RPA

Figure (4.6) Viscosity for samples tested at (10min) in RPA

10

30

50

70

0 10 20 30 40 50 60 70

Vis

cosi

ty (

c.p)

Rotation Speed for Viscometer (rpm)

Crude oil Sample 1at (5min(. Sample 2at (5min(.

Sample 3at (5min(. Sample 4at (5min(.

10

30

50

70

90

0 10 20 30 40 50 60 70

Vis

cosi

ty (c

.p)

Rotation Speed of Viscometer (rpm)

Crude oil Sample 1at (10min(. Sample 2at (10min(.Sample 3at (10min(. Sample 4at (10min(.


65

From figures (4.5) and (4.6), it can be observed that the reduction in

viscosity increases with increasing rotation speed in RPA and

homogenizing time; in which the dispersion and homogenizing process

increase. The maximum reduction from (75 cp) for crude oil to (41 c p) for

sample tested within (10 min.) is shown at maximum rotation speed (7610

rpm) in (RPA).

Figures(4.6) and (4.7), indicate that all the viscosities of

samples(1, 2, 3 and 4) are better than the sample of crude oil before

treatment with (RPA) (i.e. by lighter viscosity).

In the time of homogenization process in (RPA) the particle size

distribution is changed (i.e. mean diameter, variance, specific surface area,

etc.) and alterations of viscous properties are the consequence of the

distribution [72]. This leads to transfer crude oil to lighter viscosity.

Figures (4.7) and (4.8) show the effect of adding (LABS) to crude

oil with treatment in (RPA), which has increased the reduction in

viscosity.

The present work was undertook the influence of the surfactant

(LABS) on the viscous characteristics changes during the homogenization

process in (RPA) under different conditions [58].

The adding of (LABS) improves crude oil viscosity that was

upgraded with (RPA) as shown in figures (4.7) and (4.8), in which the

maximum reduction for sample 4 at (7610 rpm) is found to equal (34 cp)

which is lighter than from these samples which were tested at the same

time and rotation speed without (LABS) which equal to (41 cp). Therefore,

(RPA) is one of the tools for improving the rheology of crude oil


66

10

30

50

70

90

0 10 20 30 40 50 60 70

Vis

cosi

ty (c

.p)


Crude oil Sample 1at 10min with LABNS

Sample 2at 10min with LABNS Sample 3at 10min with LABNS

Sample 4at 10min with LABNS

10

30

50

70

90

0 10 20 30 40 50 60 70

Vis

cosi

ty (c

.p)


Crude oil Sample 1at 5min. with LABNSSample 2at 5min. with LABNS Sample 3at 5min. with LABNSSample 4at 5min. with LABNS

.

Figure (4.7) Viscosity for samples tested at (5min) with (LABS) in RPA.

Figure (4.8) Viscosity for samples tested at (10 min) with (LABS) in RPA

Ultrasound provides the high temperature and pressure at localized

cavitation centers. And surfactant prevents the agglomeration of the


67

asphaltenes. They have applied these two elements for petroleum

upgrading. asphaltenes could form free radicals of lower molecular weight

by bond cleavage under ultrasound[3].

4.3.3 (ASTM) Distillation curve Figures (4.9) and (4.10) refer to the (ASTM) distillation curves

for crude oil samples before and after treatment with RPA within interval

5 and 10 mins. respectively. These Figures show the increasing in volume

distilled with time and rotation speed . This indication influences

mechanical-acoustical effect in (RPA). This produces organic molecules

lower in boiling point [6, 72 and 73]. From Figure (4.9) it can be seen that

the increasing in volume distilled, where the percentage of total volume

distilled for light and intermediate fraction (IBP-104◦C), (104-157◦C), (157-

232◦C) and (232-350◦C) was (30 Vol.%) before treatment but after

treatment its increased with rotation speed within (5 min), i.e., where the

maximum total volume distilled equal to (36 Vol.%) at maximum rotation

speed for RPA(7610 rpm). Also, the percentage of volume distilled

increases for samples tested within (10 min),where the maximum volume

distilled was (39 Vol.%) more than for that tested within (5min), which

equals to (36 Vol.%) as shown in figure (4.10).


68

Figure (4.9) ASTM for fractions for samples at 5min. .

Figure (4.10) ASTM for fractions for samples at 10 min

Table (4.4) shows the experimental results in the productivity percentage of

the most importance cut points feed stocks on petroleum refinery namely

100

150

200

250

300

350

0 5 10 15 20 25 30 35 40

Tem

pera

ture

◦C

%Volume Distilled

crude oil sample1 sample 2 sample 3 sample 4

100

150

200

250

300

350

0 10 20 30 40

Tem

pera

ture

◦C

%Volume Distilled



69

(IBP-104˚C), (104-157˚C), (157-232˚C), (232-350),before and after crude

oil treatment with RPA, where sample (1) is percentage yield of the

fraction without treatment , samples (2,3,4and 5) are percentage yield of

the light and intermediate fraction with treatment of crude oil in RPA

within (5 min), and samples( 6,7,8 and9), represent the percentage yield of

the light and intermediate fraction after treatment within (10 min)

homogenizing time ,at (1614, 3925, 5267, 7610 rpm) rotation speed of

RPA, respectively.

