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Republic of Iraq

Ministry of Higher Education


& Scientific Research
University of Technology
Department of Chemical Engineering

Demulsifiers for Simulated Basrah Crude Oil


A Thesis Submitted to the Department of Chemical Engineering of
the University of Technology in Partial Fulfillment of the
Requirements for the Degree of Master of Science in Chemical
Engineering/Oil Refinery & Petrochemical Industry

By
Luma Husain Mahmood
(B.Sc. in Chem. Eng.2002)

Supervised By

Dr. Adel Sharif Hamadi

2009

"


"


)(76

Supervision's Certificate
I certify that this thesis entitled (Demulsifiers for Simulated Basrah
Crude Oil) was prepared by (Luma Husain Mahmood) under my supervision
at the chemical Engineering Department/University of Technology in partial
fulfillment of the requirements for the degree of Master of Science in
Chemical Engineering.

Signature:
Name: Dr. Adel.Sh. Hamadi
Assistant
(Supervisor)
Date: / /2009

In view of the available recommendations, I forward this thesis for Debate by the
examination committee.

Dr. Khalid A. Sukkar


Head of Post Graduate Committee
Department of Chemical Engineering
Date: / /2009

Certificate
We certify that we have read this thesis and as examining committee
the student (Luma Husain Mahmood) in its contents and that in our opinion
it meets the standard of a thesis for the degree of Master of Science in
Chemical Engineering.

Signature:

Signature:

Asst. Dr. Adel.Sh. Hamadi

Prof. Dr. Abbas H. Sulaymon

(Supervisor)

(Chairman)

Date: / /2009

Date: / /2009

Signature:

Signature:

Asst. Prof. Dr. Najat J. Saleh

Dr. Khalid A. Sukkar

(Member)

(Member)

Date: / /2009

Date: / /2009

Approved by the University of Technology

Signature:
Dr. Jamal Mane'e Ali Al-Rubeai
Acting Head of Chemical Engineering
Department
Date: / /2009

Linguistic Certification
I certify that this thesis entitled (Demulsifiers for Simulated Basrah
Crude Oil) was prepared by (Luma Husain Mahmood), under my
linguistic supervision. It was amended to meet the style of the English
Language.

Signature:
Name: Assist. Prof. Dr. Arkan Kh. Husain AL-Taie
Date:

Dedication
To
My Parents,

To My best Friends (Suzy)


&
To every one who helped me during my study
With deep respect and love

Luma
2009

Acknowledgments

Acknowledgments
Above all, praise is to Allah (SWT) who has sustained me throughout
this work.
I would like to thank my supervisor Dr. Adel Sharif
Hamadi for his guidance, advice and support.

I would like also to express my grateful migration to Dr.


Jamal Mane'e Ali Al-Rubeai, head of chemical engineering

department and also to Dr. Khalid Ajmi Sukkar the head


of post graduate committee for providing research facilities.
Special thanks are expressed to Dr. Farah Talib, Dr. Rahek
Asmeal, Ahlam Said, Rafal Ahamed, and Ahamed Algaf for their help.

I would also like to thank the chemical engineering


departments staff in the University of Technology.
Finally, I extend my grateful thanks to all who helped me.

Luma
2009

Abstract
Water in oil emulsion occurs at many stages in the production and treatment of
crude oil. The emulsion stability results from the presence of interfacial barrier
preventing coalescence of the dispersed water droplets. This is due to the presence
of polar components such as asphaltenes, resins, wax, and naphtenic acids in the
crude oil. Therefore, before transporting or refining the oil, it is essential to
separate the water for economic and operational reasons.
In the present work five demulsifirs were used (RP6000, Chimec2439, PAA, LAS
and HAS) for Al-Basrah water in oil emulsion. The experimental work was
performed under 65o

1- Demulsifier dose (10, 20, 30, 40,50,60,70 and 80) ppm.


2-Separation time (5, 10, 15, 30, 60, 90 and 120) min.
3-Types of demulsifiers (RP6000, Chimec2439, PAA, LAS and HAS).
4- Alcohols Concentration (25%, 50%, 75%, and 100%) adds into commercial
demulifiers (RP6000 and Chimec2439).
The results obtained with prepared demulsifiers (HAS, LAS and PAA) were (90
%, 88.3% and 75%), respectively. Two types of commercial demulifiers were also
used (RP6000 and Chimec2439), which gave water separation efficiency (87.5%
and 72.2%), respectively. Two types of alcohols
were used as modifier agents to

enhance the performance of demulsifiers at different mixing percentages. Methanol


and ethanol were used for this purpose and the optimum mixing percentage of
alcohols was at concentration of (25%). Methanol gave higher water separation
than ethanol, (61%) when use RP6000, (56.6%) when use Chemic2439.

II

Salt content, pH, remains of water content and density were estimated after
water separation. The minimum density obtained was (0.832 gm/cm3) at (80) ppm
of HAS, also viscosity was estimated before and after water separation. The
correlation between emulsion viscosity after water separation, shear stress and
demulsifier dose obtained is:

= 522.801 0.0548 D 0.42411 , R=93.2117 %


Also the behavior of emulsion has been checked by constructing a relationship
between shear stress and shear rate. The correlation obtained is:

= 59.0318 0.99701 , R =99.981%


Where NewtonianCbehavior
obtained and
as was
expected.
emulsionwas
temperature
water
content 30% vol (3%wt
NaCl).The parameters studied on water separation process were:-

III

List of Contents

List of Contents
Subject

Page

Acknowledgments
Abstract
List of Contents
Nomenclature

I
II-III
IV-V
VI-VII

Chapter One - Introduction


1.1 Introduction
1.2 Disadvantage of crude-oil emulsion
1.3 Demulsifiers
1.4 Aim of the work

1-2
3
3-4
4

Chapter Two - Literature Survey


2.1 Introduction
2.2 Crude Oil Emulsion Composition
2.2.1 Asphaltene
2.2.2 Resins
2.2.3 Wax
2.2.4 Finely divided Solid
2.2.5 Oil Field Brine
2.3 Crude Oil Emulsion Formations and Stability

5-6
6-7
8
9
10
11
11
12

2.3.1 Classification of Emulsions

12-13

2.3.2 Emulsion Formation

14-15

2.3.3 Emulsion Stability

15-18

2.4 Demulsification of Crude Oil Emulsion

18-19

2.5 Bottle Test


2.6 Mechanisms of demulsication process
2.7 Rhyolgy of emulsion
2.8 Demulsifiers Characteristics
2.9 Demulsifiers Classification
2.10Demulsifiers Performance
2.11 Summary

20
20-22
22-24
25-26
26-27
28-31
31

Chapter Three - Experimental Work


3.1 Introduction
3.2 Apparatus Used in Experiments
3.3 Materials
3.3.1 Crude Oil
3.3.2 Other Chemicals Used

32
32-33
33
33
34

3.3.3 Chemical Demulsifiers


3.4 Experimental Procedure

34-35
35

3.4.1 Emulsion Preparation


3.4.2 Chemical Demulsification Method (Bottle test)

35
36-37

IV

List of Contents
Subject

Page

3.4.3 Effect of RP6000 and Chimec2439(Commercial


Demulsifiers) on Water Separation Efficiency
3.4.4 Effect of Methanol and Ethanol added into RP6000 and Chimec2439
on Water Separation Efficiency
3.5 Polymerization of Acrylamide
3.6 Sulfonation of Alkylbenzene
3.7Effect of Polyacrylamide (PAA)on Water Separation
Efficiency on Water Separation Efficiency
3.8 Effect of Linear Alkylbenzene Sulfonate (LAS)and Heavy
Alkylbenzene Sulfonate (HAS) on Water Separation Efficiency
3.9 Measuring Devices
3.9.1 Evaluating Salt content
3.9.2
3.9.3
3.9.4
3.9.5

Evaluating
Evaluating
Evaluating
Evaluating

pH
the Residual Water Content
dynamic viscosity
Density

37
37
38
39-41
42
42
42
42
42
43
44-45
46

Chapter Four- Results and Discussion


4.1 Introduction

47

4.2 Effect of Demulsifiers on Water Separation Efficiency


4.3 Effect of Adding Alcohols on Water Separation Efficiency
4.4 Effect of Adding Demulsifiers Doses on Water Separation
4.5 Effect of Salt content on Water Separation
4.6 Effect of PH on Water Separation Efficiency
4.7Effect of Demulsifiers Doses on Remainder of Water Content

47-50
51-55
56
57-59
60-62
63-64

4.8 Effect of Dose on Density


4.9 Emulsion Rheology
4.10 Rheology Correlation

64-65
65-66
66

4.10.1Viscosity Correlation

66-68

4.10.2 Relationship between Shear Stress and Shear Rate

68-69

Chapter Five - Conclusions and Recommendations


5.1The Conclusions
5.2 Recommendations

References
Appendices
Appendix A
Appendix B
Appendix C

70-71
71
72-77

Nomenclatures

Nomenclatures
Symbol
a
A, B
a, b, c
k
k
m, n
N
n
R
ri
ro

Definition
The indicated by indicator in eq.(3.7)
Constants in eq.(2.5)
Constants in eq. (4.1)
Fluid consistency index in eq.(2.3)
Constant in eq. (3.7)
Constants in eq.(4.3)
Rotational speed
Power law in eq.(2.1),(2.3) and (2.4)
Correlation coefficient
Radius of inner cylinder
Radius of outer cylinder

Unit
[-]
[-]
[-]
[-]
[-]
[-]
rpm
[-]
[-]
mm
mm

Greek Symbols
Symbol
Definition

Shear rate

Angular frequency
A measure of the extend of shear

thinning in eq. (2.5)


Viscosity

Unit
sec-1
sec-1
[-]
mPa.sec

Shear stress

mPa

yield stress

mPa

VI

Nomenclatures

Abbreviations
Symbol
API
ASTM

Definition
American Petroleum Institution
American society for testing Material

BP

Boiling point (oC)

Dose

HAS

Heavy AlkylbenzeneSulfonate

LAS

Linear AlkylbenzeneSulfonate

PAA

Polyacrylamide

ppm

Part per million (mg/l)

Sp.gr.

Specific Gravity

VII

Introduction

Chapter one

Chapter One
Introduction
1.1 INTRODUCTION
Emulsion is a heterogeneous system, containing at least immiscible liquid
intimately dispersed in another in the form of droplets with a diameter, in general,
ranging between (0.1-20) microns, and it is stabilized by an emulsifying agent,
asphaltenes, resins and finely divided solids. The dispersed droplets are known as
the internal phase. The liquid surrounding the dispersed droplets is the external or
continuous phase. The emulsifying agent separates the dispersed droplets from the
continuous phase (Kenneth, 1988).
Water-in-oil emulsion is formed during the production of oil, which is often
accompanied with water.The stability of the emulsion is ranging from a few
minutes to years depending on the nature of the crude oil (Bhardwaj and
Hartland, 1998).
Crude oils consist of, in any case, a series of hydrocarbons such as alkenes,
naphtenes, and aromatic compounds as well as phenols, carboxylic acids, and
metals. A major fraction of sulfur and nitrogen compounds may be present as well.
The carbon numbers of all these components range from 1 (methane) through 50 or
more (asphaltenes). Some of these components (asphaltenes, resins, wax, and
naphtenic acids) can form films at oil surfaces. So, the tendency to form stable or
unstable emulsions of different kinds varies greatly among different oils
(Schramm, 1992).

Introduction

Chapter one

The natural petroleum emulsion resulting from the secondary production


consists of crude oil as dispersion medium and brine as dispersed phase, normally
stabilized by natural chemicals such as asphaltenes, resins, and solids such as clays
and waxes Bhardwaj and Hartland 1998. Emulsion stability is the ability of the
dispersed phase of the emulsion to resist coalescence or sticking together of
droplets. Emulsions are stabilized by the presence of a film between dispersed
droplets and the continuous phase. According to MacBain, 1950 this film is of
many molecules thick, on the other hand Fischer and Harkins, 1966 showed that
this film is only mono-molecular.
Emulsions are undesirable because the volume of dispersed water occupies
space in the processing equipment and pipelines, increased operating and capital
costs. Moreover, the characteristics and physical properties of oil change
significantly upon emulsification. The density of emulsion can increase from (800)
3

kg/m for the original oil to (1030) kg/m for the emulsion. The most significant
change is observed in viscosity, which typically increases from a few mPasec or
less to about 1000 mPasec (Fingas, et al., 2003).

Emulsion resolution is therefore an important element in handling the


petroleum, from the time it is produced until it enters the refining process. In order
to minimize the production problems related with crude oil emulsions and
environmental concerns, petroleum operators need to prevent emulsion formation
or to break it Gafonova, 2000. The treatment of water-in-crude oil emulsions
involves the application of mechanical, thermal, electrical, and chemical processes
(Grace, 1992).

