THE EFFECT OF PH AND BRINE

COMPOSITION TOWARDS EMULSION

STABILITY

MOHD LUQMAN BIN NOOR AFFENDI

A report submitted in partial fulfilment of the

requirements for the award of the degree of
Bachelor of Petroleum Engineering

Faculty of Petroleum and Renewable Energy Engineering

Universiti Teknologi Malaysia

JUNE, 2014
 iii

I dedicate this to my parents,

Noor Affendi bin Hj Abd. Muti and Samiah bte Awang,
 iv

ACKNOWLEDGEMENT

I would like to express my deepest gratefulness to Allah S.W.T., with His

willingness I was able to complete my study in the Degree of Petroleum Engineering.
I also would like mention my thanks my supervisor, Doctor Mohd Zaidi Jaafar for
his constant support and guidance throughout the period of this study.

This kind appreciation also goes to Mr. Roslan Jas, Mr. Zulkifle Nasir, Mr.
Othman Adon and all the lab technicians for their cooperation and helpful advices.

Last but not least, thank you to my parents and my siblings for their
undivided love.
 THE EFFECT OF PH AND BRINE
COMPOSITION TOWARDS EMULSION
STABILITY

MOHD LUQMAN BIN NOOR AFFENDI

A report submitted in partial fulfilment of the

requirements for the award of the degree of
Bachelor of Petroleum Engineering

Faculty of Petroleum and Renewable Energy Engineering

Universiti Teknologi Malaysia

JUNE, 2014
 iii

I dedicate this to my parents,

Noor Affendi bin Hj Abd. Muti and Samiah bte Awang,
 iv

ACKNOWLEDGEMENT

I would like to express my deepest gratefulness to Allah S.W.T., with His

willingness I was able to complete my study in the Degree of Petroleum Engineering.
I also would like mention my thanks my supervisor, Doctor Mohd Zaidi Jaafar for
his constant support and guidance throughout the period of this study.

This kind appreciation also goes to Mr. Roslan Jas, Mr. Zulkifle Nasir, Mr.
Othman Adon and all the lab technicians for their cooperation and helpful advices.

Last but not least, thank you to my parents and my siblings for their
undivided love.
 v

ABSTRACT

With the increase usage of waterflooding and surfactant flooding in

secondary and tertiary recovery, there is a potential risk of arising emulsion
formation during these processes. Surfactant which refers to naturally surface-active
agents will adsorb at the interfacial film of the emulsion and stabilize it so it will
resist coalescence. This poses numerous problems towards a lot of perspectives and
angles. Hence, a need to counter these hindrances triggered this study. The specific
objective for the study is to investigate the effect of pH and brine composition on the
emulsion stability. A series of demulsification using gravity settlement was carried
out to test the stability of the emulsion. Values of pH were fixed at 3.0, 5.0, 7.0, 9.0
and 11.0 which are acidic, neutral to basic condition respectively. While for the brine
composition, Sodium Chloride (NaCl) was added at 0, 20000 and 40000 ppm to
investigate the effect of salinity in emulsion stability. Lastly, centrifugation process
was done to obtain the basic sediment and water for the separated emulsion. The
results demonstrate the capability of sodium chloride to destabilize the emulsion and
also suggest that increase in value of pH will contribute to coalescence of the water
droplet and promote separation.
 vi

ABSTRAK

Dengan peningkatan dalam penggunaan banjiran air dan banjiran surfaktan di

perolehan kedua dan ketiga, terdapat potensi risiko yang timbul pembentukan emulsi
semasa proses ini. Surfaktan yang merujuk kepada agen semula jadi yang aktif di
permukaan akan diserap di filem antara muka dan menstabilkan ia jadi ia akan
menentang tautan. Ini mencetuskan pelbagai masalah di setiap perspektif dan sudut.
Oleh itu, keperluan untuk mengatasi masalah ini mencetuskan kajian ini. Objektif
bagi kajian ini adalah untuk mengkaji kesan pH dan komposisi air garam terhadap
kestabilan emulsi. Satu siri demulsifikasi menggunakan graviti telah dijalankan
untuk menguji kestabilan emulsi. Nilai pH telah ditetapkan pada 3.0, 5.0, 7.0, 9.0 dan
11.0 yang bersifat asid, neutral kepada bes. Untuk komposisi air garam, Natrium
Klorida (NaCl) telah ditambah pada 0, 20000 dan 40000 ppm untuk mengkaji kesan
kemasinan dalam kestabilan emulsi. Akhir sekali, proses pengemparan dilakukan
untuk mendapatkan sedimen asas dan air untuk emulsi. Hasil kajian menunjukkan
keupayaan natrium klorida untuk menjejaskan kestabilan emulsi dan juga
meningkatkan nilai pH akan menyumbang tautan titisan air dan menggalakkan
pemisahan.
 vii

TABLE OF CONTENTS

CHAPTER TITLE PAGE

TOPIC i
DECLARATON ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
ABSTRAK vi
TABLE OF CONTENTS vii
LIST OF TABLES x
LIST OF FIGURES xi
LIST OF SYMBOLS xii
LIST OF APPENDICES xiii