Table (4.5) Yield of light fraction for samples tested at 5and 10 min Yield of Light and Intermediate fraction %Vol.

Temperature for fraction

(C◦

Crude oil

)

Number of sample tested

at 5min.


at 10 min.

1 2 3 4 5 6 7 8 9

Gasoline (IBP-104)

0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6

Naphtha (104-157)

3.2 3.5 3.7 4 4.2 3.7 4 4.3 4.5

Kerosene (157-232)

11.5 12 12.5 13 13.5 12.3 13 13.5 14.1

Light Gasoil (232-343)

14.7 15.9 16.7 17.4 17.7 16.4 17.4 18.1 19.8

Total 30 32 33.5 35 36 33 35 36.5 39

From table (4.4), it is clear that maximum total percentage yield of light

and intermediate fraction in sample (9) which was tested within (10 min) of

homogenizing time and (7610 rpm) equals to (39 Vol%). As shown with

increasing of the homogenizing time in RPA at same rotation speed, will

tend to an increase in percentage yield of lighter and intermediate fraction.

The yield of light and intermediate fraction increases for

crude oil after treatment from (3.2 to 4.5 for naphtha, 11.5 to 14.1 for

kerosene and from 14.7 to 19.8 for light gasoil), for the sample tested at


70

maximum rotation speed in RPA (7610 rpm) and homogenizing time

within (10 min) .

The figure(4.10) shows that the increase in distillate volume as

sonication time increased. This result is due to the breaking of heavy

molecules into lighter free radicals by sonic-treatment. The produced

organic molecules are smaller in size and lower in boiling point (Yen, 1993

and Gunnerman, 2005)[71]. where the yields equals to 34 vol.%, but with

RPA reached to 39% at 10min. and 7610 rpm.

Figure (4.11) shows the increasing in percentage yield for light

and intermediate fraction for crude oil before and after upgraded with RPA

at homogenizing time with (5 to 10 min).

Figure (4.11) total percentage yield for samples tested at 5 min and 10

min

The yield of light and intermediate fraction for samples tested within

(10min) was more than for that tested within ( 5min) in the same various

rotation speed ,this indicates that crude oil was become lighter.

3032

33.535 36

30

3335

36.539

25

30

35

40

45

1614 3925 5267 7610

Perc

enta

ge Y

ield


Percentage yield for samples Tested at 5min

Percentage yield for samples tested at 10min


71

The effect of the addition of surfactant (LABS) on crude oil

distillation performance is shown in figures (4.12) and (4.13), which

significantly improve the efficiency of the distillation. [64].

Figure (4.12) shows that the percentage of volume distilled for

light and intermediate fraction increases with adding surfactant (2gm/lit).

The maximum volume distilled is equal to (40 Vol.%) for sample tested

within (10 min) and (7610 rpm), but for sample tested at the same

homogenizing time and rotation speed without adding (LABS) is equal to

(39 Vol.%).

Figure (4.12) ASTM for fractions for samples at 5 min with addition of

(LABS).

When increasing homogenizing time within (10 min.) when surfactant

(LABS) is added the percentage of volume distilled increases at the same

rotation speed as shown in figure (4.13).The maximum total volume

distilled for sample tested within (10 min) equals to (40 Vol.%) which is

100

150

200

250

300

350

0 5 10 15 20 25 30 35 40

Tem

pera

ture

◦C

%Volume Distilled



72

more than for that sample tested within (5min) which equals to (37 Vol.%)

at same maximum rotation speed (7610 rpm ).

Figure (4.13)ASTM for fractions for samples at 10 min with addition (LABS).

Table (4.5) shows the yield of light and intermediate fraction , where

sample (1) percentage yield of the fraction before treatment, samples

(2,3,4 and 5) percentage yield after treatment with (RPA ) within (5 min)

and samples (6,7,8 and 9) represent the percentage yield after treatment in

(RPA) within ( 10 min) at (1614, 3925, 5267and 7610 rpm) with surfactant

(LABS).

100

150

200

250

300

350

0 10 20 30 40

Tem

pera

ture

◦C

%Volume Distilled



73

Table (4.6) Yield of light fractions for samples tested at 5and 10 min.

with (LABS) Yield of Light and Intermediate fraction %Vol.

Temperature for fraction

(C◦

Crude oil

)


at 5min.


at 10 min.

1 2 3 4 5 6 7 8 9

Gasoline (IBP-104)

0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.6

Naphtha (104-157)

3.2 3.6 3.9 4.2 4.4 3.9 4.2 4.5 4.8

Kerosene (157-232)

11.5 12.4 12.9 13.3 13.6 12.6 13.5 14 14.4

Light Gasoil (232-343)

14.7 16.4 17.1 17.9 18.4 16.9 18.2 18.9 20.2

Total 30 33 34.5 36 37 34 36.5 38 40

Table (4.6) shows that percentage yield increases with increasing

homogenizing time and rotation speed and the addition of (LABS)

increases the percentage yield more than that increase without adding

(LABS) at the same residence time and rotation speed for (RPA). For

example the maximum total percentage yield within (10 min) and (7610

rpm) without (LABS) equals to (39 Vol.%), but at the same condition of

treating it is found equal to (40 Vol.%) with addition (LABS).