Introduction

Chapter one

1.2 Disadvantage of Crude-Oil Emulsion


The main disadvantages of crude oil emulsions are Tambe and Sharma, 1993:1. Expensive pumping due to increase crude oil viscosity.
2. Corrosion of pipes and pumps.
3. Poisoning of refinery catalysts.
Practically, the breaking of crude oil emulsion consists crude oil dehydration
and crude oil desalting, since the crude oil contains salts, impurities, fine
divided solids accompanied with water dispersed in crude oil. Most harmful
materials are the salts. Generally the chloride content reaches nearly 75% NaCl,
15% MgCl 2 and10% CaCl 2 and also salts may occur as crystals, during heating,
salts solution in oil evolves hydrogen chloride and consequently produce HCl.
Even small quantities of HCl enhance the corrosion of sulfur compounds Einar
et al., 1989. Also sediments or solids in oil cause damaging, plugging, abrasion,
erosion and residual product contamination (Pet, 1983).

1.3 Demulsifiers
Chemical method of resolving crude oil emulsions are based on the addition
of reagents (demulsifiers) which destroy the protective action of hydrophobic
emulsifying agents and allow the water droplets to coalesce. There are anionic,
cationic and nonionic surfactants that have been used as demulsifiers (Selvarajan
et al., 2001).

Introduction

Chapter one

Success of chemical demulsifying method is dependent upon the adequate


quantity of a properly selected chemical that must be added into the emulsion,
through mixing of the chemical with the emulsion, adequately heat may be required
to facilitate or fully resolve an emulsion. Demulsifiers permit agglomeration,
coalescence and gravity settling of the water droplets (Staiss et al., 1991).

1.4 The aim of the present work


The following steps will be studied in this research:

1. Using commercial demulsifiers to separate water from crude oil emulsion.


2. Adding alcohols (methanol and ethanol) to commercial demulsifiers to improve
their performance.
3. Preparing different types of demulsifiers by sulfonation and polymerization
methods then use them to break (W/O) emulsion.
4. Compare between the performance of commercial and laboratory prepared
demulsifiers.
5. Investigate the effect of demulsifier type (RP6000,Chimec2439,PAA,LAS and
HAS), dose(10-80) ppm , separation time (5,10,15,30,60,90 and120) min and
modifier agent (methanol and ethanol) to break crude oil emulsion.

Literature Survey

chapter Two

Chapter Two
Literature Survey
2.1 Introduction
Emulsion of oil and water is one of many problems directly associated with the
petroleum industry, in both oil-field production and refinery environments. It is
important to develop the demulsifier formulation to solve the emulsion problems.
The aspects that are important to be studied are such as crude oil composition and
characterization, emulsion, emulsion stability, and destabilization of crude oil
emulsion (Grace, 1992).
The water and oil phases are co-produced during oil production and
transportation. The dispersion of water droplets in oil or oil droplets in water will
be formed by sufficient mixing energy from the refinery. The interfacial active
agents in the crude oil such as asphaltenes, resins and naphtenic acid may
accumulate at the water-oil interface and hinder the droplets to separate.
Among these components, asphaltenes are believed to be the major causes of
stabilizing the emulsion. This is because they tend to adsorb at water-in-oil
interfaces to form a rigid film surrounding the water droplets and protect the
interfacial film from rupturing during droplet-droplet collisions. Consequently, the
formation of particularly stable water-in-oil emulsion is facilitated (Sjoblom et al.,
1990).

Literature Survey

chapter Two

Among chemical agents are demulsifiers, which weaken the stabilizing films to
enhance droplets coalescence. The formulation of commercial demulsifiers is
largely based on empirical approaches in an attempt to get the effective agent,
which can work in shorter separation times and smaller dosages (Selvarajan et al.,
2001).

2.2 Crude Oil Emulsion Composition


Crude oil contains complex mixtures of organic composites. Its composition
can vary due to its reservoirs place of origin, depth and age. Crude oils mainly
consist of mixtures of hydrogen and carbon, with little amounts of sulphur, nitrogen
and oxygen as well as structures with incorporated metallic molecules such as
nickel, vanadium, copper and iron.
There is a broad variation in physical properties from the lighter oils to the
bitumen. For this reason, several classification systems of petroleum were proposed
based on different criteria: viscosity, density (specific gravity or API gravity), pH,
surface tension and interfacial tension Speight, 1991. Crude oil is a complex fluid
containing asphaltenes, resins and napthenic acid. Asphaltenes is the heaviest and
most polar fraction in the crude oil and is responsible for rising up the variety of
stabilization of water in oil emulsion that occurred during crude oil production
(Auflem, 2002).
The method of dividing crude oil into four major fractions: saturates (including
waxes), aromatics, resins and asphaltenes is called SARA fractionation, based on
their polarity and solubility in the solvent. The method of dividing crude oil into
these four fractions is illustrated in Figure (2.1).

Literature Survey

chapter Two

Figure (2.1): Schematic of Fractionation of Crude Oils [Auflem, 2002].

Literature Survey

chapter Two

2.2.1 Asphaltenes
Asphaltenes are dark brown to black amorphous powder and have a specific
gravity just above unity, and molar masses of (1000 to 10,000) g/gmol. Asphaltenes
has no definite melting point but decomposes when the temperature exceeds (300400) C. Many researches have shown that changing in pressure, temperature and
oil composition can cause asphaltene precipitation (Speight, 1994).
Asphaltenes comprise a major portion of the surface-active components of oil,
which contain heteroatom such as N, S and O in asphaltene. Chemically,
asphaltenes represent the pentane or hexane insoluble portion of the oil (Einar et
al., 1989).
Asphaltenes represent the crude oil components. Asphaltenes are the nonvolatile and polar fraction of petroleum that is insoluble in n-alkanes such as npentane or n-heptane. The polarity, molecular weight and aromaticity of
precipitated asphaltenes rise linearly with carbon number of n-alkane precipitant.
Figure (2.2) represents the range of heavy compounds precipitated by mixing crude
oil with n-pentane and n-heptane (Auflem, 2002).

Figure (2.2) Hypothetical diagram representing the molecular characteristics of the


Asphaltenes precipitated from Petroleum by n-alkane addition [Auflem, 2002].

Literature Survey

chapter Two

2.2.2 Resins
Resins are black or dark brown semi solid, have a specific gravity near unity,
molar mass ranging from (500 to 2000) g/gmol and very adhesive materials. The
content of resin in crude oils ranges from (2- 40) wt%. The content of resin in crude
oil is higher compared to asphaltenes composition (Gafonova, 2000).

The resins are defined as the non volatile and polar fraction of crude oil that is
soluble in n-pentane, n-heptane and aromatic solvents such as toluene but are
insoluble in methanol and propanol. The resin fraction consists of carbon,
hydrogen, oxygen, nitrogen and napthenic acids. The content of these elements in
resin of various crude varies over a narrow range (Speight, 1991).

It is generally believed that resin molecules are composed of a highly polar end
group, which may incorporate sulfur, oxygen or nitrogen, and a long non-polar end
group. Nitrogen is present in resins in the form of pyrolle and indole groups.
Infrared spectroscopic data indicated the presence of ester, ketone and acid
functional groups. Sulfur is present in the form of cyclic sulfides (Gafonova,
2000).

Literature Survey

chapter Two

2.2.3 Wax
Waxes are high molecular weight alkanes. A sensible description of wax is
anything with a waxy feel and a melting point above body temperature and below
the boiling point of water. Wax is a solid crystalline mixture of straight-chain
(normal) hydrocarbons ranging from C 20 to C 30 and possible higher. Actually, the
natural waxes are mixtures of esters and frequently contain hydrocarbon Becker,
2005. Possibly undissolved (crystalline) wax dose play some role in emulsion
stability (Salager, 1990).
Emulsion stability increases as the wax crystallites increase in crude oil and
decreases when they are dissolved. The wax crystallites aggregate to a size nearly
50 m in diameter. As the temperature increases, the wax gradually dissolves until
a temperature (nearly 60 oC) is reached at which all wax is in solution as shown in
Fig (2.3).This may increase the separation efficiency of water from oil (Menon and
Wasan, 1988).

WAX CRYSTALLINITY
RECORDER OUTPUT [mV]

40

30
Series1

20

10

0
0

20

40

60

80

100

TEM PERATURE( C)

Figure (2.3) Crystalline Wax Dissolution vs. Temperature [Wasan, 1988].

10

Literature Survey

chapter Two

2.2.4 Finely Divided Solids


Asphaltenes that precipitate from bitumen contain some other insoluble material
referred to as solids. These finely divided solids such as sand, wax crystals and
clay particles can stabilize emulsions. The recent studies of Isaac and Chow, 1992
demonstrated that solids prevent thinning of the thin film and this caused the crude
oil film to be so persistent.

According to Pekdemir et al., 2003, the role, which solids play in stabilizing
emulsion is affected by the size of the solids. The presence of finely divided solids
in processes involving the contact of oil and water often results in the formation of
solids-stabilized emulsions. In petroleum recovery operation, solids-stabilized
(W/O) emulsions are formed naturally due to the intimate mixing of oil, water and
mineral fines (Menon and Wasan, 1988).
.

2.2.5 Oil Field Brine


Binks, 1993 stated that (O/W) droplets increase in size solubilizing more with
increasing salt concentration while (W/O) droplets decrease in size. At low and
high salt concentrations, the monolayer constrained to lie at the flat interface has a
preferred tendency to curve and increase the tension. At intermediate
concentrations, the tension is less because the flat monolayer has no tendency to
curve.

11

Literature Survey

chapter Two

2.3 Crude Oil Emulsion Formations and Stability


2.3.1 Classification of Emulsions
An emulsion is usually defined as a system in which one liquid is relatively
distributed or dispersed, in the form of droplets, in other substantially immiscible
liquids. The emulsion formation is a result of the co-production of water from the
oil reservoir. During processing, pressure gradients introduce sufficiently high
mechanical energy input (shear forces) to disperse water as droplets in the oil
phase. The dispersed phase is sometimes referred to as the internal phase, and the
continuous as the external phase (Aske, 2002).

In the petroleum industry the usual emulsions encountered are water droplets
dispersed in the oil phase and termed as water-in-oil emulsion (W/O), conversely,
if the oil is the dispersed phase, it is termed oil-in-water (O/W) emulsion. In
addition to the usual emulsion types, multiple emulsions for instance, water
droplets dispersed in oil droplets that are in turn dispersed in a continuous water
phase (W/O/W) can occur. Figure (2.4) shows the three simplest kinds of this
emulsion (Paul, 2001).

12

Literature Survey

chapter Two

Figure (2.4) Common Types of Crude Oil Emulsions: Oil-in-Water (O/W), Water-in-Oil (W/O),
and less common: Water-in-Oil-in-Water (W/O/W), [Paul, 2001].

The type of emulsion that is formed depends upon a number of factors. If the
ratio of phase volume is very large or very small, then the phase having the smaller
volume is frequently the dispersed phase and the emulsion type depends more on
the nature of the emulsifying agent, so that the phase which an emulsifier is more
soluble constitutes the continuous phase (Hanapi, 2006).

13

Literature Survey

chapter Two

2.3.2 Emulsion Formation


According to Fingas, 2004, there are three main criteria that are necessary for
formation of crude oil emulsion:
1. Two immiscible liquids must be brought in contact.
2. Surface active component must be present as an emulsifying agent.
3. Sufficient mixing or agitating effect must be provided in order to disperse one
liquid into another as droplets.

The pressure gradient or velocity gradient required for emulsion formation is


mostly supplied by agitation. The large excess of energy required to produce
emulsion of small droplets can only be supplied by very intense agitation, which
needs much energy. A suitable surface active component can be added to the
system in order to reduce the agitation energy needed to produce a certain droplet
size. The formation of surfactant film around the droplet facilitates the process of
emulsification and a reduction in agitation energy by factor of 10 or more can be
achieved Becker, 2005. Water-in-oil emulsion will be formed when crude oils are
mixed with sea water (which have their natural brine, NaCl) and produce droplets
of water dispersed in the oil as shown in figure (2.6) (Lee, 1999).

14

Literature Survey

chapter Two

Figure (2.6) Formation of Water-in-Oil Emulsion [Modified from Lee, 1999].

2.3.3 Emulsion Stability


Stability is widely used to refer to the persistence of an emulsion in the
environment, and has been identified as an important characteristic of water-in-oil
emulsions. Some emulsions quickly decompose into separate oil and water phases
once removed from the sea surface, while more stable emulsions can persist for
days to years. Recent work indicates that the viscosity of an emulsion is related to
its stability (NRT Science & Technology Committee, 1997).