1.0 INTRODUCTION 1
1.1 Background 1
1.2 Problem Statement 3
1.3 Objectives 4
1.4 Scopes of Study 4
 viii

2.0 LITERATURE REVIEW 5

2.1 Introduction 5
2.2 Crude Oil Emulsion Composition 6
2.2.1 Asphaltenes 6
2.2.2 Resins 8
2.2.3 Waxes 9
2.2.4 Solids 10
2.2.5 Hydrocarbons 11
2.2.6 Oilfield brine 12
2.3 Emulsion Stability 12
2.3.1 Surface Films and Stability to Coalesce 13
2.3.2 Factors Affecting Stability 13
2.3.2.1 Heavy Polar Fraction in Crude Oil 14
2.3.2.2 Temperature 15
2.3.2.3 Droplet Size 15
2.3.2.4 pH Value 16
2.3.2.5 Brine Composition 17
2.3.3 Demulsification of Emulsion 17
2.3.2.1 Method of Demulsification 18

3.0 METHODOLOGY 21
3.1 Introduction 21
3.2 Materials 22
3.3 Material Preparation 22
3.3.1 Crude Oil Samples 22
3.3.2 Oilfield Brines 23
3.3.3 Emulsion Preparation 23
3.4 Experimental Procedures 24
3.4.1 Demulsification Process 24
 ix

4.0 RESULTS AND DISCUSSIONS 26

4.1 Introduction 26
4.2 Effect of Salinity and pH Value of the Brine 27
4.3 Experimental Results 27
4.3.1 Discussion on the Effect of Time on 29
Emulsion Stability
4.3.2 Discussion on the Effect of Salinity on 30
Emulsion Stability
4.3.3 Discussion on the Effect of pH on 32
Emulsion Stability

5.0 CONCLUSIONS AND RECOMMENDATIONS 34

5.1 Conclusions 34
5.2 Recommendations 36

REFERENCES 37

APPENDICES 40
 x

LIST OF TABLES

TABLE TITLE PAGE

4.1 Emulsion Separation Index at Given Salinity 31

4.2 Emulsion Separation Index at Given pH 32
 xi

LIST OF FIGURES

FIGURE TITLE PAGE

2.1 Hypothetical Diagram Representing the Molecular 7

Characteristics of the Asphaltenes Precipitated from
Petroleum by N-Alkane Addition
2.2 Hypothetical Representation of an Average Asphaltene 8
Molecule
2.3 Hypothetical Structure of an Average Resin Molecule 9
2.4 Average Structure of Paraffin Wax Molecule 10
2.5 Droplet Stabilization by Solids 11
2.6 Photomicrograph of an Emulsion Showing Interfacial Films 13
2.7 Interfacial Viscosity as a Function of pH 17
2.8 Typical Demulsifier Molecular Formula 20
3.1 Magnetic Hotplate Stirrer 24
4.1 Clear Separation between Water and Emulsion 29
4.2 Water Separation of Emulsion with Time for 30 minutes 30
4.3 Water Separation of Emulsion with Different Salinity for 30 31
Minutes
4.4 Water Separation of Emulsion with Different pH Value for 33
30 Minutes
 xii

LIST OF ABBREVIATIONS

W/O Water-in-oil
O/W Oil-in-water
W/O/W Water-in-oil-in-water
EOR Enhanced Oil Recovery
% Percentage
wt% Percent by weight
rpm Rotation per minute
ml Milliliter
ppm Part per million
min Minute
∑ Total
t Time
cm2 Centimeter square
ESI Emulsion Separation Index
 xiii

LIST OF APPENDICES

APPENDIX TITLE PAGE

A Data Of Test Done to Obtain Water 40

Separation
 x

LIST OF TABLES

TABLE TITLE PAGE

4.1 Emulsion Separation Index at Given Salinity 31

4.2 Emulsion Separation Index at Given pH 32
 xi

LIST OF FIGURES

FIGURE TITLE PAGE

2.1 Hypothetical Diagram Representing the Molecular 7

Characteristics of the Asphaltenes Precipitated from
Petroleum by N-Alkane Addition
2.2 Hypothetical Representation of an Average Asphaltene 8
Molecule
2.3 Hypothetical Structure of an Average Resin Molecule 9
2.4 Average Structure of Paraffin Wax Molecule 10
2.5 Droplet Stabilization by Solids 11
2.6 Photomicrograph of an Emulsion Showing Interfacial Films 13
2.7 Interfacial Viscosity as a Function of pH 17
2.8 Typical Demulsifier Molecular Formula 20
3.1 Magnetic Hotplate Stirrer 24
4.1 Clear Separation between Water and Emulsion 29
4.2 Water Separation of Emulsion with Time for 30 minutes 30
4.3 Water Separation of Emulsion with Different Salinity for 30 31
Minutes
4.4 Water Separation of Emulsion with Different pH Value for 33
30 Minutes
 xii

LIST OF ABBREVIATIONS

W/O Water-in-oil
O/W Oil-in-water
W/O/W Water-in-oil-in-water
EOR Enhanced Oil Recovery
% Percentage
wt% Percent by weight
rpm Rotation per minute
ml Milliliter
ppm Part per million
min Minute
∑ Total
t Time
cm2 Centimeter square
ESI Emulsion Separation Index
 xiii

LIST OF APPENDICES

APPENDIX TITLE PAGE

A Data Of Test Done to Obtain Water 40

Separation
 CHAPTER 1

INTRODUCTION

1.1 Background

The existence of stable emulsion in oilfield industry especially in production

is one of most problematic hindrance that need to be controlled effectively. Increased
usage of surfactant as a tertiary oil recovery technique and well stimulation involving
acid injection possibly creating this problem and researchers throughout the world
are searching for the best and effective method to diminish it. Emulsion can be
categorized into three classification, which are water-in-oil emulsion (W/O), oil-in-
water emulsion (O/W), and complex emulsion such as water-in-oil-in-water
emulsion (W/O/W) or oil-in-water-in-oil emulsion (O/W/O). The most common one
occurs in oil industry is water-in-oil emulsion (W/O).