74

The yield of light and intermediate fraction increases after treatment

from (3.2 to 4.8 for naphtha, 11.5 to 14.4 for kerosene and from 14.7 to

20.2 for light gasoil) at(10 min ) and ( 7610 rpm) with (LABS).

Figure (4.14) shows the percentage yield for light and

intermediate fraction for samples tested within (5to10 min.) with (LABS).

Figure (4.14) total percentage yield for samples tasted at 5and 10 min. with LABNS.

as in Tables (4.4) and (4.5) are constructed, it is clear that the effect of

addition of (LABS) is to increase the yield of light and intermediate

fraction from ( 4.5 to 4.8 for naphtha, 14.1 to 14.4 for kerosene and from

19.8 to 20.2 for light gasoil ) within (10min) and (7610 rpm) for sample(9).

3033 34.5 36 37

3034

36.5 38 40

5

15

25

35

45

0 1614 3925 5267 7610

Perc

enta

ge Y

ield


Percentage yield for samples tested at 5min with LABS

Percentage yield for samples tested at 10min with LABS


75

4.3.4

Figure (4.15) flash point for samples

Flash Point Figure (4.15) shows flash points at different residence time and

rotation speed ,with and without adding (LABS). It is clear from

figure(4.15) that the reduction in flash point after treatment with RPA

increases with homogenizing time , where the flash point for crude oil

before upgrading equals to (75◦C), but after upgrading within ( 5 min)

equals to (57◦C) and the reduction increases within (10 min) to (54◦C) at

same rotation speed of (RPA), and the addition of (LABS) increases the

reduction in flash points at same rotation speed of (RPA) and residence

time, which equals to ( 52◦C) and (50◦C) within (5 to 10 min), respectively.

Samples (1,2,3,4,5,6,and 7 ) are the samples of treated crude oil

with RPA at (1614,2189,3925,4425,5267,6225 and 7610 rpm) rotation

speed respectively.

45

50

55

60

65

70

75

80

1000 2000 3000 4000 5000 6000 7000 8000

Flas

h Po

int◦

C


Samples at 5min Samples at 10min

Samples at 5min with LABS Samples at 10min with LABS


76

The percentage reduction in flash points for crude oil upgraded within ( 5

to 10 min) residence time at various (rpm) for (RPA) is shown in figure

(4.16) ,where the reduction increase with residence time and rotation

speed of ( RPA).

Figure (4.16) percentage reduction in flash points for samples tested at 5

and 10 min. at various rotation speed of RPA.

Figure (4.17) shows the percentage reduction in flash points crude oil

within (5 to 10 min) at various rotation speed with addition (LABS),

where the percentage reduction increases more than that for samples tested

without surfactant (LABS) at same homogenizing time and rotation speed

in (rpm).

7

1113

1720 21

24

9

15 16

2023

27 28

0

5

10

15

20

25

30

1614 2189 3925 4425 5267 6225 7610Perc

enta

ge R

educ

tion

in F

lash

Poi

nt


Samples tested at 5min Samples tested at 10min


77

Figure (4.18) percentage reduction in flash points for samples tested at 5

and 10 min. with addition (LABS).

Under long-term vigorous cavitation, the C-C bonds are broken in the wax

molecules, as a result of which the physicochemical parameters are altered

(the molecular mass, crystallization temperature, etc.), and the properties of

the petroleum derivatives (viscosity, density, flash point) are lowered [47].

11

16 1721

2729

31

13

19 2024

2932 33

0

5

10

15

20

25

30

35

1614 2189 3925 4425 5267 6225 7610

Perc

enta

ge R

educ

tion

in F

lash

Poi

nt


Samples tested at 5min with LABS Samples tested at 10min with LABS


78

4.3.5

Figure (4.18) pour point for samples

The percentage reduction in pour points for samples tested within( 5 to10

min) at various rotation speed is shown in figure (4.19), where the

reduction increases with time and (rpm) for (RPA).

Pour point Figure (4.18) shows pour points for crude oil before and after

treatment in RPA at different residence time and rotation speed in( rpm),

with and without addition (LABS). It is clear from figure that the reduction

in pour points after treatment with RPA increases with time , where the

pour point for crude oil before upgrading equals to (-10◦C) and after

upgrading within ( 5 min) in RPA equals to (-30◦C) and the reduction

increase with increasing time to (10 min) to(-32◦C) at same rotation speed

for (RPA), and the addition of (LABS) increases the reduction at same

rotation speed and residence time, which found equals to ( -33◦C) and

(-36◦C) within ( 5 to 10 min), respectively.

Samples (1,2,3,4,5,6,and 7) are the treated samples in RPA at

(1614,2189,3925,4425,5267,6225and 7610 rpm), respectively.