15

Literature Survey

chapter Two

Stability is a consequence of the small droplet size and the presence of an


interfacial film on the droplets in emulsions, which make stable dispersions. That is
the suspended droplets do not settle out or float rapidly, and the droplets do not
coalesce quickly. According to Schramm,2007 the definition of emulsion stability,
it is considered against three different processes; creaming (sedimentation),
aggregation and coalescence" as shown in Figure (2.5).

Figure (2.5) Processes Taking Place in an Emulsion Leading to Emulsion Breakdown and
Separation [Auflem, 2002].

16

Literature Survey

chapter Two

According to NRT Science & Technology Committee, 1997, emulsion can be


categorized into stable, unstable and meso-stable emulsions according to stability:

Stable emulsions will persist for days, weeks and longer. In addition, stable
emulsion will increase with viscosity over time. Increasing alignment of
asphaltenes at the oil-water interface may cause increasing of viscosity.

Unstable emulsions usually persist for only a few hours after mixing stops. These
emulsions are ready to separate into oil and water due to insufficient water particle
interactions. However, the oil may retain small amounts of water, especially if the
oil is viscous.

Meso-stable emulsions are probably the most common emulsion that was formed
in the fields. These emulsions can be red or black in appearance. This emulsion has
the properties between stable and unstable emulsions. It is suspected that these
emulsions contain either insufficient asphaltenes to render them completely stable
or contain too many destabilizing materials such as smaller aromatics. The
viscosity of the oil may be high enough to stabilize some water droplets for a
period of time. Particles, which are water-wet, tend to stabilize (O/W) emulsions
while those oil-wet tend to stabilize (W/O) emulsions (Auflem, 2002).

17

Literature Survey

chapter Two

There are two factors that affect the emulsion stability stated by Kim, 1995:
Viscosity: The application of heat and the addition of demulsifiers can
reduce the viscosity. As the results, the rate of water droplets settlement and
the mobility of water are increased and lead to collisions, coalescence, and
further increase in the rate of separation.

Density difference: Heat application to the emulsion will decrease the


density of the oil at a greater rate than that of water and thus allows more
rapid settling of the water. This is because the difference in densities of the
two liquid phases may be increased. Dehydration of heavier oil is typically
more difficult compared with light oil, as its density is closer to that of
water.

2.4 Demulsification of Crude Oil Emulsion


Crude oil is found in the reservoir in association with gas and saline formation
water. The number of wells now co-producing water with crude oil is steadily
increasing, these immiscible fluids are readily emulsified by the simultaneous
action of pressure drop at the well head (Bhattacharyya, 1992).
Demulsification or emulsion breaking of water-in-crude oil emulsion is carried
out by using either four methods such as mechanical, thermal, chemical and
electrical Gafonova, 2000. The knowledge of the properties and characteristics of
the emulsion and the mechanisms that are taking place during coalescence of water
droplets are required for fast separation (Ese et al., 2006).

18

Literature Survey

chapter Two

There are many kinds of mechanical separation tools that are typical
equipment used in destabilization the crude oil emulsion such as cyclones,
gravity settling tanks, centrifugal separators and many materials had been
suggested to be used as porous coalescers such as fiberglass, glass, Teflon.
Other materials such as clay, magnesium silicate, or silica gel had been
used as a filter aid in conventional filter press (Auflem, 2002).
Thermal method is carried out by the addition of heat to enhance emulsion
breaking in oil field. An increase in temperature above the paraffin melting
point ranging between (50-65) C may completely destabilize an emulsion.
So, the optimum operating temperature at refinery is (65) C. The
application of heat alone is insufficient to break emulsion and often require
the addition of chemicals (demulsifires) (Grace, 1992).
Electrical method is the principle of electrostatic dehydration in
demulsification for oil-field production. This process does not typically
resolve emulsions completely by itself, although it is an efficient and often
require the addition of chemicals or heat (Grace, 1992).
Chemical demulsification is the most widely applied method of treating
water-in-oil and oil-in-water emulsions and involves the use of chemical
additives (demulsifiers) to accelerate the emulsion breaking process. The
stability of emulsions is largely affected by the nature of the interface/film
and surfactant adsorption mechanisms. The most common method of
demulsification in both oil-field and refinery application is the combination
of heat and application of chemical design to neutralize and eliminate the
effects of emulsifying agents (Grace, 1992).
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2.5 Bottle Test


The method of determining relative emulsion stability for lab-scale is the
simple bottle test. The bottle test is an empirical test in which varying amounts of
potential demulsifiers are added into a series of tubes or bottles containing sub
sample of an emulsion to be broken. After some specific time, the extent of phase
separation and appearance of the interface separating the phases are noted (Auflem,
2002).
Success of chemical demulsifying method depends upon the following:
1. An adequate quantity of a properly selected chemical must enter the emulsion.
2. Thorough mixing of the chemical in the emulsion must occur.
3. Sufficient heat may be required to facilitate or fully resolve an emulsion.
4. Sufficient residence time must exist in treating vessels to permit settling of
demulsified water droplets.

2.6 Mechanism of demulsification process


Chemical demulsification is a dynamic process since it is a phenomenon that
occurs under non- equilibrium conditions. This demulsification activity promotes
coalescence of the water droplets in the emulsion, which in turn causes separation
of water and lowering of viscosity. Since the stability of emulsions can be traced to
the presence of surfactant films at the water/oil interface, the rupture of the thin
film separating droplets in a water-in-oil emulsion is affected primarily by the
demulsifier. The role of the demulsifier is the suppression of the interfacial tension
gradient in addition to the lowering of interfacial viscosity, thus causing accelerated
film drainage and coalescence (Fiocco, 1999).

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Demulsifiers are very similar to emulsifiers because both are surfactant in


nature. Consequently, the action of the demulsifier in emulsion breaking is to
unlock the effect of the emulsifying agents present. This unlocking is
accomplished in two fundamental steps, which are flocculation and coalescence
(Leopold, 1992).
Flocculation is the first action of the demulsifier on an emulsion. It involves a
joining together of flocculation of the small water droplets. When magnified, the
flocks take on the appearance of bunches of fish eggs. If the emulsifier film
surrounding the water droplets is very weak, it will break under this flocculation
force and coalescence will take place without further chemical action.
Coalescence is the rupturing of the emulsifier film and the uniting of water
droplets. Once coalescence begins, the water droplets grow large enough to settle
out. Figure (2.7) shows the level of demulsification of water in oil emulsion (Kim,
1995).

Figure (2.7) The Level of Demulsification Process of Water in Oil Emulsion (Separation of
Water from Water in Oil Emulsion) [Kim, 1995].

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Ese et al., 2006 showed that the kinetics of chemical demulsification process is
caused by three main effects:
1. The displacement of the asphaltenic film from the (water/oil) interface by the
demulsifier.
2. Flocculation.
3. Coalescence of water droplets.
Bhardwaj and Hartland, 1998 summarized in their work that a lowering of
interfacial tension and adsorption of demulsifier at the crude oil/water interface is
necessary, but not a sufficient condition for an effective demulsifier. More
important characteristics of a good demulsifier are sufficient surface pressure and
good partition between the water phase and oil phase.

2.7 Rheology of Emulsions


The viscous water in oil emulsions formed are undesirable as they not only
cause serious processing problems but also lead to significant cost increases for
pumping, transportation (Pekdemir, 2003).
Six factors which may affect the rheological properties of emulsion described in
(Becker, 2005), are:

1. Viscosity of the external (continuous) phase.


2. Volume concentration of the dispersed phase.
3. Viscosity of the internal (dispersed) phase.
4. Nature of the emulsifying agent and the interfacial film formed at the
interface.
5. Droplet size distribution in the continuous phase.
6. Shear rate.
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Rheology is usually defined as the science of deformation and flow properties.


One of the important rheological parameters characterizing the properties of
emulsion is the viscosity. The most emulsions show more complex (nonNewtonian) flow behavior. In non-Newtonian systems, viscosity is a function of
the shear rate (i.e. a series of different viscosity values can be obtained by
measurement on the some liquids). Thus, it is most inaccurate to refer to these
measurements as liquid viscosity; the very useful designation "apparent viscosity"
is widely used. The other most important factor on the viscosity of emulsion is the
presences of surface- active materials which influence also the other mechanical
properties of the (W/O) interface (Becker, 2005).
Emulsions exhibit various types of flow properties depending on fluid type, they
are, (Wilson, 2001):
Newtonian Model : If the viscous shear stress and the shear rate are linearly
related by
= - du/dr , n=1 ..... (2.1)
Where: n represents the power law
Bingham plastic: Bingham plastics satisfy a slightly modified constitutive
relationship, usually written in the form
= y - du/dr.............................................(2.2)
Where: y represents the yield stress of the fluid.
Power law fluids: These fluids, without yield stress, satisfy the power law
Model in the following Equation
= k (- du/dr) n . (2.3)
Herschel-Bulkley fluids: This model combines power law with yield stress
characteristics
= y + k (- du/dr) n.. (2.4)
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Ellis fluids: Ellis fluids satisfy a more complicated constitutive relationship


= - du/dr / (A + B 1).................................... (2.5)
Where: and B are constants
Dozens of additional rheological models appear in the literature Wilson, 2001
typical qualitative features of the associated velocity profiles are shown in Figure
(2.8).

Figure (2.8) Typical Non-Newtonian Velocity Profiles [Wilson, 2001].

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2.8 Demulsifiers Characteristics


Demulsifiers are molecules that aid the separation of oil from water usually at
low concentrations. They prevent formation of water in oil mixture. The structures
of demulsifiers are not easily categorized as emulsifiers. Some demulsifiers are
polymers, others have structures similar to non-ionic emulsifiers. Demulsifiers are
surfactants that are important in breaking the emulsion system (Aske, 2002).
The best demulsifiers are one that can reduce the interfacial shear viscosity
increases the interfacial mobility and destabilizing the water-oil emulsion. To
ensure the high quality performance, a demulsifier should posses the following
characteristics (Krawczyk et al., 1991):

The demulsifier should be able to partition into the water phase and oil phase.
Dissolved in the oil phase.
The concentration of the demulsifier in the droplet must be sufficient to ensure a
high enough diffusion flux to the interface.
The demulsifier must be high enough to suppress the interfacial tension gradient,
thus accelerating the rate of film drainage hence promoting coalescence.

Since demulsifiers are surfactants, understanding the role of demulsifiers as


surface active agents is very important. Basically, there are two groups in the
demulsifier molecule; hydrophobic (water disliking) group and a hydrophilic group
(water liking group) Ariany, 2003. A demulsifier molecule can be shown as in
Figure (2.9)

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The hydrophilic effect is referred to the water-preferring nature of species


(atom, molecule, droplet and particle). Hydrophilic usually means that a species
prefers the aqueous phase rather than the oil phase.
The hydrophobic effect is referred to the water-avoiding nature of a species
(atom, molecule, droplet, and particle). Hydrophobic usually means that a
species prefers the oil phase to the aqueous phase (Ese, 2006).

Ahydrophobic part- water disliking

Ahydrophilic part water liking

Figure (2.9) Demulsifier Particle Structure [Porter, 1994].

2.9 Demulsifiers Classification


There are three types of demulsifiers that are used to break the crude oil
emulsion. They are anionic, nonionic and cationic Porter, 1994:

1. Anionics are used in practically every type of detergents, which are the main
application of demulsifiers. This is because they are easy to produce and have low
manufacturing cost. Anionics are manufactured and used in greater volume
compared to the other types of demulsifiers.

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The surface-active part of the anionics molecule carries a negative charge and has
a long chain hydrophilic carrying the negative charge. The anionics have the
advantage of being high and stable foaming agents; however, they do have the
disadvantage of being sensitive to minerals and the presence of minerals in water
(water hardness) or pH changes.

2. Nonionic demulsifiers are surfactants that do not have a charged group. Nonionic
surface-active agents have a hydrophobic/hydrophilic balance where there is
neither a negative nor a positive charge in either part of the molecule, thus giving it
the nonionic terminology.
These surface-active agents have the advantage that they are not affected by
water hardness or pH changes as the anionic and cationic demulsifiers

and in

many cases it is an advantage that they are considered medium to low foaming
agents. It is especially advantageous when a very low foaming surface-active
agent is required.

3. Cationic demulsifiers: demulsifiers that carry a positive charge on the active


portion of the molecule. Cationic surfactants play an important role as antiseptic
agents in cosmetics, as general fungicides and germicides. Basically cationic are
classified as follows:
Amine salts (primary, secondary and tertiary).
Quaternary ammonium compounds.