Almost two-third of the world’s crude oil are produced along with emulsions
and need to be demulsified in order to be acceptable in a market standard. The
treatment of the hydrocarbon containing emulsion will increase as the field gets older
with high water cut values.
 2

During the production of crude oil, water-in-oil emulsion is often formed

along with water. Ranging from few seconds to few months, the stability of the
emulsion depends on the crude oil’s nature and also the water properties. The
dispersion of water due to the high pressure drop of the fluid passing through a choke
created a small droplets and promotes the formation of the emulsions.

The composition of crude oil is complex, including naphthenic acids and

carboxylic acids, as well as the heavier hydrocarbon which is greater than 50 of its
carbon numbers. These constituents are the contributors for making the emulsions to
be more stable as some of their properties are surface active.

Waterflooding can also cause the formation of emulsions as the crude oil
becomes the dispersion medium and brine becomes the dispersed phase and usually
stabilized by compound that originally exist in the formation such as asphaltenes,
resins, solids and waxes. Furthermore the presence of heteroatoms in asphaltenes
imparts amphiphilic characteristic in essentially aromatic structure (Selvarajan et al.,
2001).

Because of emulsion contains a significant volume of dispersed water that is

occupying the space in the processing equipment, it will greatly increase the
operating and capital cost. Upon emulsification, the characteristic and the properties
of the oil will be affected in a way that the density of oil increase significantly as
well as its viscosity.

Water-in-oil emulsions can be treated by the means of thermal, electrical,

chemical application as well as their combinations. Thermal process or usually called
by the heat treatment is based on the economics and ergonomics of the treatment
plant. However, extreme heat generated is not desirable when adding chemicals and
execution of electrostatic heat are more economically feasible.

By disturbing the surface tension of each droplet, electrical methods reorient

the polar molecules and causing the films around the droplet to be weakened (Grace,
1992). Typically this method is combined with the addition of heat or chemicals
because this process does not resolve emulsions altogether but just reduces energy at
 3

the droplets surface. In both oil field and refinery, chemical addition to break
emulsion is the most common methods available. Ultimately the process can be
coupled with the heat treatment to give effective results by being able to resolve
emulsions without additional equipment.

It is crucial to have a good understanding in regarding the stabilization of the

emulsion which then provide a platform for executing the most favorable treatment
for water-in-oil emulsions. Therefore, controlling the parameters that govern the
stability of the emulsions is a very important step towards the effective emulsion
breaking mechanisms.

1.2 Problem Statement

For this study, pH and brine composition of water-in-crude oil emulsion will
be investigated to test its stability by using gravity settlement along with
centrifugation as its demulsification processes. There are several questions that might
come up such as below:-

1. How does the pH values affect the stability of the emulsion

2. What are the composition or ions that will promote destabilization of the
emulsion
3. What is the optimum destabilization point with the values of pH and brine
composition are being altered
 4

1.3 Objectives

The objective of this study are:-

1. To investigate the effect of pH values towards the stability of the emulsion.

2. To investigate the effect of brine composition on the destabilization of the
emulsion.

1.4 Scope of Study

This study will focus on the crude oil from Angola oilfields only as for the
upcoming years Petronas will be implementing Enhance Oil Recovery (EOR) on the
local oilfields and the formation of emulsion will be encountered sooner. Tapis is one
of the example of an oilfield that will potentially produce emulsions when an EOR
project is executed sometime in year 2014 by Exxonmobil. Moreover, only water-in-
oil emulsion (W/O) will be studied because of majority of the emulsions formed
throughout the world is this type of emulsion. The study will be held in stationary
condition which no flowing condition will be constructed and standard room
temperature is applied.
 CHAPTER 2

LITERATURE REVIEW

2.1 Introduction

Asphaltenes, resins and naphthenic acid are compounds exist in crude oil.
Among those, asphaltenes is the most polar fraction and the most substantial
contained in the crude oil. During the oil production, it is responsible for the
formation of stabilized water-in-oil emulsion (W/O) by deposition and flocculation
of asphaltenes when the production disturbs the thermodynamic equilibrium of the
fluid.

The recovery factor of the oil production will be reduced if the deposition of
asphaltenes occurred. The phenomenon can triggers wettability changes of the
formation from water-wet to oil-wet. This is unfavorable especially near the wellbore
as it generally reduces the volume of recoverable oil. Furthermore the deposition of
asphaltenes at the inner walls of casing or tubing can also reducing the oil
production.
 6

During oil production and transportation, water is being produced along with
oil. The energy is supplied from the pressure drop of the choke or from the process in
the refinery. The surface active agents such as asphaltenes and resins adsorbed at the
interfacial films and impede the coalescence of the droplets. The stability of the
emulsions get strengthened by the acidity of the emulsion and by the high
concentration of Ca++ ions which can form rigid films around the water droplet.

Hence, the key to ensuring the easy emulsion breaking lies within the
destabilization of the emulsion itself. The adjustment of pH values and the initial
brine composition are the important parameters that need to be studied.

2.2 Crude Oil Emulsion Composition

2.2.1 Asphaltenes

Having molar masses of 1000 to 10,000 g/mol, asphaltenes is a black

amorphous powder which have no specific melting point. However when the
temperature is beyond 300-400oC, they start to decompose. Asphaltenes precipitation
may occur with changing temperature, pressure and oil composition.