-40

-30

-20

-100 2000 4000 6000 8000

Pour

Poi

nt ◦C


Samples at 5min Samples at 10min

Samples at 5min with LABS Samples at 10min with LABS


79

Figure (4.19) percentage reduction in pour points for samples tested at 5

and 10 min. at various rotation speed in RPA.

Figure (4.20) shows the percentage reduction in pour points after treatment

within (5 to10 min) at various rotation speed , with addition of (LABS),

where the percentage reduction increases more than that for samples tested

without surfactant at the same homogenizing time and rotation speed. The

results show a significant decrease in pour point after treatment with

additive, which agrees with the results obtained in [67].

Figure (4.20) percentage reduction in pour points for samples tested at 5

and 10 min. at various rotation speed with addition (LABS).

3341

5057 60 64 67

4150

5560 62 66 69

0

20

40

60

80

1614 2189 3925 4425 5267 6225 7610

Perc

enta

ge R

educ

tion

in P

our

Poin

t


Samples tested at 5min Samples tested at 10min

44

5258

6366

69 70

5055

62 6467

71 72

20

40

60

80

1614 2189 3925 4425 5267 6225 7610

Perc

enta

ge R

educ

tion

in P

our

Poin

t


Samples tested at 5min with LABS Samples tested at 10min with LABS


80

After treatment, the paraffin molecules in crude oil are surrounded by a

solvated layer in frontier, which makes reduce agglomerating possibility of

high molecular weight paraffin, so the crude oil pour point and viscosity

were reduced as the result [73].

The addition of (LABS), with increasing homogenizing time and

rotation speed for (RPA), leads to an increase of percentage yield of light

and intermediate fraction, reduces flash point, reduces pour point, and

therefore this leads the heavy crude oil gradually to transfer into low

viscosity and lighter fraction and loses rigidity, thus providing better

handling properties and then additional possibilities of being transported in

pipe lines.

Chapter five Conclusions and Recommendation

81

Chapter Five Conclusions and Recommendations for Future

Work 5.1 UConclusions U The following conclusions could be obtained

1. The density, specific gravity, viscosity, flash point and pour point for

crude oil decrease after treatment in (RPA) with increasing

homogenizing time and rotation speed in rpm.

2. API and The total percentage yield of light and intermediate fraction

for crude oil after treatment in RPA increase with increasing

homogenizing time and rotation speed rpm.

3. The effect of addition (LABS) as surfactant leads to enhancement the

process of upgrading crude oil with (RPA), where the results show

that (API gravity) and the total percentage yield for light and

intermediate fraction increase more than treatment without (LABS)

at the same homogenizing time and rotation speed in rpm.

4. Flash point, pour point, viscosity decrease with the effect of (LABS)

more than that treatment without it in (RPA) at the same

homogenizing time and rotation speed in rpm.

Chapter five Conclusions and Recommendation

82

5.2 Recommendations for Future Work Rotary-Impulsed Apparatus is intended for treatment of liquids,

mixes liquid-and-liquid, liquid-and-gas. The RPA can be used in both in line or batch operation. The project also

provides the most demanding chemicals and technical services in the

following areas:

1. Asphalt industry, emulsion.

2. Heavy fuel oil emulsion.

3. Studying the effect of adding solvents in upgrading heavy crude oil with

(RPA)

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of Oil in Water Emulsions during Homogenization”, Colloid and Polymer

Science, Vol.256, No.12, pp. (1177-1179), (1978).

73. Tung, N. Ph., Vinh, N. Q., Trang, N. Th., and Dung, N.A., “Modeling

Rheological Improved Effect of Magnetic Fields on Paraffin Crude Oil

Flow in Non-Newtonian Fluid Area”, Proceedings of 8th German-

Vietnamese Seminar on Physics and Engineering, Erlangen, Institute of

Materials Science, Hochiminh City Branch , Erlangen,03-08 April,(2005).

Appendix A

]1A-[

Appendix: A

Calculation of Viscosity

Table (A.1) for the range of (rotation viscometer) to select the

appropriate rotor and speed according to this table, in which for crude oil

use large rotor and fast speed (High speed and Rotor1):

4

3

2

1

Rotor

Range (mpa.s)

rpm

Step

200X 10P

4 40X 10P

4 10 X 10P

4 2 X 10P

4 0.3

L 100X 10P

4 20X 10P

4 5 X 10P

4 1 X 10P

4 0.6 40 X 10P

4 8 X 10P

4 2 X 10P

4 4 X 10P

3 1.5 20 X 10P

4 4 X 10P

4 1 X 10P

4 2 X 10P

3 3.0 10 X 10P

4 2 X 10P

4 5 X 10P

3 1 X 10P

3 6 H 5 X 10P

4 1 X 10P

4 2.5 X 10P

3 500 12 2 X 10P

4 4 X 10P

3 1 X 10P

3 200 30 1 X 10P

4 2 X 10P

3 500 100 60

Appendix A

]2A-[

Table (A.2) Coefficient (K) where the reading indicator on

the graduated disk should multiply with the particular coefficient in

table of Range to get the absolute viscosity (mpa.s) i.e.