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2.10 Demulsifiers Performance

Different types of demulsifiers will give different ways in demulsification


process. Knowledge of formation and stability of crude oil emulsions, types of
demulsifiers, demulsification mechanisms and are very important since it can be
useful in the demulsification process of crude oil emulsions. Thus, it is frequently
observed in studies of parameters that can affect the formation of stability of the
crude oil emulsion.

The parameters that are being identified to affect demulsifiers performance are:

1. Temperature: The suitable temperatures considered for demulsification process


for lab-scale are between 50 to 70C, which are similar to the dehydration
processes in the actual refinery process. The interfacial viscosity of the internal
phase will decrease with increasing of the temperature. This is because the rate of
film drainage is increased proportional to the temperature. The momentum between
two water droplets will increase before coalescence is occurred. The two phases of
immiscible liquids will be separated due to the different density among them
(Grace, 1992).

2. pH: The oil-in-water emulsions are preferential at low pH value ranging between
4 to 6, while water-in-oil emulsions are favored at high pH values that are between
pH 8 to 10. Tambe and Sharman, 1993 showed that the stability of oil-in-water
emulsion formed increased as pH was increased from 4 to 6, but further increasing
in pH, from 6 to 8 and finally 10 resulted in formation of relatively less stable oilin-water emulsions and more stable water-in-oil emulsions.
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Chemical method of resolving crude oil emulsion are based on the addition of
reagents (demulsifiers) which destroy the protective action of hydrophobic
emulsifying agents and allow the water droplets to coalesce. Table (2.1) lists briefly
the chemicals used as demulsifiers since the beginning of the century (Schramm,
1992).
Table (2.1) the development of Chemical demulsifiers (Aamir, 1998; Selvarajan
et al., 2001 and Hanapi, 2006).
Year

Demulsifiers

1930-1940

Soap, naphtenic acid salts and alkylaryl sulphonate,


sulphated caster oil
Petroleum sulphonates, derivatives of sulpho-acid
oxidized caster oil and sulphosucinic acid ester

1940-1950

Fatty acids, fatty alcohols, alkyl phenols

1950-1960

Ethylene oxide/propylene oxide copolymer, Alkoxylated


cyclic alkyl phenol formaldehyde resins

1960-1970

Amine alkoxylate

1970-1980

Alkoxylated cyclic p-alkyl phenol formaldehyde resins

1980-1990

Polyester amine and blends

1920-1930

1998

Sodium silicat, sodium hydroxide, phenol

2006

Acrylic acid anhydrous, Methacrylic acid, Butyl acrylate

Dodd, 1954 concluded that the demulsifiers that be soluble in both phases are
effective in breaking crude oil emulsions, provided that very small amounts of
hydrochloric or Sulfuric acid are also added. He suggested the use of Phenol and
Sulfuric acid.

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De Groote, 1954 suggested that the effect of demulsifying agent, which usually
contains both hydrophobic and hydrophilic group, is to form with the
predominantly hydrophobic emulsifying agent an adsorption complex which is
hydrophilic, or at least water-wet.
Salager, 1990 showed that, the most effective mechanism for destabilization of
an (O/W) or (W/O) emulsion is removal of the surfactant from the water oil
interface by trapping of the former in a micro emulsion. He also pointed out that,
the physical and chemical phenomena involved in dehydration processes can be
interpreted by simulating both the surfactant which occurs naturally in the crude oil
and the addition of a chemical demulsifiers, to produce extremely unstable
emulsions.
Sjoblom et al., 1990 investigated two synthetic (W/O) emulsion model
systems and real crude oil emulsions. They made a qualitative comparison in
describing the interaction between demulsifiers and these model interfaces. They
found that, the best individual destabilizers are fatty amines, followed by fatty
alcohols, and the highest destabilizing efficiency is obtained when combining a
fatty acid and amine. From the comparison between the destabilization behavior of
the model systems and true crude oil has obvious similarities and also distinct
dissimilarities. Staiss et al., 1991 presented a new emulsion breaker (demulsifier),
generally polyester amines. Their advantages over classic demulsifiers are more
complete migration to the interface, improved emulsion breaking and coalescence,
improved water quality and partial corrosion inhibition. They also observed that the
advantages of the combination of the new demulsifiers with classic emulsion
breakers.

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Aamir, 1998 showed that the mixture of phenol and sulfonic acid was the best
chemical additive used to separate water from the crude oils.
Al-Shamrani et al., 2003 used dissolved air flotation process to remove the oil
from wast water. They stated that the coagulation and flocculation are very
important as pre-treatment steps for dissolved air flotation in order to increase the
oil recovery of the proceed. The use of inorganic coagulant such as aluminum
sulphate enhanced the separation process.
Hanapi, 2006 investigated that the combination of oil soluble demulsifiers and
water-soluble demulsifiers produced great result in water separation. He also
observed that the formulation demulsifiers is better than other commercial
demulsifier.

2.11 Summary
Emulsion problems in crude oil production and processing have gained serious
consideration either from fundamental and practical aspects by oil companies as
well as researchers for the last few decades. One of the focuses on developing
effective demulsifiers, which involves preparation, testing and demulsification
study of crude oil demulsification process. This study will address some of the
fundamental and practical aspects of these areas of interest. In the present work,
demulsifiers RP6000 and Chimec2439 (commercial), and preparation ( LAS, HAS,
and PAA) are used to separate water from crude oil and to study their effect on oil
viscosity, density, salt content, remained water content and pH measurement.

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Chapter Three
Experimental Work
3.1 Introduction
This chapter includes the details of experimental work of the present study.
The target is to experimentally investigate the effect of demulsifier type, dose and
separation time and modifier agent to break crude oil emulsion. Five demulsifiers
have been used; two commercial types (RP6000 and Chimec2439) and the other
prepared (PAA, LAS and HAS). Chemical method will be considered to break
crude oil emulsion. Water separation efficiency, Oil-phase viscosity, density,
remained water content in (W/O) emulsion, salt content in (W/O) emulsion and pH
were measured.

3.2 Apparatus Used in Experiments


The equipment used were:
1. Water bath with temperature controller type (Haak-G and Haak-D) made in
Germany.
2. Water bath type (Gerhardt Bonn EV2) connects with thermocouple.
3. Batch reactor with stirrer.
4. Electrical mixer with standard turbine impeller type (RL10 M 24684). The mixer
calibrated using Dual Digital Tachometer (DT-2268) made in Germany.
5. Electronic balance type (Ntrols mod. Mark 2200) with 0.05g accuracy.
6. Digital pH meter type (90 Metrohm AG CH -9100 Herisau) with accuracy
( 0.01).
7. Conductivity meter type (YK-43CD).
8. Clock timer.
.
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Experimental work

chapter three

9. Thermometer.
10. Cylinders (10 ml) and Beakers (100 ml).
11. Separator funnel.
12. Burette.
.

3.3 Materials
3.3.1 Crude Oil
Experimental work was carried out on sample of Basrah crude oil. The physical
properties of crude oil are given in Table (3.1) analyzed in Daura refinery.

Table (3.1) Physical Properties of the Basrah crude oil (Daura refinery).
Property
Sp.Gr. at 15.6oC
API
Salt content (%wt.)
Water and Sediment
content (%vol.)
Asphaltene (%wt.)
Ash content (%wt.)
Sulfur content (%wt.)
Viscosity (cp) at 20oC
Conductivity (mS)

33

Basrah Crude Oil


0.8849
28.4
0.0006
0.05
2.22
0.0151
2.1
50
0

Experimental work

chapter three

3.3.2 Other Chemicals Used


The chemical Materials that were used in experimental work are listed in Table
(3.2).

Table (3.2) Properties of Chemical Materials


Substance

Formula

Molecular Specific
Melting Supplier Purity%
Weight Gravity* Point(oC)

Methanol

CH3OH

32.04

0.792

B.D.H

99.9

Ethanol

C2H5OH

46.069

0.7180

G.C.C

99.9

Toluene

C6H5CH3

44

0.866

G.C.C

Sulfuric
acid
Sodium
Hydroxide

H2SO4

98.08

1.84

10.49

NaOH

40

2.13

318.4

Reidel
dehaen
Farak

Acrylamide

CH2:CHCONH2

71.08

1.122**

84-5

persulfate
Potassium

K2S2O8

270.32

2.477

D.<100

Thomas
Baker
Fluka

98
100
100
100

* Specific gravity at 20 oC, ** at 30 oC

3.3.3 Chemical Demulsifiers


Five demulsifiers used in present work are:

1. RP6000 (commercial) and the chemical composition of this demulsifier is not


known .The PERTROLITE Company adopted this demulsifier in desalting process
in East Baghdad oil field.

2. Chimec2439 (commercial), which is a blend of non-ionic oil soluble surfactants


and the physical properties given from (CHIMEC S.P.A, Italy) Company, are given
in Table (3.3):
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Experimental work

chapter three

Table (3.3) Physical Properties of Chimec2439 (CHIMEC S.P. Company, Italy).


Appearance

Brown liquid

Sp.Gr.at 20 oC

0.940.02

Viscosity at 20 oC (cp)

<50

Pour point oC

<-30 oC

Flash Point oC

>62 oC

3. PAA (prepared by polymerization method).


4. LAS and HAS (prepared by sulfonation LAB and HAB where brought from

ARADET Company, Iraq), are given in Table (3.4):


Table (3.4) Properties of LAB and HAB (ARADET Company, Iraq).
Substance

Molecular

Density at

Viscosity at

Flash point

Weight

20 oC

20 oC

Linear Alkyl benzene

242

0.8573

7.7

145

LAB
Heavy Alkyl benzene

0.8825

95

188

HAB

3.4 Experimental Procedure


3.4.1 Emulsion Preparation
In this study, the brine solution was used in preparing the emulsion system. The
brine solution was prepared by dissolving (3) gm NaCl in (100) ml water in order
to obtain the required salinity similar to crude oil field. The emulsion was prepared
by adding water 30% vol. (3% wt. NaCl) to the crude oil at room temperature. The
emulsification was carried out by using a mixer at a speed of (5000) rpm for (60)
min to get a stable emulsion.

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Experimental work

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3.4.2 Chemical Demulsification Method (Bottle test)


The demulsification tests have been performed on emulsion based blend of
Basrah crude oil, which was a good representative of a crude oil giving rise to
stable emulsion at room temperature since it has high asphaltene content
(2.22wt%). The demulsifiers were tested by using bottle test method Lissant, 1983.
Figure (3.1) shows the laboratory equipment used in the experimental work in
separation water process. The purpose of this testing process is to test the
effectiveness of demulsifiers in breaking crude oil. The following procedure was
followed:
To four beakers (100ml) filled with the (W/O) emulsion samples,
demulsifier or chemical compound was added in different doses (1080)ppm to the contents of the beakers.
A series of four condensers were joined with water bath. The water was
pumped from the reservoir tank at 65 oC into condensers, at the same time
the contents of the beakers were added to the condensers to separate water
from crude oil emulsion at different time intervals such as (5,10,15,30,60,
90 and 120)min.

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Experimental work

chapter three

Figure (3.1) Water Separation Equipment

3.4.3 Effect of RP6000 and Chimec2439 (Commercial) Demulsifiers


on Water Separation Efficiency
In this set of experiments, the effect of RP6000 and Chimec2439 (commercial)
was investigated. The (W/O) emulsion has been prepared at the following
conditions temperature (65)oC, water content 30% vol. (3% wt. NaCl). The doses
of these compounds were (10, 20, 30, 40, 50, 60, 70 and 80) ppm.

3.4.4 Effect of Methanol and Ethanol added into RP6000 and


Chimec2439 on Water Separation Efficiency
In this set of experiments, the effect of methanol and ethanol concentrations
added to RP6000 and Chimec2439 was investigated. The concentrations studied for
both Methanol and Ethanol were (25, 50, 75, and 100%).
Where M= 4:1 methanol to water ratio.
E= 4:1 Ethanol to water ratio.
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Experimental work

chapter three

3.5 Polymerization of Acrylamide


Polymerization of acrylamide takes place in distilled water. The acrylamide
monomer and a small amount of the initiator (persulfate Potassium) at (70)oC and
(15) min that react to form the polymer (equation 3.1). This corresponds to the use
of acryl amide as a water thickener, although the solution becomes dense Robert
A, 1999. Figure (3.2) Shows the laboratory equipment used in polymerization
process.
n H2C CH
C O
NH2
A.A

K2S2O8
70oC

CH2 CH n .....(3.1)
C O
NH2
P.A.A

Figure (3.2) Equipments Used in Polymerization Process

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Experimental work

chapter three

3.6 Sulfonation of Alkylbenzene


It is required to sulfonate alkyl benzene using sulfuric acid (H2SO4 conc. 9598% vol.) as sulfonating agent to produce sodium alyklbenzene sulfonate which is
the pave for production of solid detergent De Groot, 1991. Figure (3.3) shows the
equipment used in sulfonation process and Figure (3.4) shows the block diagram of
sulfonation process.
The procedure of preparation is:
1. (195) gm of sulfuric acid (conc. 98% vol.) is added to (130) gm alkyl benzene
with continuous mixing (use water bath to control the heat of sulfonation
conversion and maintain the temperature at about 55oC, the time of reaction was
one hour.

