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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 [-]
a Indicated by indicator for crude oil after treatment (sample2)
2 [-]
a Indicated by indicator for crude oil after treatment (sample3)
3 [-]
a Indicated by indicator for crude oil after treatment (sample4)
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].
Chapter One Introduction
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.
Chapter One Introduction
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
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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.
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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,
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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 hydro- dynamical 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].
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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-
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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.
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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].
Chapter Two Literature Survey
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
Chapter Two Literature Survey
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]
Chapter Two Literature Survey
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).
Experimental Work Chapter Three
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).
Experimental Work Chapter Three
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).
Experimental Work Chapter Three
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.
Experimental Work Chapter Three
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).
Experimental Work Chapter Three
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.
Experimental Work Chapter Three
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).
Experimental Work Chapter Three
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
Experimental Work Chapter Three
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].
Experimental Work Chapter Three
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
Results and Discussion Chapter Four
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
Results and Discussion Chapter Four
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
Results and Discussion Chapter Four
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
Results and Discussion Chapter Four
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
Rotation Speed (rpm)
percentage increasing in API fo samples tested at 5min
percentage increasing in API fo samples tested at 10min
Results and Discussion Chapter Four
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
Rotation Speed (rpm)
Percentage increasing in API for samples tested at 5min with LABS
percentage increasing in API for samples tested at 10min with LABS
Results and Discussion Chapter Four
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(.
Results and Discussion Chapter Four
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
Results and Discussion Chapter Four
66
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 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)
Rotation Speed of Viscometer (rpm)
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
Results and Discussion Chapter Four
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).
Results and Discussion Chapter Four
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
crude oil sample1 sample 2 sample 3 sample 4
Results and Discussion Chapter Four
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.
Number of sample tested
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
Results and Discussion Chapter Four
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
Rotation Speed (rpm)
Percentage yield for samples Tested at 5min
Percentage yield for samples tested at 10min
Results and Discussion Chapter Four
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
crude oil sample1 sample 2 sample 3 sample 4
Results and Discussion Chapter Four
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
crude oil sample1 sample 2 sample 3 sample 4
Results and Discussion Chapter Four
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
)
Number of sample tested
at 5min.
Number of sample tested
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).
Results and Discussion Chapter Four
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
Rotation Speed (rpm)
Percentage yield for samples tested at 5min with LABS
Percentage yield for samples tested at 10min with LABS
Results and Discussion Chapter Four
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
Rotation Speed (rpm)
Samples at 5min Samples at 10min
Samples at 5min with LABS Samples at 10min with LABS
Results and Discussion Chapter Four
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
Rotation Speed (rpm)
Samples tested at 5min Samples tested at 10min
Results and Discussion Chapter Four
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
Rotation Speed (rpm)
Samples tested at 5min with LABS Samples tested at 10min with LABS
Results and Discussion Chapter Four
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
Rotation Speed (rpm)
Samples at 5min Samples at 10min
Samples at 5min with LABS Samples at 10min with LABS
Results and Discussion Chapter Four
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
Rotation Speed (rpm)
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
Rotation Speed (rpm)
Samples tested at 5min with LABS Samples tested at 10min with LABS
Results and Discussion Chapter Four
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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“Surfactants in Petroleum Refining Processes”, Chemistry and Technology
of Fuels Oils, Vol.33, No.1, pp. (20-21), January, (1997).
65. Szabo, J. L., and Lakatos, I., “Effect of Non-Ionic Surfactants on
Interfacial Rheological Properties of Crude Oil/Water System”, Progress in
Colloid and Polymer Science, Chemistry and Materials Science, Vol.105,
pp. (302-310), (1997).
66. Mittal, K. L., “Solution Chemistry of Surfactants”, Colloid and Surface
Science Symposium, University of Tennessee, Plenum Press, New York,
Vol.2, pp. (195-205), (1979).
67. Boukadi, A., and Amri, H., “Flow Improvement of a Waxy Crude Oil
by Chemical Additive Utilization”, Pakistan Journal of Biological
Sciences, Vol.8, pp. (1131-1136), (2005).
68. Cong, F., “Linear Alkylbenzene Sulphonic Acid”, LABSA, Dodeyle
Alkyl Benzene Sulfonic Acid, Free Press Release, January 8, (2009).
www.Free-release.com.
69. Riazi, M.R., “Characterization and Properties of Petroleum
Fractions”, 1st Edition, American Society for Testing and
Materials,pp.(135-138), (2005).
70. Baltimor, M.D., “Manual on Flash Point Standards and Their Use:
Methods and Regulations”, ASTM International, September, (1992).
References
90
71. Yen, T. F., and Lin, J. R., “An Upgrading Process through Cavitation
and Surfactant”, Energy and Fuels, vol. 7, pp. (111-118), (1993).
72. Djakovij, L. M., and Dokij, P.P., “Changes of Viscous Characteristics
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-[
Table (A.4) shows the measurement of viscosity by using rotational
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
Table (A.5) shows the measurement of viscosity by using rotational
viscometer for crude oil before and after treatment at 10 min. with
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-[
Table (A.6) shows the measurement of viscosity by using rotational
viscometer for crude oil before and after treatment at 10 min. with
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
Samples Tested at 5 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.12) Boiling points curve before and after treatment at
homogenizing time 10 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 2 140 142 145 148 162 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.13) Boiling points curve before and after treatment at
homogenizing time 5 min. at various rotation speed of RPA as shown in
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.14) Boiling points curve before and after treatment at
homogenizing time 10 min. at various rotation speed of RPA as shown in
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
Samples Tested at 10 min. in RPA
Flash Point(P
◦PC) for
Samples Tested at 5
min. in RPA
Sample Number
75
75
75
75
crude oil before treating
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.
Samples Tested at 10 min. in
RPA
Samples Tested at 5 min. in 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).
Samples Tested at 10 min. in
RPA
Samples Tested at 5 min. in 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
Samples Tested at 10 min. in RPA
Pour Point(P
◦PC) for
Samples Tested at 5
min. in RPA
Sample Number
-10
-10
-10
-10
crude oil before treating
-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
and 10 min. for samples tested at rotation speed showed in table (C.2) in
RPA.
Samples Tested at 10 min. in
RPA
Samples Tested at 5 min. in 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
and 10 min. for samples tested at rotation speed showed in table (C.2) in
RPA with (LABS).
Samples Tested at 10 min. in
RPA
Samples Tested at 5 min. in 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
Rotation Speed (rpm)
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