μ = k.a

4

3

2

1

Rotor

Coefficient

RPM

Step

20000 4000 1000 2 00 0.3

L 10000 2000 500 100 0.6 4000 800 200 40 1.5 2000 400 100 20 3.0 1000 200 50 10 6

H 500 100 25 5 12 200 40 10 2 30 100 20 5 1 60

Table (A.3) shows the measurement of viscosity by using rotational

viscometer for crude oil before and after treatment at 5 min . with different

rotation speed in RPA shows in table (C.6).

Rotation

Speed for

Viscometer

(rpm)

K

Crude oil Before Treatment

Samples of Crude Oil After Treatment in RPA

aR◦

μR◦

aR1

μR1

aR2

μR2

aR3

μR3

aR4

μR4

6 10 7.5 75 6.5 65 6 60 5.5 55 4.5 45

12 5 13 65 11.4 57 10.2 51 9.4 47 7.4 37

30 2 27.5 55 20 40 16.5 33 14 28 12.5 25

60 1 50 50 35 35 28 28 23 23 21 21

Appendix A

]3A-[


viscometer for crude oil before and after treatment at 10 min. with

different rotation speed in RPA shows in table (C.6).

Rotation

Speed for

Viscometer

(rpm)

K

Crude Oil Before Treatment

Samples of Crude Oil After Treatment in

RPA

aR◦

μR◦

aR1

μR1

aR2

μR2

aR3

μR3

aR4

μR4

6 10 7.5 75 5.7 57 5.2 52 4.7 47 4.1 41

12 5 13 65 10.6 53 9.6 48 8 40 6.8 34

30 2 27.5 55 22.5 45 18.5 37 16 32 13 26

60 1 50 50 37 37 29 29 25 25 19 19



different rotation speed in RPA shows in table (C.6) with (LABS).

Rotation

speed for

viscometer

(rpm)

K

crude oil before treatment

Samples of crude oil after treatment in RPA

aR◦

μR◦

aR1

μR1

aR2

μR2

aR3

μR3

aR4

μR4

6 10 7.5 75 5.5 55 5 50 4.5 45 3.9 39

12 5 13 65 5 50 8.8 44 7.8 39 6.8 34

30 2 27.5 55 21 42 17.5 35 15.5 31 12.5 25

60 1 50 50 35 35 29 29 24 24 18 18

Appendix A

]4A-[



different rotation speed in RPA shows in table (C.6) with (LABS).

Rotation

speed for

viscometer

(rpm)

K

crude oil before

treatment

Samples of crude oil after treatment in RPA

aR◦

μR◦

aR1

μR1

aR2

μR2

aR3

μR3

aR4

μR4

6 10 7.5 75 5 50 4.4 44 3.8 38 3.4 34

12 5 13 65 9.5 46 8 40 6.6 33 5.8 29

30 2 27.5 55 20 40 16 32 14 28 12 24

60 1 50 50 31 31 27 27 22 22 16 16

Appendix B

]1B-[

Appendix: B Calculation Density, Specific Gravity and API Gravity for Crude Oil UCalculation Density for Crude Oil From experimental work Weight of empty Picknometer =10.06 gm Weight of picknometer filled with distilled water =19.03 gm Weight of picknometer filled with crude oil =17.96 gm UCalculation

Weight of distilled water = Weight of picknometer _ Weight of empty

filled with distilled water picknometer

Weight of distilled water = 19.03 - 10.06 = 8.97 gm ρ of water = 𝑤𝑤𝑤𝑤𝑤𝑤𝑤𝑤 ℎ𝑡𝑡 𝑜𝑜𝑜𝑜 𝑑𝑑𝑤𝑤𝑑𝑑𝑡𝑡𝑤𝑤𝑑𝑑𝑑𝑑𝑤𝑤𝑑𝑑 𝑤𝑤𝑤𝑤𝑡𝑡𝑤𝑤𝑤𝑤

𝑣𝑣𝑜𝑜𝑑𝑑𝑣𝑣𝑣𝑣𝑤𝑤 𝑜𝑜𝑜𝑜 𝑑𝑑𝑤𝑤𝑑𝑑𝑡𝑡𝑤𝑤𝑑𝑑𝑑𝑑𝑤𝑤𝑑𝑑 𝑤𝑤𝑤𝑤𝑡𝑡𝑤𝑤𝑤𝑤 ρ of water = 1 𝑤𝑤𝑣𝑣/𝑐𝑐𝑣𝑣3

Then

𝑉𝑉. 𝑜𝑜𝑜𝑜 𝑤𝑤𝑤𝑤𝑡𝑡𝑤𝑤𝑤𝑤 = wt .of water

ρ of water 𝑉𝑉. 𝑜𝑜𝑜𝑜 𝑤𝑤𝑤𝑤𝑡𝑡𝑤𝑤𝑤𝑤 = 8.97 gm

�1 gmcm 3�

=8.97 CmP

3

Weight of heavy crude oil = wt. of picknometer _ wt. of empty

filled with crude oil picknometer

Wt. of crude oil = 17.96 – 10.06

7.9 gm =

Appendix B

]2B-[

ρ 𝑜𝑜𝑜𝑜 𝑐𝑐𝑤𝑤𝑣𝑣𝑑𝑑𝑤𝑤 𝑜𝑜𝑤𝑤𝑑𝑑 = 7.9 gm8.97 𝑐𝑐𝑣𝑣3

=0.8807 gm/cmP

3P

UCalculation of specific gravity for crude oil 𝑆𝑆𝑆𝑆 = ρ of liquid at temperature T