2. Distilled water is added carefully with mixing so the temperature should not
exceed 60 oC.

3. The reaction mixture is placed in separating funnel for two hours. The mixture
was separate into two layers. The upper was the sulfonating layer while the lower is
the spent acid layer.

4. The sulfonated product is neutralized with NaOH (5N) solution under control
temperature (55oC).

39

Experimental work

chapter three

The reaction for production detergents are:


1. Alkylbenzene sulfonation:R
+ H2SO4

50oC

SO3H + H2O ....................(3.2)

2. Neutralization reaction:-

SO3H + NaOH

55oC

SO3Na + H2O

(3.3)

Figure (3.3) Equipments Used in Sulfonation Procedure

40

Experimental work

chapter three

H2SO4 conc. (98%)


Wt. =195 gm
LAB, HAB
Wt. =130 gm
Reactor with stirrer
(50-55) oC, (1 atm),
one hour

Washing (30-40) oC

Unreact acid
Unreact A.B
H2O
Wt. = 217.3gm
Vol. = 140 ml

H2O
V=80 ml

Separator
A.B.S acid
Wt. = 179.7 gm
Vol. = 180 ml

Neutralization

(5N)NaOH
V= 113 ml

Surfactant

Figure (3.4) Block Diagram of Sulfonation Process

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Experimental work

chapter three

3.7 Effect of Polyacrylamide (PAA) on Water Separation Efficiency


The experiments were conducted to investigate the effect of PAA on the
separation of water from the Basrah crude oil emulsion. The doses studied for PAA
were (10, 20, 30, 40, 50, 60, 70 and 80) ppm.

3.8 Effect of Linear Alkylbenzene Sulfonate (LAS) and Heavy


Alkylbenzene Sulfonate (HAS) on Water Separation Efficiency
In this set of experiments, the effect of LAS and HAS on the separation of water
from the Basrah crude oil was investigated. The doses studied for both LAS and
HAS were (10, 20, 30, 40, 50, 60, 70 and 80) ppm.

3.9 Measuring Devices


3.9.1 Evaluating Salt Content
The salt content in the crude oil has been measured using calibrated
conductivity meter. The calibration curve for giving salt concentration was shown
in Appendix (A).

3.9.2 Evaluating pH
The acid function of water separated from (W/O) emulsion has been measured
using pH meter type (90 Metrohm AG CH -9100 Herisau) with accuracy ( 0.01)
and calibrated with buffer solution having pH (4, 7 and 9).

42

Experimental work

chapter three

3.9.3 Evaluating the Residual Water Content


The residual water content in the (W/O) emulsion after breaking emulsion has
been evaluated using Dean-Stark method as shown in the Figure (3.5). The
apparatus consists of a round bottom flask of capacity (500) ml connected to a
liebig condenser by a receiving tube of capacity. The following procedure was
followed:
1. Measure (25) ml of sample.
2. Added (25) ml of pure toluene.
3. Heating the mixture to the BP. of the solution, to distilled the water with
toluene, then heated gently (decreasing the heating temperature gradually),
with proceeding distillation process.
4. The process processed until the water removed.
The residual water content can be calculated as follow (Francis and Peters,
1980):

%Water =

Volume of Water
Volume of Sample

100

. (3.4)

Figure (3.5) Water Content Equipment


43

Experimental work

chapter three

3.9.4 Evaluating Dynamic Viscosity


After the formation of the water in crude oil emulsion and breaking emulsion,
the next step was evaluating the viscosity of the emulsion before and after water
separation using rotational viscometer (model NDJ-4), to measure viscosity
Dynamic at room temperature. Before taking the measurement, the calibration of
viscometer was checked with laboratory standard viscosity oil. The viscometer was
thoroughly cleaned between measurements of samples. This apparatus has four
rotational low speeds (0.3, 0.6, 1.5 and 3) rpm and four rotational high speeds (6,
12, 30 and 60) rpm. An electrical motor drives the rotor. The viscosity (scale
reading) is determined, from the rotational speed Bird et al., 2002. This instrument
consists of two cylinders, the inner is rotates and the outer is fixed as shown in
Figure (3.6). The Sample of viscosity and shear stress calculation is described in
Appendix (C).

Figure (3.6) Viscosity Measuring Device


44

Experimental work

chapter three

The rotational viscometer has dimensions as follows:

ri=radius of inner cylinder=18.8mm


ro=radius of outer cylinder=36.2mm

= 2N / 60 .. (3.5)
Where:
= angular frequency (Sec-1)
N= rotational speed (rpm)

r2
r2 ri 2 (3.6)

Where:

= Shear rate (Sec-1)

= ak

.. (3.7)

Where:

= Viscosity (mPa.sec).
a= is the indicated by indicator,

K= Constant.

.. (3.8)

Where:

= Shear stress (mPa).

45

Experimental work

chapter three

3.9.5 Evaluating Density


The residual oil content in the (W/O) emulsion after breaking emulsion to
calculate density using standard method specific gravity picnometer. This method
refers to (D 941-83, ASTM, 1988).

API =

141.5
131.5 (3.9).
s. p.g .at15 / 15 C

46

Results and discussion

chapter four

Chapter Four
Results and Discussion
4.1 Introduction
This chapter includes two sections; the first section concerns with the
description of water separation efficiency (for breaking the crude oil emulsion) and
the influence of operating variables studied on the oil-phase viscosity, density,
remained water content in (W/O) emulsion, pH of aqueous phase and salt content
in (W/O) emulsion. The second section deals with the rheology correlation
estimation. The data for the experimental runs are shown in Appendix (B).

4.2 Effect of Demulsifiers on Water Separation Efficiency


Water separation efficiency was studied using emulsion contains 30% of brine
with concentration (3% NaCl). Figures (4.1) and (4.2) show the effect of RP6000
and Chimec2439 on water separation efficiency with time intervals. From Figure
(4.1), it can be observed that the water separation efficiency for RP6000 increases
sharply with time until it reaches 30 min, after that the increasing becomes slight;
where the maximum separation efficiency obtained at 120 min and (80) ppm
RP6000 was 87.5%. These results are in agreement with the results obtained by
Aamir, 1998. Figure (4.2) shows the separation efficiency of water for
Chimec2439 which was increases with time until it reaches 30 min then the
increasing becomes slightly, where 72.2% was obtained at 120 min.
Figure (4.3) and (4.4) show the effect of adding PAA and LAS on water
separation efficiency with time intervals. It can be observed that the separation
efficiency increases with increasing time, where separation of water was sharp with
time until it reaches 30 min, after that the increasing becomes slight, where
maximum separation efficiency obtained was 75% for PAA and 88.3% for LAS at
120 min.
47

Results and discussion

chapter four

Figure (4.5) shows the effect of adding HAS on separation water efficiency,
where the separation of water increases with time sharply until 60 min then
becomes slight. Maximum water separation obtained was 90% at 120 min that
means HAS is the best demulsifier suggested to be used.
Slightly increasing after 30 min for RP6000, Chimec2439 and PAA and LAS and
for HAS after 60min, because the active chemical groups (OH, COOH, C=O,
OSO 2 , SO 2 OH) in hydrocarbons chains for crude oil begin to be less effective, so
the separation becomes slower and hence the increasing in separation efficiency
becomes slightly. These results are in agreement with the results obtained by
(Dodd, 1954; Nimat, 1998; Aamir, 1998 and Hanapi, 2006) which they used
different demulisfiers types.
Water Content = 30%vol.
Salt in Water = 3%wt.
T= 65 oC

%Water Separation

100
80
60

RP6000=10ppm
RP6000=20ppm

40

RP6000=30ppm
RP6000=40ppm

20

RP6000=50ppm
RP6000=60ppm
RP6000=70ppm

0
0

30

60

90

Time(min)

120

150

RP6000=80ppm

Figure (4.1) Effect of Adding RP6000 at Different Doses with Time Interval

48

Results and discussion

chapter four

Water Content = 30%vol.


Salt in Water = 3%wt.
T= 65 oC

%Water Separation

100
80

Chimec2439 =10 ppm

60

Chimec2439= 20 ppm
Chimec2439= 30 ppm

40

Chimec2439= 40 ppm

20

Chimec2439= 50 ppm
Chimec2439= 60 ppm

Chimec2439= 70 ppm

30

60

90

120

150

Chimec2439= 80 ppm

Time (min)

Figure (4.2) Effect of Adding Chimec2439 at Different Doses with Time Interval

Water content=30%vol.
Salt content=3%wt.
o
T=65 C

100
%Water Separation

80
60

PAA=10ppm
PAA=20ppm

40

PAA=30ppm
PAA=40ppm

20

PAA=50ppm
PAA=60ppm

PAA=70ppm

30

60

90

120

150

PAA=80ppm

Time (min)

Figure (4.3) Effect of Adding PAA at Different Doses with Time Interval

49

Results and discussion

chapter four

Water Content = 30%vol.


Salt in Water = 3%wt.
T= 65 oC

%Water Separation

100
80

LAS = 10 ppm

60

LAS= 20 ppm
LAS = 30 ppm

40

LAS= 40 ppm
LAS = 50 ppm

20

LAS= 60 ppm

LAS= 70 ppm

30

60

90

120

150

LAS= 80 ppm

Time(min)

Figure (4.4) Effect of Adding LAS at Different Doses with Time Interval

Water Content = 30%vol.


Salt in Water = 3%wt.
T= 65 C0

%Water Separation

100
80
60

HAS=10ppm
HAS=20ppm

40

HAS=30ppm
HAS=40ppm

20

HAS=50ppm
HAS=60ppm

HAS=70ppm

30

60
90
Time (min)

120

150

HAS=80ppm

Figure (4.5) Effect of Adding HAS at Different Doses with Time Interval

50

Results and discussion

chapter four

4.3 Effect of Adding Alcohols on Water Separation Efficiency


The effect of adding alcohols on water separation efficiency was carried out by
using two types of alcohols methanol and ethanol, where M= 4:1 (methanol to
water ratio), and E=4:1(ethanol to water ratio) were used as a modifier agent to
enhance the performance of demulsifiers. Solubility of alcohol with water is greater
in emulsion compared in case of solubility of alcohol without water.
Figures (4.6) and (4.7) show the effect of adding different concentrations of
alcohols (methanol and ethanol) on water separation efficiency. Figure (4.6) shows
the water separation efficiency increasing with decreasing methanol concentration,
where maximum separation efficiency 61% was obtained at concentration
(25%methanol +75% RP6000), 120 min and mixture dose of 20 ppm. Figures (4.8)
and (4.9) show the increasing of water separation efficiency with decreasing
(methanol and ethanol) concentrations with time interval. Maximum separation
efficiency reaches 56.6% at concentration (75%), 20 ppm Chimec2439 and 120
min.
Figure (4.10) shows a comparison between using methanol and ethanol with
RP6000 and without adding alcohols. It can be observed that methanol has larger
effect on water separation efficiency than ethanol, where maximum separation
efficiency 61% was obtained at concentration (25%) methanol. The same
conclusion obtained for Chimec2439 as shown in Figure (4.11).
On the other hand, this is attributed to that the short and medium chain alcohols
are soluble in aqueous phase therefore; methanol has a good ability in promoting
water separation for the emulsion system compared to ethanol. This is because
short chain alcohols are very soluble in water and long chain alcohols are very
soluble in oil. These results are in agreement with the results obtained by Srdjan,
2007.
51

Results and discussion

chapter four

Figure (4.12) shows a comparison between three types of demulsifiers (RP6000,


75% RP6000+25%M, and HAS) for water separation. It can be observed that water
separation increases with increasing time, but maximum separation efficiency
64.1% was obtained for HAS. There for HAS can be considered as the best
demulsifier to separate water rather among types.
Attributed to the fact that the chemical active groups (hydrophilic and
hydrophobic) found in HAS structural formula, where these groups promote and
change the nature of affinity to emulsion drops to change from hydrophilic to
hydrophobic. This can be explained as the active groups break up the film around
the water droplets causing break up emulsion. These results are in agreement with
the results obtained by Hanapi, 2006.