Asphaltenes is insoluble in n-alkanes such as n –heptane. They are non-

volatile and polar fraction that can be represented as a petroleum component instead
of a chemical class. The carbon number of n-alkane is directly proportional with the
molecular weight, polarity and aromacity of asphaltenes. Figure 2.1 shows the
molecular characteristic of asphaltenes with the addition of n-alkane
 7

Figure 2.1: Hypothetical diagram representing the molecular

characteristics of the asphaltenes precipitated from petroleum
by n-alkane addition (Auflem, 2002)

A few possible structures have been introduced due to the

understanding of asphaltenes is not completely established. Figure 2.2 shows
the structure of asphaltenes including sulphur, nitrogen and oxygen.
 8

Figure 2.2: Hypothetical representation of an average

asphaltene molecule (Gafonova, 2000)

Acting as a microcolloid, asphaltenes particle contain one or more aromatic

sheets that stabilize the colloidal suspension. The molecules are believed to be
holding together with π - bonds, hydrogen bonds, and electron donor-acceptor bonds
(Aske, 2002).

2.2.2 Resins

Resins are black components which are made up of high molecular weight,
aromatic ring compounds, polar and polycyclic. Compared to the asphaltenes, resins
have same volatility as the equal sized hydrocarbon. Lighter resins tend to be less
colored, while the heavy one almost resemble red color. Counterpart with
asphaltenes, which do not dissolve in crude oil, resins is readily soluble in oil.
Content of resins in crude oil is approximately 1-40 wt%.
 9

Some studies shows that resins molecules consist of a highly polar end group,
which composed of sulfur and a non-polar group chain as well. Nitrogen takes
shapes as pyrolle and indole groups. The molecular structure of resin is shown in
Figure 2.3.

Figure 2.3: Hypothetical structure of an average resin molecule (Gafonova,

2000)

2.2.3 Waxes

Waxes are alkanes with high molecular weight which have a waxy texture.
They can precipitate when the reservoir’s equilibrium conditions are disturbed hence
the solubility of the waxes is reduced. Generally, they are the mixtures between
hydrocarbon and esters. From solubility and inductive force, they can form a highly
ordered structure and measured by the concentration and molecular weight. At a
given temperature and pressure, waxes are possible to coexist in multiple physical
condition.
 10

Basically, the waxes molecules can amalgamated with the fatty acids
presence in the mixtures and form a stabilized interfacial film. Figure 2.4 shows the
structure of the paraffin wax molecule system.

Figure 2.4: Average structure of paraffin wax molecule (Mussen,

1998)

2.2.4 Solids

Solids refer to insoluble materials which came from the precipitation of

asphaltenes from bitumen. Solids can increase the stabilization of the emulsion and
the factors affecting the stabilization are the solid particle size, interparticle
interactions, and the wettability of the solids. By the diffusion between solid particle
and the oil-water interface, they prevent the coalescence of the water droplets. In
addition, the interface may be electrically charged, thus enhancing the stability of
emulsion further.

In some cases, where the oil droplets is fairly larger than the diameter of the
solids particle, the solids are considered as in continuous phase. Although the size
distribution can be considerably similar, they cannot be treated as oil droplets. The
 11

viscosity of the emulsion contained in the crude oil increases significantly with the
presence of solids. Figure 2.5 shows that the interfacial film is being adsorbed by
viscoelastic solid film (Fanchi et al., 2006)

Figure 2.5: Droplet stabilization by solids

2.2.5 Hydrocarbons

Depending on the number of carbon atoms and the arrangement of whether

aromatic or cyclic structure, hydrocarbon can exist in all physical state. At the
atmospheric pressure and temperature, carbon numbers up to four will be in gaseous
state, where as the numbers between 20 or more will formed as liquids and solids.

Methane is the lightest compound exists in the hydrocarbon which made up of

one carbon atom and four hydrogen atoms. As the number of the hydrocarbon
increases, the molecular weight of the hydrocarbon also increases which results in
the change of physical and chemical properties. The structure may form into straight
chain, branched chain or cyclic chain. Petroleum crude oils contain hundreds of
different hydrocarbons, each with different chemical formulas.
 12

2.2.6 Oilfield brine

Increase of the salinity of the brine will affect the stability of emulsion
whether in water-in-oil emulsion or in oil-in-water emulsion. Binks (1993) have
shown in his experiment that droplet size distribution increases with the increase of
salt concentration in oil-in-water emulsion and vice versa in its counterpart.

2.3 Emulsion Stability

The durability of an emulsion to resist coalescence is a benchmark for

qualitative and quantitative measure of its stability. Emulsion is thermodynamically
unstable, which means at some point, the emulsion will start to resolve when the
interfacial energy gets converted into another form. However, most emulsion acquire
kinetic stability which in other words, it is stable over period of time. Emulsion is
categorized on the basis of their degree of kinetic stability.

Considered as a special liquid-liquid colloidal dispersion, stability of water-

in-oil emulsions is a result of tiny droplet size and the presence of an interfacial film
around water droplets and is caused by stabilizing agents. Emulsifiers can hinder
several mechanisms to destabilize the emulsion such as sedimentation, aggregation,
coalescence and phase inversion. Without change in the surface area, aggregation or
flocculation group water droplets together in the emulsion. In coalescence process,
the water droplets fuse together to form a larger drop with reduce the total surface
area.
 13

2.3.1 Surface Films and Stability to Coalesce

The interfacial films exist in the emulsion are believed to result from the
adsorption of high-molecular-weight polar molecules that interfacially active. There
are three types of film mobility, namely solid which form relatively soluble skins as
oil is withdrawn, highly mobile where it gives a momentary distortion and transition
that shows no distortion under compression (Strassner, 1968). By increasing the
interfacial viscosity, the films is further stabilized. High interfacial viscosity prevents
the coalescence during the oil-film drainage which leads to poor emulsion
breakdown. Figure 2.6 shows the persistence film in water –in-oil emulsion.