ρ of water at temperature T

The density of liquid water is 0.999 g/cm3 or almost 1 gm/cm3. 𝑆𝑆𝑆𝑆 for crude oil =

ρ of crude oilat 60˚F in gcm 3

0.999 gcm 3

𝑆𝑆𝑆𝑆 for crude oil =0.8807 gm

cm 31g𝑣𝑣cm 3

Then 𝑆𝑆𝑆𝑆 for crude oil = 0.8807

UCalculation of API gravity for crude oil

𝐴𝐴𝐴𝐴𝐴𝐴 = 141.5SG (at 60˚F)of crude oil

− 131.5

29.168 =

Appendix C

]1C-[

Appendix: C

Experimental Results

Table (C.1) ASTM method (volume distilled % verse temperature).True

Boiling Point Curve for fraction before treatment

Temperature( P

◦PC) Vol.%

Distilled 97 0

136 2 162 4 178 6 193 8 207 10 223 12 239 14 255 16 270 18 280 20 292 22 300 24 311 26 328 28 343 30

UAPI Gravity

Table (C.2) shows the samples tested at various rotation speeds for RPA in

(rpm).

Sample Number

Number of Rotation

(rpm)

1 1614 2 2189 3 3925 4 4425 5 5267 6 6225 7 7610

Appendix C

]2C-[

Table (C.3) API gravity for crude oil before and after treatment with RPA

for samples tested at rotation speed showed in table (C.2) (with and without

(LABS)).

API for Sample

Tested at 10 min. in RPA with (LABS)

API for Sample

Tested at 5 min. in RPA with (LABS)

API for Sample

Tested at 10 min. in RPA

API for Sample

Tested at 5 min. in RPA

Sample Number

29

29

29

29

crude oil before treating

36 34 32 30 1 37 35 33 31 2 38 36 34 33 3 39 37 36 35 4 42 39 37 36 5 43 42 38 37 6 45 44 40 38 7

Table (C.4) percentage increasing% in API for samples tested at 5 and 10

min. in RPA.

Samples Tested at 10 min. in RPA


Sample Number

9 3 1 12 6 2 15 12 3 19 17 4 22 19 5 24 22 6 28 24 7

Appendix C

]3C-[

Table (C.5) percentage increasing% in API for samples tested at 5 and 10

min. in RPA with (LABS).

Samples Tested at 10 min. in

RPA with (LABS)

Samples Tested at 5 min. in RPA with (LABNS)

Sample Number

19 15 1 22 17 2 24 19 3 26 22 4 31 26 5 33 31 6 36 34 7

UViscosityU

Table (C.6) Viscosity for crude oil before and after treatment in RPA at

different homogenizing time of 5 and 10 min. in which samples number

refer to the samples tested at different rotation speed of RPA as shown in

this table.

Rotation Speed in (rpm) Sample Number After Treatment with RPA

1614 1

3925 2

5267 3

7610 4

Appendix C

]4C-[

Table (C.7) viscosity for samples tested at homogenizing time 5 min. at

rotation speed showed in table (C.6) for RPA.

4

3

2

1

Crude Oil Before

Treatment

Sample

Number .

Viscosity (mpa.s)

Rotation Speed (rpm) for Viscometer

45 55 60 65 75 6 37 47 51 57 65 12 25 28 33 40 55 30 21 23 28 35 50 60

Table (C.8) viscosity for samples tested at homogenizing time 10 min. at

rotation speed showed in table (C.6) for RPA.

4

3

2

1

Crude Oil Before

Treatment

Sample

Number .

Viscosity (mpa.s)

Rotation Speed (rpm) for Viscometer

41 47 52 57 75 6 34 40 48 53 65 12 26 32 37 45 55 30 19 25 29 37 50 60

Appendix C

]5C-[

Table (C.9) viscosity for samples tested at homogenizing time 5min. at

rotation speed showed in table (C.6) for RPA with (LABS).

4

3

2

1

Crude Oil Before

Treatment

Sample

Number .

Viscosity (mpa.s)

Rotation Speed (rpm) for viscometer

39 45 50 55 75 6 34 39 44 50 65 12 25 31 35 42 55 30 18 24 29 35 50 60

Table (C.10) viscosity for samples tested at homogenizing time 10min. at

rotation speed showed in table (C.6) for RPA with (LABS).

4

3

2

1

Crude Oil Before

Treatment

Sample

Number .

Viscosity (mpa.s)

Rotation Speed (rpm) for viscometer

34 38 44 50 75 6 29 33 40 46 65 12 24 28 32 40 55 30 16 22 27 31 50 60

Appendix C

]6C-[

True Boiling points and Distillation Curve (ASTM Method) For Fractions Before and After Treatment With RPA

Table (C.11) Boiling points curve before and after treatment at

homogenizing time 5 min. at various rotation speed of RPA as shown in

table (C.6).