Water Content = 30%


Salt in Water = 3%
Dose=20ppm
T= 65 oC

%Water Separation

100
80
60
40
20

0% RP6000 +100% M
25% RP6000 +75% M

0
0

30

60

90

120

150

50% RP6000 +50% M


75% RP6000 +25% M

Time(min)

Figure (4.6) Effect of Adding Methanol to RP6000 on Water Separation Efficiency


at Different Concentrations

52

Results and discussion

chapter four

Water Content = 30%


Salt in Water = 3%
Dose=20ppm
T= 65 oC

%water separation

100
80
60
40
20

0% RP6000 +100%E
25% RP6000 +75% E

0
0

30

60

90

120

50% RP6000 +50% E

150

75% RP6000 +25% E

Time (min)

Figure (4.7) Effect of Adding Ethanol to RP6000 on Water Separation Efficiency at


Different Concentrations

Water content =30%


Salt content = 3%
Dose =20 ppm
T=65 oC

% water separation

100
80
60
40
20

0% Chimec 2439 + 100% M


25% Chimec 2439 + 75% M

0
0

30

60

90

120 150

50% Chimec 2439 +50% M


75% Chimec 2439 + 25 %M

Time (min)

Figure (4.8) Effect of Adding Ethanol to Chimec2439 on Water Separation


Efficiency at Different Concentrations
53

Results and discussion

chapter four

Water Content = 30%


Salt in Water = 3%
Dose= 20 ppm
T= 65 oC

% Water Separation

100
80
60
40

0% Chimec 2439 + 100% E

20

25% Chimec 2439 +75% E

50% Chimec 2439 + 50% E

30

60

90

120

150

75 %Chimec 2439 + 25% E

Time (min)

Figure (4.9) Effect of Adding Ethanol to Chimec2439 on Water Separation


Efficiency at Different Concentrations

Water Content = 30%


Salt in Water = 3%
Dose=20ppm
T= 65 oC

% Water Separation

100
80
60
40
20

RP6000

75% RP6000+25% E

30

60

90

120 150

75% RP6000+25% M

Time (min)

Figure (4.10) Comparison between Methanol and Ethanol Effect to RP6000 on


Water Separation Efficiency with Time

54

Results and discussion

chapter four

Water Content = 30%


Salt in Water = 3%
Dose= 20 ppm
T= 65 oC

%Water separation

100
80
60
40
20

Chimec 2439
75% Chimec 2439 +25% M

0
0

30

60

90

120 150

75% Chimec 2439 +25% E

Time (min)

Figure (4.11) Comparison between Methanol and Ethanol Effect to Chimec2439


on Water Separation Efficiency with Time

Water content=30%vol.
Salt content =3%wt.
Dose =20ppm
T =65 oC

%Water Separation

100
80
60

RP6000

40

75%RP6000+25%M

20

HAS

0
0

30

60

90

120

150

Time (min)

Figure (4.12) Comparison between (RP6000, 75% RP6000+25%M, and HAS) on


Water Separation Efficiency with Time

55

Results and discussion

chapter four

4.4 Effect of Adding Demulsifiers Doses on Water Separation


Figure (4.13) shows the effect of demulsifier dose on water separation
efficiency at time of 120 min for RP6000, Chimec2439, PAA, LAS and HAS. It
can be observed that water separation increases with increasing demulsifiers dose.
The maximum removal of water 87.5% was obtained at 80 ppm of RP6000, which
was higher separation of water than Chimec2439 at the same time and dose.
Three types of demulsifiers had been prepared (PAA, LAS and HAS), then
used in water separation test. It can be observed that water separation increases
with increasing demulsifier dose. Maximum value of separation 90% was obtained
for HAS. That means HAS has a good ability to promote separation of water than
other types due to its chemical and physical properties specially structural formula.
Where the active chemical groups play important rules in water separation process.
This behavior is similar to the trend obtained by (Nimat, 1998 and Hanapi, 2006).

%Water Separation

100
Water Content = 30%
Salt in Water = 3%
T= 65 oC, 120 min

80
60
40

Chimec2439
PAA

20

LAS
RP6000

0
0

20

40

60

80

100

HAS

Dose(ppm)

Figure (4.13) Effect of Doses on Water Separation for


RP6000, Chimec2439, PAA, LAS and HAS at 120 min

56

Results and discussion

chapter four

4.5 Effect of Salt content on Water Separation


Figure (4.14) shows the effect of salt content on water separation efficiency. It
can be observed that water separation efficiency increases with decreasing salt
content for both types of demulsifiers (RP6000 and Chimec2439), where maximum
separation for water reaches 87.5% and 72.2% for RP6000 and Chimec2439.
Figures (4.15) and (4.16) show the effect of salt content on water separation
efficiency using improved (RP6000) and (Chimec2439) with (25%) methanol and
(25%) ethanol as modifiers agents. It can be observed from figures that water
separation efficiency increases even after adding alcohols as modifiers agents.
Maximum separation efficiency obtained 61% for (75% RP6000+25% M) and
58.2% for (75% RP6000+25% E) and for Chimec2439 were 56.6% for (75%
Chimec2439+25% M) and 55.9% for (75% Chimec2439+25% E).
Figure (4.17) shows the effect of salt content on water separation efficiency
using prepared demulsifiers. From Figure (4.17), it can be observed that the
separation of water efficiency increases with decreasing salt content for all types of
prepared demulsifiers, where maximum water separation efficiencies were 90%,
88.3% and 75% for HAS, LAS and PAA respectively.
The reason of decreasing salt content in the oil phase with increasing of water
separation efficiency, attributed to the chemical activity of hydrophilic and
hydrophobic group present in the demulsifier molecular.

57

Results and discussion

Salt Content (mg/l)

30

chapter four

Water Content = 30%


Salt in Water = 3%
T= 65 oC , 120min.

70 ppm
10 ppm 60
70ppm
ppm

25

50 60
ppm
ppm
40 ppm
50 ppm
30 ppm
30 ppm
40 ppm
20 ppm
40 ppm
10 ppm
30 ppm
50 ppm
20 ppm
60 ppm
10 ppm
70 ppm

20 ppm

20
15
10

80 ppm

5
0

Chimec2439

20

40

60

80

100

RP6000

%Water Separation

Figure (4.14) Effect of Salt Content on Water Separation Efficiency Using Pure
RP6000 and Chimec2439

Water Content = 30%


Salt in Water = 3%
T= 65 oC , 120 min
Dose =20 ppm

Salt Content (mg/l)

30
25

%100E+

20

%75E+

%100M+

%50E+

%75M+

15

%50M+

10

%25E+
%25M+

RP6000+M
RP6000+E

0
0

20

40

60

80

100

%Water Separation

Figure (4.15) Effect of Salt Content on Water Separation Efficiency Using


(RP6000 + Alcohol)

58

Results and discussion

chapter four
Water Content = 30%
Salt in Water = 3%
T= 65 oC, 120 min.
Dose= 20 ppm

Salt Content (mg/l)

30
25

%100E+

%100M+

%75E+

20

%75M+

%50E+ %100M+
%50M+
%75M+
%25M+
%25E+ %50M+

15
10

%25E+

%25M+

5
Chimec2439+M

0
0

20

40

60

80

100

Chimec2439+E

%Water Separation

Figure (4.16) Effect of Salt Content on Water Separation Efficiency Using


(Chimec2439 + Alcohol)

Water Content = 30%


Salt in Water = 3%
T= 65 oC , 120 min

Salt Content (mg/l)

30
25

10 ppm
20 ppm
80 ppm
30 ppm
70 ppm

20

40 ppm
60 ppm
50 ppm50 ppm60 ppm
40 ppm
70 ppm
30 ppm
20 ppm
80 ppm
10 ppm

15
10
5

PAA
LAS

0
0

20

40

60

80

100

HAS

%Water Separation

Figure (4.17) Effect of Salt Content on Water Separation Efficiency Using PAA,
LAS and HAS

59

Results and discussion

chapter four

4.6 Effect of pH on Water Separation Efficiency


The (W/O) emulsions are stabilized by absorbed film of organic acids and bases
in different amounts. The films are very strongly influenced by adding the acids
and bases. Consequently, the physical properties of the interfacial film were also
affected (Strassner, 1968 and Einar, 1989).
Figure (4.18) shows the effect of pH change on water separation efficiency. It
can be observed that water separation efficiency increases with increasing of pH,
where maximum water separation is 87.5% at pH = 7.5 for pure

RP6000 and

72.2% at pH = 7.43 for Chimec2439. Figure (4.19) shows that water separation
increases with increasing of pH using modified demulsifier (RP6000+M and
RP6000+ E). It can be observed that separation efficiency of water reaches the
maximum value up to 61% when methanol was used as a modifier agent, where it
gave higher separation efficiency than ethanol. In case of using ethanol of (25%)
the separation efficiency was only 58.2%. Methanol is more effective with
increasing of pH than ethanol this is due to the methanol solubility in water is more
than that of ethanol. Figure (4.20) shows a comparison between using methanol and
ethanol with Chimec2439. The same trends could be obtained as in the case using
of RP6000.
Figure (4.21) shows the effect of pH on water separation efficiency using three
types of prepared demulsifiers (PAA, LAS and HAS). It can be observed that water
separation efficiency increases with increasing of pH, up to 90% was obtained at
pH= 7.6 for HAS. This behavior is similar to the trend obtained by Aamir, 1998.
It can be seen from these figures that the increasing of water separation causes
an increase in pH of the solution. This is due to that the removal of water increased
the amount of salt removed. Hence, the quality of oil will be improved.

60

Results and discussion

chapter four

80 ppm
Water
70 ppm
Salt in
60 ppm

%Water Separation

100

Content = 30%vol.
Water = 3%wt.
o
T= 65 C, 120 min

50 ppm
40 ppm
30 ppm

80

80 ppm
70 ppm

60

60 ppm
50 ppm

40

40 ppm

10 ppm

30 ppm

20
20 ppm

Chimec2439

0
6.8

7.2

7.4

7.6

RP6000

pH

Figure (4.18) Effect of pH on Water Separation Efficiency Using Pure RP6000 and
Chimec2439

Water Content = 30%vol.


Salt in Water = 3%wt.
T= 65 oC , 120 min
Dose =20 ppm

% Water Separation

100
80
%25 M+

60

%50 M+

%25E+

%75 M+
%100 M+

40

%50 E+
%75E+

%100 E+

20

%25 M+
%50 M+

%75 M+

%25 E+

RP6000+M
RP6000+E

%50 E+

0
7

%75 E+

7.1

%100 E+

7.2

7.3

7.4

pH

Figure (4.19) Effect of pH on Water Separation Efficiency


Using RP6000+ Alcohols

61

Results and discussion

chapter four

Water Content =30%vol.


Salt in Water = 3%wt.
T= 65 oC , 120 min
Dose= 20 ppm

%Water Separation

100
80
%25 M+

60
40

%50 M+

%25 M+
%25 E+

%75M+
%50 M+
%100 M+
%50 E+
%75 M+
%75 E+
%100 E+
%75 E+

20

%25 E+

Chimec 2439 + M

%50 E+

Chimec 2439 + E

%100 E+

0
6.9

7.1

pH

7.2

7.3

7.4

Figure (4.20) Effect of pH on Water Separation Efficiency


Using Chimec2439+ Alcohols

80 ppm
70 ppm
60 ppm

%Water Separation

100

50 ppm
40 ppm
30 ppm

80

Water Content = 30%vol.


Salt in Water = 3%wt.
T= 65 oC , 120 min

20 ppm
80 ppm
70 ppm
60 ppm
50 ppm
40 ppm
30 ppm

60

10 ppm

40
20 10 ppm

PAA
LAS

HAS

6.8

7.2

7.4

7.6

7.8

pH

Figure (4.21) Effect of pH on Water Separation Efficiency


Using PAA, LAS, and HAS

62

Results and discussion

chapter four

4.7 Effect of Demulsifier Dose on Remainder of Water Content


The dose of demulsifier has a great effect on remainder water content. Figure
(4.22) shows the remainder water content decreases with increasing dose for both
types of demulsifiers (Chimec2439 and RP6000). It can be observed that RP6000
has less remainder water content than Chimec2439. This attributed to the fact that
its ability to remove water is greater for high dose. Minimum value of remainder
water content was obtained at (80) ppm or both RP6000 and Chimec2439. Figure
(4.23) shows the effect of dose on remainder water content using three types of
prepared demulsifiers (PAA, LAS and HAS). The same behavior was observed for

%Remained water content

RP6000 and Chimec2439.