Figure 2.6: Photomicrograph of an emulsion showing interfacial films

(Kokal, 2005)

2.3.2 Factors Affecting Stability

Interfacial films are primarily responsible for the emulsion formation and its
stability. However there are some factors that give an absolute effect which can
 14

promote the further stabilization of the emulsion. The important ones are heavy polar
fractions, as discussed before which is asphaltenes and resins, temperature, droplet
size and its distribution, pH value of the brine and the brine composition.

2.3.2.1 Heavy Polar Fraction in Crude Oil

As discussed in the previous section, the polar molecules that can affect the
stability of the emulsion are asphaltenes, resins, and oil-soluble organic acids and
bases.

Asphaltenes are surface-active and this behavior makes them a good

emulsifiers. The compound has a polar part which have affinity toward water and
non-polar part which prefers oil. This dual affinity acts as bridge to connect both oil
and water interface to form a film.

Resins however make a combination with the asphaltenes to form a rigid

films. Some study shows that resins alone did not promote the rigidity of the film.

Waxes which is naturally presence in the crude oil similar like resins do not
exhibit the stabilization of the interfacial film when alone. However with the addition
of a nominal amount of asphaltenes to oils containing wax can form a stabilized
emulsions. This phenomenon is probably due to the synergy interaction between
waxes and asphaltenes.

Fine solid particles have the effectiveness of stabilizing the emulsions in

terms of the solid particles size, interparticle interactions and wettability of the solid.
The wettability of the particle affect greatly on the emulsion’s stability. When the
contact angles near to 90o results in an intermediate wetted solid generally induce the
tightest emulsion.
 15

2.3.2.2 Temperature

As the temperature can affect the physical properties of all the phases exist in
the emulsion, it is undeniable that temperature has its effect to the interfacial film
thus to the stability of the emulsion. The viscosity can be reduced by the increase of
the temperature and as explained in the previous section, viscosity is directly
proportional to the function of the stability of the emulsion. Rise in the temperature
of the emulsion increases the thermal energy of the droplet and increases the
frequency of the droplet collisions.

Although it seems efficient to increase the temperature indefinitely, Jones et

al. (1978), had shown that even at high temperature, a kinetic barrier prevent droplet
to coalesce still exist. Temperature influences the rate of buildup of interfacial films
by changing the adsorption rate and characteristic of the interface. It also affect the
film compressibility by changing the solubility of the crude oil surfactants in the bulk
phase.

2.3.2.3 Droplet size

The size of droplets in emulsion ranging from less than a micron to more than
50 microns. Emulsion that have smaller droplets will generally be more stable. It will
take a longer time to let all of the small-sized droplet to coalesce. Furthermore,
droplet size is also affecting the viscosity of emulsion. It is believed that emulsion
which have narrow droplet size distribution will acquire higher viscosity (Fortuny,
2006).
 16

2.3.2.4 pH value

Adding inorganic acids and bases strongly affect the stability of the
emulsions. According to Verzaro et al., (2002), pH will affect several parameters
such as droplet size and viscosity of the emulsion. The stability of emulsion is based
on the contents of heavy fraction molecules. For example with the presence of
asphaltenes, the interfacial films exhibit the strongest resistance to coalescence while
in the presence of resins the stability of the emulsion is the strongest in basic.

In addition, pH also has the influence on the type of emulsion formed. At low
pH values which is in acid, the emulsion formed is water-in-oil emulsion and for
basic pH condition it tends to form oil-in-water emulsions. Optimum pH for
demulsification is approximately 10 in the absence of demulsifier (Fortuny et al.,
2006).

Brine composition also has its relationship with the pH values of the
emulsions towards its stability. Effect of bicarbonate brine and distilled water on the
emulsion stability with the function of pH shows that the optimum pH for the
demulsification process is no longer 10 but it drops to 6 to 7. Figure 2.7 shows the
relationship between film’s viscosity and pH of the brine
 17

Figure 2.7: Interfacial viscosity as a function of pH

2.3.2.5 Brine composition

Specific ion present in the brine can also influence the interfacial film
rigidity. Water produced from the production consists of several ions and the most
common concentration of ions exist are sodium and chloride. The hydrophilic group
presence in the emulsion can react with these ions to form insoluble salts. Brine with
high Ca++ ions and a high Ca++/Mg++ ratio may form a non-relaxing, rigid films
around the water droplets, resulting stable emulsion. As many other compound and
polar molecule present in the emulsion, synergistic effect may occr when several
different cations are present at the same time.

2.3.3 Demulsification of Emulsion

Breaking of emulsion into separate parts which are water and oil is called
demulsification. There are three aspects that qualitative and quantitatively define the
measure of demulsification process. The first one is the rate of speed for the
 18

emulsion to get separated. The time taken for emulsion to be broken is an indicator
that shows the stability of the emulsion as the tight emulsion with small droplets
resist to coalesce with each other results in longer retention time. The second one is
the amount of water in the crude oil left after the breaking of emulsion. This is
generally important as the minimum requirement for the water content in the wet oil
that needs to be transported to handling facilities must be lower than 0.2% basic
sediment and water (BS&W) and at 10 pounds of salt per thousand barrels. The last
one is the quality of the water separated for disposal. Nearly all oil-producing
country implement a regulation against pollution to protect wildlife and the
environment nearby.