Temperature (P

◦PC) Vol.%

Distilled Sample

4 Sample

3 Sample

2 Sample 1 Crude Oil Before

Treatment 97 97 97 97 97 0 136 136 136 136 136 2 140 142 145 150 162 4 146 151 160 170 178 6 156 162 178 184 193 8 172 178 190 196 207 10 180 188 198 209 223 12 190 198 212 220 239 14 203 214 224 232 255 16 218 224 235 242 270 18 227 233 246 252 280 20 241 250 261 270 292 22 256 261 272 283 300 24 263 273 286 299 311 26 278 291 304 316 328 28 291 308 315 326 343 30 310 320 333 343 32 325 334 343 34 343 343 36

Appendix C

]7C-[



table (C.6).

Temperature (P

◦PC) Vol.%

Distilled Sample 4 Sample 3 Sample 2 Sample 1 Crude Oil Before

Treatment 97 97 97 97 97 0

136 136 136 136 136 2 140 142 145 148 162 4 144 148 155 163 178 6 153 155 161 178 193 8 160 163 180 187 207 10 168 176 188 198 223 12 177 185 198 216 239 14 189 198 215 225 255 16 198 210 223 235 270 18 213 221 236 248 280 20 225 239 255 265 292 22 243 252 267 276 300 24 258 271 280 291 311 26 270 285 298 313 328 28 285 294 308 318 343 30 295 310 219 329 32 302 319 332 343 34 318 333 343 36 335 343 38 343 39

Appendix C

]8C-[



table (C.6) with (LABS).

Temperature (P

◦PC) Vol.%

Distilled Sample 4 Sample 3 Sample 2 Sample 1 Crude Oil

Before Treatment

97 97 97 97 97 0 136 136 136 136 136 2 142 142 145 148 162 4 146 148 154 161 178 6 152 154 160 175 193 8 158 162 175 187 207 10 167 174 185 196 223 12 178 188 198 215 239 14 185 198 212 225 255 16 196 209 222 234 270 18 208 220 232 249 280 20 218 236 246 265 292 22 230 250 258 274 300 24 248 260 270 288 311 26 261 272 289 301 328 28 278 288 297 316 343 30 292 300 312 330 32 309 320 328 343 34 328 343 343 36 343 37

Appendix C

]9C-[



table (C.6) with (LABS).

Temperature (P

◦PC) Vol.%

Distilled Sample 4 Sample 3 Sample 2 Sample 1 Crude Oil

Before Treatment

97 97 97 97 97 0 136 136 136 136 136 2 144 144 145 148 162 4 147 148 154 161 178 6 151 153 160 175 193 8 158 161 175 187 207 10 165 170 185 196 223 12 172 179 198 215 239 14 179 188 212 225 255 16 186 198 222 234 270 18 198 211 232 249 280 20 211 223 246 265 292 22 222 235 258 274 300 24 235 245 270 288 311 26 244 256 289 301 328 28 257 271 297 316 343 30 269 288 312 330 32 280 301 328 343 34 298 324 343 36 325 343 38 343 40

Appendix C

]10C-[

Flash Point

Table (C.15) flash point for crude oil before and after treatment for

samples tested at rotation speed showed in table (C.2) for RPA (with and

without (LABS)).

Flash point(P

◦PC) for

Samples Tested at 10 min. in RPA with (LABS)

Flash point(P

◦PC) for

Samples Tested at 5

min. in RPA with (LABS)

Flash point (P

◦PC) for


Flash Point(P

◦PC) for

Samples Tested at 5

min. in RPA

Sample Number

75

75

75

75


65 67 68 70 1 61 63 64 67 2 60 62 63 65 3 57 59 60 62 4 53 55 58 60 5 51 53 55 59 6 50 52 54 57 7

Table (C.16) percentage reduction% in flash point for samples tested at 5

and 10 min. for samples tested at rotation speed showed in table (C.2) in

RPA.


RPA


Sample Number

9 7 1 15 11 2 16 13 3 20 17 4 23 20 5 27 21 6 28 24 7

Appendix C

]11C-[

Table (C.17) percentage reduction % in flash point for samples tested at

5 and 10 min. for samples tested at rotation speed showed in table (C.2) in

RPA with (LABS).


RPA


Sample Number

13 11 1 19 16 2 20 17 3 24 21 4 29 27 5 32 29 6 33 31 7

Pour point

Table (C.18) pour point for crude oil before and after treatment for

samples tested at rotation speed showed in table (C.2) in RPA (with and

without (LABS)).

Pour Point(P

◦PC) for

Samples Tested at 10 min. in RPA with (LABS)

Pour Point(P

◦PC) for

Samples Tested at 5

min. in RPA with (LABS)

Pour Point (P

◦PC) for


Pour Point(P

◦PC) for

Samples Tested at 5

min. in RPA

Sample Number

-10

-10

-10

-10


-20 -18 -17 -15 1 -22 -21 -20 -17 2 -26 -24 -22 -20 3 -28 -27 -25 -23 4 -30 -29 -27 -25 5 -34 -32 -30 -28 6 -36 -33 -32 -30 7

Appendix C

]12C-[

Table (C.19) percentage reduction% in pour point for samples tested at 5


RPA.