Water Content = 30%


Salt in Water = 3%
T= 65 oC, 120 min

0.6
0.5
0.4
0.3
0.2
0.1

Chimec2439

0
0

20

40

60

80

100

RP6000

Dose (ppm)

Figure (4.22) Effect of Dose on Remainder Water Content Using


RP6000 and Chimec2439

63

Results and discussion

chapter four

Water content=30%
Salt content=3%
T=65 oC,120 min.

%Remained water content

0.6
0.5
0.4
0.3
0.2
0.1

PAA

LAS

20

40

60

80

100

HAS

Dose (ppm)

Figure (4.23) Effect of Dose on Remainder Water Content Using


PAA, LAS, HAS

4.8 Effect of Dose on Density


As was discussed before dose of demulsifier has a great effect on physical and
chemical properties of emulsion. Figure (4.24) shows the effect of doses for
different types of demulsifiers (RP6000, Chimec2439, PAA, LAS, and HAS). It
can be observed that the dose of demulsifier increases, the density of emulsion after
water separation decreases. Generally for all types of demulsifiers it can be seen
that the lowest density is at dose (80 ppm), but HAS has the biggest effect on
reducing density of emulsion. Where the density of emulsion at (80 ppm) was
0.832gm/cm3 when HAS was used. This is because of HAS has a great ability to
remove water from emulsion, where at this dose it can reaches 90% separation
water efficiency.

64

Density (gm/cm 3)

Results and discussion

chapter four

1.02
1
0.98
0.96
0.94
0.92
0.9
0.88
0.86
0.84
0.82

PAA
LAS
HAS
RP6000
Chimec2439

20

40

60

80

100

Dose (ppm )

Figure (4.24) Effect of Dose Demulsifier on Emulsion Density after Water


Separation at Temperature 65oC and water content 30%vol. (3%wt. NaCl)

4.9 Emulsion Rheology


Figure (4.25) shows the effect of shear stress on emulsion viscosity before and
after water separation. From this figure it can be seen that the emulsion viscosity
decreases rapidly with increasing shear stress until it reaches about (200 dyne/cm2).
Where at this zone the velocity is very low so the emulsion has a non Newtonian
behavior. After that the viscosity becomes almost constant with shear stress so the
emulsion behave like Newtonian fluid. It can be observed also at (80 ppm) of HAS
the viscosity has the smallest value 49 (mPa.sec). This is because of HAS has a
great ability to remove water from emulsion and hence the viscosity decreases
when large amount of water was removed.

65

Results and discussion

chapter four
Water content =30%
Salt in water=3%
T =65 oC

Viscosity(mPa.s)

250
200
150

HAS=0ppm
HAS =20ppm

100

HAS =40ppm

50

HAS =60ppm
HAS =80 ppm

0
0

200

400

600

800

1000

Shear Stress(dyne/cm 2)

Figure (4.25) Effect of Shear Stress on Viscosity Using Different doses from
demulsifier (HAS)

4.10 Rheology Correlation


4.10.1 Viscosity Correlation
Viscosity of emulsion after water separation has been correlated with dose of
HAS and shear stress equation (4.1), then the correlation coefficient and predicted
observed values has been plotted. As was expected viscosity of emulsion has
inverse proportionality to each demulsifier dose and shear stress and this enhance
the results obtained in Figure (4.25). The correlation obtained is:

= a b D c ... . (4.1)
Where the coefficients a, b and c are constants
The coefficients of equation (4.1) where estimated by statistically analysis using
statistic software version (6).

= 522.801 0.0548 D 0.42411 (4.2)

66

Results and discussion

chapter four

Figure (4.26) shows the three dimensional graph where dose and shear stress
has inverse proportionality to emulsion viscosity. The correlation coefficient (R)
was 93.2177%. Figure (4.27) shows the observed predicted value of viscosity.

Figure (4.26) 3D Plot for Emulsion Viscosity Correlation

67

Results and discussion

chapter four
Observed versus Predicted Values

130
120

Observed Values

110
100
90
80
70
60
50
40
50

60

70

80

90

100

110

120

130

140

Predicted Values

Figure (4.27) Predicted Observed Values for Emulsion Viscosity Correlation

4.10.2 Relationship between Shear Stress and Shear Rate


To prove that the relationship between shear stress and shear rate obeys the
Newtonian law, a mathematical correlation has been evaluated equation (4.3),
where the correlation coefficient is R= 99.954% as shown in Figures (4.28) and
(4.29). The correlation obtained is:

= m n

. (4.3)

Where the coefficients m, n are constants


The coefficients of equation (4.3) where estimated by statistically analysis using
statistic software version 6.

= 59.0318 0.99701 .. (4.4)


From the above correlation it can be seen that the power of () shear rate is
close to one. That means the emulsion behave like Newtonian fluid.
68

Results and discussion

chapter four

y=(59.0318)*x^(.909769)
(.99701)
Shear Stress (dyne/cm2)

500

400

300

200

100

0
0

(sec-1)1)
Shear Rate (sec
Figure (4.28) Relationship between Shear Rate and Shear Stress

Observed versus Predicted Values


450
400

Observed Values

350
300
250
200
150
100
50
0
0

50

100

150

200

250

300

350

400

450

Predicted Values

Figure (4.29) Predicted Observed Value of Shear Stress Correlation


69

Conclusions and Recommendations

chapter Five

Chapter Five
Conclusions and Recommendations
5.1 The Conclusions
The following conclusions could be obtained:
1. Water separation efficiency increases with increasing separation time for all
types of demulsifiers, where maximum separation obtained is at (120min).
2. Water separation efficiency increases with increasing dose of demulsifiers
where maximum separation for water obtained is at (80ppm) for all types of
demulsifiers.
3. Adding alcohols as modifier agents improve the performance of
demulsifiers, where methanol and ethanol were used, and optimum alcohol
percent with demulsifier was (25%). Methanol gave higher water separation
than ethanol due to the short chain in methanol and higher solubility in water
than ethanol.
4. Two types of commercial demulsifiers has been used (RP6000 and
Chimec2439), where they gave (87.5%) and (72.2%) water separation
efficiency, respectively. Three types of prepared demulsifiers has been used
(PAA, LAS and HAS). HAS gave higher removal efficiency of (90%), and
(88.3%, 75%) for LAS and PAA respectively.
5. Density of emulsion after water separation has an inverse proportionality to
demulsifier dose where minimum emulsion density obtained was
(0.832gm/cm3) when HAS was used.

70

Conclusions and Recommendations

chapter Five

6. Viscosity emulsion after water separation has an inverse proportionality to


shear stress and dose of demulsifier. This was proved by a mathematical
correlation between viscosity, shear stress and demulsifier dose.
7. The emulsion behavior after water separation behaves as Newtonian fluid.
This was proved by a correlation between shear stress and shear rate by using
power formula. The power of shear rate was (0.99701) that means close to
Newtonian fluid, as for Newtonian fluids the power should be equal to one.

5.2 Recommendations
The following recommendations may be made for future work:
1. Study the effect of changing temperature on water separation process.
2. Study the effect of mixing on emulsion stability.
3. Using other types of modifier agents to improve the performance of
demulsifiers.
4. Work needs to be carried out using natural crude oil emulsion.
5. Studying the combination between the three methods namely, Thermal,
electrical and chemical methods.

71

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77

Appendix (A)
11

Conductivity (mS)

10

4
0

10

20

30

40

50

60

70

Brine Cocentration (mg/l)


Figure (A.1) Calibration Curve of Brine Concentration vs. Conductivity

80

Appendix

Appendix (B)
The Data for the Experimental Runs
Table (B.1) Effect of RP6000 on the separation of water from Basrah crude oil
emulsion, Temperature = 65oC, and water content =30% vol. (3% wt. NaCl).
P

Separation Time (min)


Dose
(ppm)

10
20
30
40
50
60
70
80

16.6
24
35.5
43.1
44.5
50.1
54.5
55

10

15

30

60

90

120

45.5
53.4
60.6
63.5
76
80.3
86.3
85

45.6
57.4
63.5
66
77.8
83
86.3
87.5

45.6
57.4
63.5
66.7
77.8
83.5
86.4
87.5

Water Separation (%)


18.6
26.7
36
44.5
45.6
67.2
57.3
58.5

20.1
36.9
40
48
53
75
77.3
78

30.4
46.3
50.1
57.5
68.6
78.2
79.7
84.6

Table (B.2) Effect of Chimec2439 on the separation of water from Basrah crude
oil emulsion .Temperature =65oC, and water content =30%vol. (3%wt. NaCl).
P

Separation Time (min)


Dose
(ppm)

10
20
30
40
50
60
70
80

0
0
0
0
0
0
0
0

10

15

30

60

90

120

15.5
17.8
23.5
30.5
40.1
50.7
63.1
70.5

17.5
17.9
28.5
35.4
44.6
58.3
63.7
72.1

17.6
18
28.6
36
44.7
58.3
64.1
72.2

Water Separation (%)


0
0
0
0
0
0
0
0

8.6
10.2
19.5
20.5
26.3
38.3
47.5
50.3

11.1
13.8
20.1
24.3
28.3
48.1
55.1
63.1

Appendix
Table (B.3) Effect of adding Methanol to RP6000 on the separation of water
from Basrah crude oil emulsion. RP6000+M =0+100%, 25%+75%, 50%+50%
and 75%+25%, Temperature =65oC, and water content =30%vol. (3%wt. NaCl).
P

Where M= 4:1methanol to water ratio.


Separation Time (min)
Dose
(ppm)

20
20
20
20

10.5
12.3
20.7
28.1

10

15

30

60

90

120

36.7
40.1
53
60.5

36.8
42.1
54
61

Water Separation (%)


14.3
17.6
21.3
35.3

18.5
20.2
24.6
47

20.5
23.1
40.5
55

34.4
37.5
50.3
58.5

Table (B.4) Effect of adding Ethanol to RP6000 on the separation of water from
Basrah crude oil emulsion. RP6000+E =0+100%, 25%+75%, 50%+50% and
75%+25%, Temperature =65oC, and water content =30%vol. (3%wt.
P

NaCl).Where E=4:1ethanol to water ratio.

Separation Time (min)


Dose
(ppm)

20
20
20
20

8.4
10.5
21.3
26.1

10

15

30

60

90

120

34.2
38
48.1
58.2

34.5
38.5
48.8
58.2

Water Separation (%)


12.5
15.3
21.9
33.1

17.5
20
21.1
45

21.3
22
35.5
53.5

33
36.3
47
58

Appendix

Table (B.5) Effect of adding Methanol to Chimec2439 on the separation of


water from Basrah crude oil emulsion. Chimec2439+M =0+100%, 25%+75%,
50%+50% and 75%+25%, Temperature =65oC, and water content =30%vol.
P

(3%wt. NaCl).Where M=4:1methanol to water ratio.


Separation Time (min)
Dose
(ppm)

10

15

30

60

90

120

30.1
35.4
44.9
56.6

30.5
35.8
45
56.6

Water Separation (%)


20
20
20
20

8.3
14.4
21
27.7

10.5
18.4
25.1
31.5

19.5
21.6
34.1
35.9

22.3
28.1
38
42.5

28.9
32.2
40.5
48.9

Table (B.6) Effect of adding Ethanol to Chimec2439 on the separation of water


from Basrah crude oil emulsion. Chimec2439+E=0+100%, 25%+75%,
50%+50% and 75%+25%, Temperature =65oC, and water content =30%vol.
P

(3%wt. NaCl). Where E=4:1 ethanol to water ratio.