2.3.3.1 Methods Of Demulsification

Processes in breaking the emulsion are application specific because of the

huge range of crude oil types, the content of brines, and type of equipment for the
separation process and variety of chemical demulsifiers. Moreover, the properties of
emulsion can change over time, which add complexity to the treatment. In the
industry, it is not uncommon to use the application of heat and addition of chemical
demulsifier. Some of oil companies use electrostatic coalescence means to promote
gravitation settling as the emulsion is thermodynamically unstable.

Thermal methods reduces the oil viscosities and also the interfacial film’s
viscosity. Furthermore, the frequency of the droplets collide with each other increase
the number of possibility of them to coalesce by the absorption of thermal energy.
However, with this application alone rarely solve the problem and it needs to be
coupled with other technique such as chemical demulsifier to promote efficient
breaking. There are several downside of this method such as it costs more expense to
generate more heat. It also can result in the loss of light hydrocarbon which can leads
to reduced API gravity of the crude oil. Also, scale deposition and corrosion to the
treating vessel can occur with high operating temperature.
 19

Mechanical methods provide wide variety of mechanical equipment to be

used with different type of mechanism. One of the equipment is free-water knockout,
which separate the free water from the crude oil although it may be some associated
gas presence in the drums. Three-phase separators can provide substantial separation
with pre-set retention time at a given throughput rate. Readily available in the
market, the types are horizontal, vertical or spherical design in which has their own
unique feature. Based on Stoke’s Law, the settling rate of water droplet is given by:

2𝑔𝑟 2 (𝜌𝑤 −𝜌𝑜 )

v= ,
9𝜇

where v is the settling velocity of the water droplets, g is the gravitational

acceleration, r is the radius of the droplets, (𝜌𝑤 − 𝜌𝑜 ) is the difference in density
between water and oil, and 𝜇 is the oil viscosity. While this is applied to the treating
system, one must be caution because the operating condition changes throughout the
life of the reservoir, hence the design of this separator should be flexible enough to
cope with altering properties of the crude oil produced. Desalter is another equipment
which generally use a combination of chemicals, electrostatic treating and settling
time. Sometimes fresh water is added to reduce the concentration of the dissolved
salt.

Electrical methods sometimes used for demulsification. Effective use of high

voltage electricity generally theorized that water droplet have an associated net
charge, and by the application of the electric field, the droplets quickly collide with
each other so the coalescence process will happen quicker. It also disturbs the film
between oil and water interface by rearranging the polar molecules. Other than that,
with combination with heat treatment, electrostatic dehydration proven reduce the
heat required to break the emulsion.

Chemical methods is the most common technique available in the industry.

The process involves the addition of demulsifier which is a surface active compound
 20

which slips through between the oil and water interface and rupture and weaken the
rigid film and promote water coalescence. Usually this treatment is also combined
with heat, electric grids and coalescers to demulsify the emulsion. Demulsifier
consists of three parts. The first part is solvent which acts as carriers for the active
ingredients of the demulsifier. For instance, benzene, toluene and xylene are usual
solvents used. The next part is the surface-active ingredients that characterized by
hydrophilic-lipophilic balance (HLB) values. Low HLB value describe as the
chemicals having hydrophilic properties. Hence, higher value of HLB will
destabilize the emulsion which normally clocks greater than 8. The last one is
flocculants which defined as chemicals that flocculate the water droplets to collide
them thus promoting coalescence. Nevertheless, the amount of demulsifier added for
the treatment must be in optimal volume where too little of these compound will
leaves the emulsion unresolved and overtreated emulsion can form higher stability of
emulsion as the demulsifier is a surface-active agents. Figure 2.8 shows the typical
demulsifier used in the oil field.

Figure 2.8: Typical demulsifier molecular formula

 CHAPTER 3

METHODOLOGY

3.1 Introduction

This chapter is subdivided into two parts mainly the preparation of the
materials and the experimental procedures. The first part is regarding the synthesis of
water-in-oil emulsion. Whereas the second part concerning the experimental
procedures in measuring the stability of the water-in-oil emulsion. By adjusting the
pH and the composition of the brine, the optimum properties for demulsification can
be obtained. For the preparation of water-in-oil emulsion, crude oil and brine water is
mixed together. In stability analysis, in order to measure the stability of the emulsion,
emulsion separation index (ESI) is used after demulsification process. A preliminary
test is conducted to decide on the optimum speed and time of the rotation in
formation of emulsion. All of the test are conducted with the same crude oil and
emulsion system.
 22

3.2 Materials

The apparatus used in this experiment are:

1) Centrifugation equipment
2) Beaker
3) Measuring cylinder
4) Stirrer
5) Centrifuge tube

The material used in the experiment are:

1) Crude oil
2) Sodium Hydroxide (NaOH)
3) Hydrochloric acid (HCl)
4) Sodium Chloride (NaCl)
5) Dionized water

3.3 Material Preparation

3.3.1 Crude Oil Samples

Samples from Angola Field is used for this experiment. This crude oil is
provided from the FPREE store which characterized as medium to light oil with its
viscosity is at 8.32 centipoise in standard room condition.
 23

3.3.2 Oilfield Brines

The oil field brine which was used in this experiment will be a synthetic one
because of the ability to change their properties. According to Hing (1998), the
synthetic oilfield brine can be produced by using the equation:

Salinity Equation: Y= 8.3566X – 0.3582

Where,
Y = Salinity (%w/w); % in per thousand
X = NaCl concentration (ppm)

3.3.3 Emulsion Preparation

Water-in-oil emulsion is prepared in the laboratory with the use of Magnetic

stirrer as shown in Figure 3.1 which can acquire a maximum agitation speed up to
2000 rpm. However the speed is manually controlled and there is no automatic time
setting at the stirrer. The emulsion was prepared by mixing crude oil with 50%
synthetic brine by volume. About 1600ml of emulsion was prepared for this
experiment.
 24

Figure 3.1: Magnetic Hotplate Stirrer

3.4 Experimental Procedures

The experiment was done in the reservoir lab in N11, Universiti Teknologi
Malaysia. All of the apparatus and materials were either obtained from the lab or
from center store.