RPA


Sample Number

41 33 1 50 41 2 55 50 3 60 57 4 62 60 5 66 64 6 69 67 7

Table (C.20) percentage reduction % in pour point for samples tested at 5


RPA with (LABS).


RPA


Sample Number

50 44 1 55 52 2 62 58 3 64 63 4 67 66 5 71 69 6 72 70 7

Appendix D

]1D-[

Appendix: D It is important to make calibration for the (RPA) equipment to define

each number on the gear box how much equal rotation speed in (RPA) and

also measure the temperature rise for crude oil in each rotation speed in

rpm, as shown in table (D.1).

Table (D.1) set numbers verses rotation speed of (RPA)

Set Number

Number of Rotation (rpm)

Temperature

(P

◦PC)

1 1614 40

2 2189 44

3 3925 50

4 4425 54

5 5267 59

6 6225 64

7 7610 68

Appendix D

]2D-[

Figure (D.1) shows the calibration for temperature (◦C) versus rotation

speed of (RPA) in (rpm) ,where the relation between them is liner.

Figure (D.1) Temperature Verses Rotation Speed (RPA)

y = 0.004x + 32.75R² = 0.987

40

50

60

70

1500 3500 5500 7500

Tem

pera

ture◦C


الخالصة بعض النفوط الخام تكون اقل استقرارية ومالئمة للمعالجة وكلفة معالجتها عالية، وعندما تزداد اللزوجة

فان مشاكل المعالجة تزداد من ناحية متطلبات معدات المعالجة وكذلك استخدام ظروف شديدة وقاسية

من درجة حرارة وضغط ، كذلك يحتاج الى معدات اضافية للتسخين وهذا بدوره يمثل كلف اضافية،

عالوة على ذلك هناك صعوبة في المحافظة على اللزوجة المخفضة ،حيث ان بعض النفوط تعود الى

لزوجتها االصلية بعد فترة من الزمن بعد المعالجة.

ستخدام اتمت دراسة تحسين مواصفات النفط الخام (خليط بصرة- كركوك) بواسطة طريقة التقليدية ب

. حيث تم دراسة تحسين المواصفات في ) )RPAمنظومة الخلط التوربينية (جهاز نابض دوار نفاث (

دورة/دقيقة) وكذلك تم 7610 وبسرع متدرجة تصل الى (دقيقة) 5-10 مجانسة ضمن مدى(أوقات

ومن ثم تم تقييم مواصفات استخدام مادة (الكيل بنزين صوديوم سلفونيت) كمادة خافضة للشد السطحي

النسبة الحجمية للقطفات الخفيفة إن القياسية ,حيث وجد )ASTM طريقة (باستخدامالنفط الخام

و)IBP-104˚C ,()104-157˚C,() 157-232˚C الحرارة التالية ( والمتوسطة ضمن مدى درجات

232-350 ˚C)() بعد المعالجة بواسطة RPA )39)نسبة مئوية حجمية إلى (% 30) ) ازداد من %

).RPAعند زيادة وقت التجانس وسرعة الدوران في (

) إلى (29 من API) يؤديان إلى الزيادة في RPAإن الزيادة في وقت المجانسة وسرعة الدوران في (

) (C˚54) إلى (C˚75 وزيادة في نسبة القطفات الخفيفة والمتوسطة ويخفض نقطة الوميض من (40)

وبالتالي يؤدي هذا التحسن 32) -˚ (C إلى10)- (C˚وكذلك يخفض درجة الضباب واالنسكاب من

في خواص الجريان للنفط الخام و إلى سهولة نقله عبر خطوط األنابيب.

كمادة خافضة LABS)باإلضافة إلى ذلك فان استخدام مادة (الكيل بنزين صوديوم سلفونيت الخطي) (

للشد السطحي, ساعدت في تسهيل عملية معالجة النفط الخام حيث انه يقلل من إجهاد القص.والنتائج

(C˚ 50)و انخفضت نقطة الوميض إلى (45 ) ) إلىAPIأظهرت صحة ما ورد مسبقا حيث ازداد(

وأخيرا نسبة القطفات الخفيفة والمتوسطة C)˚-(36وكذلك نقطة الضباب واالنسكاب انخفضت إلى

(% 40).ازدادت إلى

العالي و البحث العلميوزارة التعليم

الجامعة التكنولوجية

قسم الهندسة الكيمياوية

دراسة تكسير نفط خام (خليط بصرة- كركوك) باستخدام التأثير الصوتي والميكانيكي المشترك

رسالة مقدمة الى

الجامعة التكنولوجية كجزء من متطلبات نيل درجة الماجستير في / قسم الهندسة الكيمياوية

علوم الهندسة الكيمياوية

من قبل غفران رحيم حمود

) 2008 (بكالوريوس هندسة كيمياوية,

بآشراف

د. عادل شريف حمادي

2011 1432

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