Separation Time (min)


Dose
(ppm)

20
20
20
20

5.9
10.1
18.5
25.5

10

15

30

60

90

120

25.4
30.1
41.5
54.4

26.5
30.2
41.6
55.9

Water Separation (%)


9.8
13.5
20.6
30.3

14.4
18.9
27.5
37.3

19.5
22.1
32.2
41.7

20.5
28.3
35.5
42.2

Appendix

Table (B.7) Effect of PAA on the separation of water from Basrah crude oil
emulsion. PAA = 0.5%, Temperature =65o

Separation Time (min)


Dose
(ppm)

10
20
30
40
50
60
70
80

14.5
20.8
25.5
29.6
33.4
46.6
50
53

10

15

30

60

90

120

30.5
46.8
55.5
60.5
64.8
69.3
71
75

32.6
46.8
56
61
65.7
70
73
75

32.7
46.9
56.5
61.8
65.7
70.1
73.8
75

Water Separation (%)


17.6
28.6
32.1
40
42.1
53.5
55
57.5

20.3
35.7
48.7
49
57
60.1
64
62.5

27.3
46.7
50.7
60.5
64.8
69.3
71
73.8

Table (B.8) Effect of LAS on the separation of water from Basrah crude oil
emulsion. Temperature =65oC, and water content =30%vol. (3%wt. NaCl).
P

Separation Time (min)


Dose
(ppm)

10
20
30
40
50
60
70
80

16
24
30.6
33.7
40.1
42.5
55.7
58.1

10

15

30

60

90

120

35.6
48.2
57
63.6
65.9
73
77
88.3

35.6
48.2
57.3
63.7
65.9
73.5
77.1
88.3

Water Separation (%)


19.5
27.1
36.1
38.1
49.1
61
63.1
68

21.6
37.4
39.5
43.1
53.3
65.1
68.9
76.3

28.7
44.8
46.7
54.6
60.5
72.1
75.9
84.5

34.3
47.3
56.8
59.5
62.1
72.6
75
87.6

Appendix
Table (B.9) Effect of HAS on the separation of water from Basrah crude oil
emulsion. Temperature =65o
C, and water content =30%vol.
(3%wt. NaCl).
5
Dose
(ppm)
10
20
30
40
50
60
70
80

15.5
29.8
31
34
42.1
46.4
55.1
58.6

Separation Time (min)


10

15

30

60

90

120

35.7
64.1
64.5
65.2
68.1
78
87.1
90

35.7
64.1
64.5
65.3
68
78
87.1
90

Water Separation (%)


18.7
38.5
33.5
39.1
45.3
60.2
64.3
67.3

22.1
47.3
47.6
55.3
57.1
68
73.1
76.5

29
59.9
60
64
64.5
72
83.6
85.1

30.5
63
63.3
65.2
65.5
76.3
85.5
88.1

Table (B.10) Effect of demulsifier dose on water separation efficiency at time


(120 min) for both RP6000 and Chimec2439. Temperature =65oC, and Water
P

content =30%vol. (3%wt. NaCl).

Dose
( ppm)

10
20
30
40
50
60
70
80

Separation Time
120 (min)
Water Separation (%)
RP6000
Chimec2439
45.6
57.4
63.5
66.7
77.8
83.5
86.4
87.5

17.6
18
28.6
36
44.7
58.3
64.1
72.2

Appendix
Table (B.11) Effect of demulsifier dose on water separation efficiency at time
o
C, and(3%wt.
Water content
and Water
content=65
=30%vol.
NaCl).
(120 min) for PAA, LAS andC,HAS.
Temperature
P

=30%vol. (3%wt. NaCl).

Dose
( ppm)

10
20
30
40
50
60
70
80

Separation Time
120 (min)
Water Separation (%)
PAA
LAS
HAS
32.7
46.9
56.5
61.8
65.7
70.1
73.8
75

35.6
48.2
57.3
63.3
65.9
73.5
77.1
88.3

35.7
64.1
64.5
65.3
68
78
87.1
90

Table (B.12) Effect of salt content on water separation efficiency at time (120
min) for both types of demulsifiers (RP6000 and Chimec2439). Temperature
=65oC, and water content =30%vol. (3%wt. NaCl).
P

Salt content (mg/l)

Separation Time
120 (min)
Water Separation (%)

RP6000
17.2
13.6
12.1
11.1
7.8
6
4.9
4.6

Chimec2439
25.6
25.5
22.3
19.3
17.5
13.4
11.6
9.2

RP6000
45.6
57.4
63.5
66.7
77.8
83.5
86.4
87.5

Chimec2439
17.6
18
28.6
36
44.7
58.3
64.1
72.2

Appendix
Table (B.13) Effect of salt content on water separation efficiency at time
(120min) for RP6000+M and RP6000+E=0%+100%, 25%+75%, 50%+50% and
75%+25%.Temperature=65oC,and water content =30%vol.(3%wt. NaCl).Where
P

M=4:1 methanol to water ratio and E=4: 1 ethanol to water ratio.

Salt content
(mg/l)

Separation Time
120 (min)
Water Separation (%)

RP000+M

RP000+E

RP000+M

RP000+E

19.8
18.2
14.7
12.6

20.5
19.3
16.2
13.4

36.8
42.1
54
61

34.5
38.5
48.8
58.2

Table (B.14) Effect of salt content on water separation efficiency at time


(120min) for Chimec2439+M and Chimec2439+E =0%+100%, 25%+75%,
50%+50% and 75%+25%. Temperature =65oC, and water content =30%vol.
P

(3%wt. NaCl).Where M=4:1 methanol to water ratio and E=4:1 ethanol to water
ratio.
Separation Time
120 (min)
Water Separation (%)

Salt content
(mg/l)

Chimec2439+M Chimec2439+E Chimec2439+M


21.7
20.1
17.4
13.9

22.9
21.8
18.4
14.1

30.5
35.8
45
56.6

Chimec2439+E
26.5
30.2
41.6
55.9

Appendix
Table (B.15) Effect of salt content on water separation efficiency at time
(120min) for types of demulsifiers (PAA, LAS and HAS). Temperature =65oC,
P

and water content =30%vol. (3%wt. NaCl).

Separation Time
120 (min)
Water Separation (%)

Salt content
( ppm)
PAA
21
16.8
13.9
12.3
11.1
9.8
8.7
8.4

LAS

HAS

PAA

LAS

HAS

20.2
16.4
13.7
11.9
11.1
8.8
6.9
4.4

20.1
11.6
11.4
11.3
10.5
7.5
4.7
3.9

32.7
46.9
56.5
61.8
65.7
70.1
73.8
75

35.6
48.2
57.3
63.7
65.9
73.5
77.1
88.3

35.7
64.1
64.5
65.3
68
78
87.1
90

Table (B.16) Effect of pH on water separation efficiency at time (120min) for


both types of demulsifiers (RP6000 and Chimec2439), Temperature =65oC, and
P

water content =30%vol. (3%wt. NaCl).

Separation Time
120 (min)

pH

Water Separation (%)


RP6000

Chimec2439

HAS

Chimec2439

7.14
7.23
7.33
7.37
7.40
7.46
7.50
7.50

6.85
6.88
6.98
7.05
7.15
7.29
7.34
7.43

45.6
57.4
63.5
66.7
77.8
83.5
86.4
87.5

17.6
18
28.6
36
44.7
58.3
64.1
72.2

Appendix
Table (B.17) Effect of pH on water separation efficiency at time (120min) for
RP66000+M and RP6000+E=0%+100%, 25%+75%, 50%+50% and 75%+25%,
Temperature =65oC, and water content =30%vol. (3%wt. NaCl).Where M=4:1
P

methanol to water ratio and E=4:1 ethanol to water ratio.

Separation Time
120 (min)
Water Separation (%)

pH
RP6000+M
7.07
7.10
7.32
7.36

RP6000+E
7.03
7.09
7.26
7.30

RP6000+M
36.8
42.1
54
61

RP6000+E
34.5
38.5
48.8
58.2

Table (B.18) Effect of pH on water separation efficiency at time (120 min) for
Chimec2439+M and Chimec2439+E = 0%+100%, 25%+75%, 50%+50%
and75%+25%, Temperature =65oC, and water content =30%vol. (3%wt. NaCl).
P

Where M=4:1 methanol to water ratio and E = 4:1 ethanol to water ratio.
Separation Time
120 (min)
Water Separation (%)

pH
Chimec2439+M
7.03
7.06
7.15
7.29

Chimec2439+E Chimec2439+M
6.96
7.01
7.12
7.26

30.5
35.8
45
56.6

Chimec2439+E
26.5
30.2
41.6
55.9

Appendix
Table (B.19) Effect of pH on water separation efficiency at time (120min) for
types of demulsifiers (PAA, LAS and HAS). Temperature =65oC, and water
P

content =30%vol. (3%wt. NaCl).

Separation Time
120 (min)
Water Separation (%)

pH
PAA

LAS

HAS

PAA

LAS

HAS

7.01
7.17
7.26
7.32
7.36
7.41
7.44
7.46

7.06
7.18
7.27
7.34
7.36
7.43
7.48
7.59

7.06
7.18
7.28
7.35
7.38
7.48
7.56
7.60

32.7
46.9
56.5
61.8
65.7
70.1
73.8
75

35.6
48.2
57.3
63.3
65.9
73.5
77.1
88.3

35.7
64.1
64.5
65.3
68
78
87.1
90

Table (B.20) Effect of demulsifiers doses on remainder of water at constant time


(120min) for both types of demulsifiers (RP6000 and Chimec2439).
Temperature =65oC, and water content =30%vol. (3%wt. NaCl).
P

Separation Time 120 (min)


Dose
(ppm)
10
20
30
40
50
60
70
80

Remained water content (%)


RP6000

Chimec2439

0.32
0.25
0.22
0.20
0.18
0.15
0.082
0.075

0.49
0.49
0.42
0.38
0.33
0.25
0.21
0.16

Appendix
Table (B.21) Effect of demulsifiers doses on remainder of water at time
(120min) for types of demulsifiers (PAA, LAS and HAS). Temperature =65oC,
and Water content =30%vol. (3%wt. NaCl).
Dose Remained water content
(ppm)
(%)
PAA
LAS
HAS
10
20
30
40
50
60
70
80

0.4
0.31
0.26
0.22
0.2
0.18
0.16
0.15

0.38
0.31
0.25
0.21
0.2
0.16
0.13
0.07

0.38
0.21
0.21
0.2
0.19
0.13
0.07
0.06

Table (B.22) Effect of doses of different types of demulsifiers (PAA, LAS,


HAS, RP6000 and Chimec2439) on density at time (120min), Temperature
=65oC, and water content =30%vol. (3%wt.NaCl).
P

Dose
(ppm)

PAA

LAS

10
20
30
40
50
60
70
80

0.993
0.991
0.988
0.972
0.964
0.945
0.92
0.881

0.988
0.97
0.956
0.945
0.923
0.901
0.882
0.861

Density (gm/cm3)
HAS
RP6000
P

0.981
0.966
0.945
0.934
0.921
0.88
0.856
0.832

0.989
0.983
0.971
0.966
0.946
0.924
0.893
0.874

Chimec2439
0.998
0.993
0.973
0.966
0.956
0.934
0.922
0.901

Appendix
Table (B.23) Effect of shear stress on emulsion viscosity before and after water
separation Using different doses from demulsifier (HAS) =0, 20, 40, 60 and 80
ppm at time (120min), Temperature =65o

Shear stress (dyne/cm2)


P

8.4
15.8
31.8
52.5
92.7
173
587
987

5
9.8
26
48.7
96.3
185
460
909.1

4.6
8.8
20.9
36.1
73.3
147
360.3
721.5

Viscosity (mPa.sec)

4.1
7.1
18
28.7
55
107.6
266.4
532.5

3.6
6.6
14
23.1
44.8
89.9
212.3
420.9

211
197
144.6
125
116
109
108
106

125
123
119
116
112
107
107
107

116
110
95.3
86.1
85.3
85
84
84

104
89.5
82
68.5
64
62.2
62.1
62

91.5
83
64
55.2
52.1
52
49
49

Appendix

Appendix (C)
Sample of viscosity and shear stress calculation:
= ak
Where:
= Viscosity (mPa.sec).

a= is the reading indicated by indicator, K= Constant


K

200
100
40
20
10
5
2
1

0.62
1.23
2.98
5.8
11.2
21.4
53.5
107

= 2N / 60
Where:
= angular frequency (Sec-1)
P

N= rotational speed (rpm)

r2
r2 ri 2

Where:

= Shear rate (Sec-1)


P

r i =radius of inner cylinder=18.8mm


R

r o =radius of outer cylinder=36.2mm


R

(mPa.sec)
125
123
119
116
112
107
107
107

Appendix

=
Where:

= Shear stress (mPa).


N

(rpm

(Sec-1)

0.3

0.031

0.6

(mPa.sec)

(Sec-1)

(mPa)

125

0.04

0.063

123

0.08

9.8

1.5

0.16

119

0.22

26

0.31

116

0.42

48.7

0.63

112

0.86

96.3

12

1.26

107

1.73

185

30

3.14

107

4.29

460

60

6.28

107

8.5

909.1



) ( .
.
) (RP6000,Chimec2439,PAA,LAS,HAS
. 65 ) . (30%
:
-1 ).ppm (80,70,60,50,40,20,10
-2 ) (120,90,60,30,15,10,5 .
-3 ).(RP6000,Chimec2439,PAA,LAS ,HAS
-4 ) (100% 75% 50% 25%

).(RP6000 ,Chimec2439
)(HAS, LAS, PAA
) (90%88.3%75% ) ( RP6000,Chimec2439
) (87.5% 72%

) (25%

(61%) (56.6% )RP6000


.Cimec2439 ) ( pH

) (0,832gm/cm3 HAS .
P

= 522.801 0.0548 D 0.42411 :

, R=93.2117

= 59.0318 0.99701 , R=99.981


.

2009