3.4.1 Demulsification Process

The demulsification apparatus, centrifugation was used in this research.

Emulsions were prepared in eight sets. The experiment is divided into two parts,
which are:
 25

1) Effect of pH on emulsion stability

a. The first brine sample with 20000 ppm NaCl was added with HCl
until the pH values reached 3.0 measured using pH meter
b. The brine and crude oil were mixed by using magnetic stirrer
c. Mixture of water-in-oil emulsion was poured into a beaker and
labelled as 3(pH)
d. The emulsion was allowed to age for one minute
e. The emulsion was allowed to separate by gravitational force
f. The mixture was put into centrifugation for 10 minutes
g. The Emulsion Separation Index was calculated
h. Step (a) was repeated for value 3.0, 5.0, 7.0, 9.0 and 11.0
i. Results was recorded

2) Effect of brine composition on emulsion stability

a. The first brine sample with 0 ppm was poured into a beaker and
labeled as 0 ppm
b. The brine and crude oil were mixed by using magnetic stirrer
c. The emulsion was allowed to age for one minute
d. The emulsion was allowed to separate by gravitational force
e. The mixture was put into centrifugation for 10 minutes
f. The Emulsion Separation Index was calculated
g. Step (a) was repeated for 20000 ppm and 40000 ppm
h. Results was recorded
 CHAPTER 4

RESULTS AND DISCUSSIONS

4.1 Introduction

The effect of pH and the salinity of the brine towards the emulsion stability as
reported in the literature was reviewed and discussed in Chapter 2. This chapter
presents all results obtained in demulsification process with the salinity of the brine
and the pH of the emulsion being altered.

In this experiment, there are no emulsifier added as the screening of the

chemicals is unnecessary to determine the stability of the emulsion. The main aim for
this experiment is to investigate the effect of salinity and pH value of the brine in
order for the emulsion to be unstable and promoting faster separation.

The formulation which is called emulsion separation index (ESI) was

calculated based on the total volume of water that is separated from the emulsion.
 27

4.2 The Effect of Salinity and pH Value of the Brine

In this study, the rate of demulsification of the emulsion is observed to be

dependent on the salinity and the pH value of the brine. The content of the crude oil
such as asphaltenes and waxes which act as stabilizers preventing the water droplets
to coalesce together and hinder fast separation process. Emulsion which is commonly
seen in the upstream process during the production is the water-in-oil emulsion
system. Oil which is continuous phase enclosed the water droplets where the
interfacial film of the drops is preventing the coalescence of water phase. McLean
and Kilpatrick (1997) pointed out that at high values of pH (10-13), charged densities
increase caused by polarization of polar groups, thus lowers the mechanical strength
of the interfacial film.

When the emulsion is formed, the droplets of water in oil phase are unable to
coalesce due to the presence of thin film covering the droplets. The stability of the
emulsion is measured on the resistant of the droplets to coalesce. The longer it takes
for the droplets to coalesce, the more stable it is. Since there are some inorganic
materials presence in the crude oil, it then further stabilize the emulsion by adsorbing
to the film of the droplets, hence increase the mechanical strength of the film. The
introduction of NaCl to the emulsion system will disturb the interfacial tension of the
films promoting destabilization of the emulsion.

4.3 Experimental Results

To investigate the effect of pH and the salinity of the brine towards emulsion
stability, two experiments were carried out. Water separation is observed in both
experiment as being shown in Figure 4.1. Based on the observation, the water
 28

droplets coalesce with each other indicating the water-in-oil emulsion system. It is
correspond with the scope of this study.

However, this experiment may be prone to some errors, such as sampling

errors, operator error and unable to read the exact level of water being separated due
to tendency of oil to adsorb to the surface of the container. Experiment is done in
very delicate manner and the same experiment is repeated twice to get the
reproducibility of the results.

The evaluation of demulsification is based on the percentage of water which

is separated over its initial water content, or Emulsion Separation Index (ESI). The
formula is given by:

𝛴 𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙. 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 𝑠𝑒𝑝𝑎𝑟𝑎𝑡𝑒𝑑 𝑎𝑡 𝑎 𝑔𝑖𝑣𝑒𝑛 𝑡𝑖𝑚𝑒 (%)𝑥100

𝛴 𝑡𝑜𝑡𝑎𝑙 𝑣𝑜𝑙. 𝑜𝑓 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑤𝑎𝑡𝑒𝑟 (%) ∗ 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑥𝑝𝑒𝑟𝑖𝑚𝑒𝑛𝑡

The total volume of water separated is the volume of water coalesce over
time and volume of initial water is the volume of the brine before it is being mixed
with the crude oil. The percentage shows the effectiveness of the demulsification
process. With high ESI value, it shows that it will be much more successful in
destabilizing the emulsion.
 29

Figure 4.1: Clear Separation between Water and Emulsion

4.3.1 Discussion on the Effect of Time on Emulsion Stability

Figure 4.2 shows that the graph of the emulsion stability on the separation of
water with respect with time. It is used to determine the settlement rate without
having its salinity or pH value being altered. The emulsion stability is tested for
certain period of time and lastly were centrifuged. The water content is 50% by
volume with respect to oil and its salinity is 0 ppm having 7 of its pH value. From
figure 4.2, the water separated is less than 1% at 30 minutes observation time. This
small change in separated water shows that a tight emulsion was formed which are
very difficult to break even in longer time. Note that during the first 5 minutes of the
gravity settlement there is no water separated at all with the highest percentage of
water is at 0.8%. The sample is then centrifuged for 10 minutes to completely
separate the water. The ESI for this particular experiment is 20.4%.
 30

0ppm, 7pH
0.9
0.8
0.7

Water separated, %
0.6
0.5
0.4
0.3
0.2
0.1
0
0 5 10 15 20 25 30 35
Time, minutes

Figure 4.2: Water Separation of Emulsion with Time for 30 minutes

4.3.2 Discussion on the Effect of Salinity on Emulsion Stability

For this means of experiment, three values of salinity of the brine were tested
for determining the optimum level of NaCl. Three sets of brine were formulated and
they were mixed with the crude oil at the same time. Measurement of NaCl was done
by using the Electronic Balance with having its sensitivity up until five decimal
places in milligram. The result of this experiment is shown in Figure 4.3. The sample
was tested with fixed pH value which is 7 and the experiment is held in standard
room temperature and pressure.

It is observed that the water separation is increasing when the salinity of the
brine increases. For the first five minutes, it is observed that 0 ppm salinity of the
brine yields no water at all, whereas for 20000 ppm and 40000 ppm salinity of brine
yield 0.8% and 2.6% respectively. This shows the positive effect of NaCl content
when the electrolyte is present in the emulsion. During 30 minutes of the experiment,
 31

40000 ppm salinity of the brine gives 32% of water separation with gravity
settlement alone, in contrary to the 0 ppm salinity which only marks at 0.85% of the
total water separated. This indicate that the NaCl disturbs the interfacial tension of
the film and the droplets start to coalesce rapidly with external forces except for the
gravitational force alone. Okasha et al (2009) point out that the interfacial tension
between the crude oil and the brine is increasing with the increase salinity of the
brine. Hence, this explained why the oil and the water phase separated with the
increase of salinity of the brine. It also should be noted at the beginning of the
experiment, up until the first 15 minutes of the experiment, 20000 ppm and 40000
ppm show similar amount of water separated until it reaches 20 minutes when
suddenly 40000 ppm abruptly increases its water separated content. Further study
should be done to investigate this phenomenon.

Emulsion separation index for each salinity are given in Table 4.1 below.
Note that at 40000 ppm of NaCl presence in the brine yields the highest percentage
indicating its unstability to form emulsions.

Table 4.1: Emulsion Separation Index at Given Salinity

Salinity ESI
0 ppm 12.991

20000 ppm 22.775

40000 ppm 27.025

35
30
Water separated, %

25
20
0ppm
15
20000ppm
10
40000ppm
5
0
0 5 10 15 20 25 30 35
Time, minutes

Figure 4.3: Water Separation of Emulsion with Different Salinity for 30 minutes
 32

4.3.3 Discussion on the Effect of pH on Emulsion Stability

One of the factors contributing to destabilization of emulsion system is the

pH value of the brine. An experiment was conducted to see the validation of this
claim and determine the optimum pH level of the brine for demulsification. For this
experiment, the pH value was controlled by adding HCl for acidic and NaOH for
alkaline.

Figure 4.4 points out the water separated from the emulsion after leaving it to
settle down by using gravitational force. It is notable that at pH lower than 7 yield no
water content at all and at pH 3 the water content after centrifuge it for 10 minutes
with 1000 rpm is 12.5 ml. This indicates that the emulsion form is tight type, resist to
coalesce even with centrifugal force is being applied. On the other hand, emulsions
with higher value of pH give better water separation than the lower ones. Hence, the
statement made by McLean and Kilpatrick in 1997 is proven to be a match from this
experiment.

The ESI for this experiment is given in the Table 4.2. Centrifugation
experiment is also included in this index calculation.

Table 4.2: Emulsion Separation Index at Given pH

pH Value ESI
3 6.25
5 12.5
7 22.3975
9 58.065
11 67.44
 33

80

70

60 3pH

Water separation, %
50 pH7
pH9
40
pH11
30
pH5
20

10

0
0 5 10 15 20 25 30 35
Time, minutes

Figure 4.4: Water Separation of Emulsion with Different pH Value for 30 minutes
 CHAPTER 5

CONCLUSIONS AND RECOMMENDATIONS

5.1 Conclusions

Asphaltenes, resins and waxes are common solids which are present in the
crude oil. These agents act as a stabilizer which contribute emulsion formation that
can occur during production phase or in flowlines. Stability of an emulsion
characterized as the persistence of the droplets to coalesce and separated due to its
properties and several factors including the presence of particle such as solids.

Oil in the reservoir is produced together with brine water. This is the leading
cause of emulsion formation and crude oil is invaluable if the water content is more
than 0.1%. Hence, crude oils must be treated by using demulsification process. There
are four types of emulsion; W/O, O/W, W/O/W and O/W/O but in the petroleum
industry, the most common emulsion formed is W/O.

Brine composition and its pH value plays an important roles in determining

the optimum condition for demulsification. The brine content varies from one oilfield
 35

to another thus the degree of stability of an emulsion also different when comparing
crude oil from another location.

Bottle test method or jar test method is commonly used in water separation
measurement in the demulsification of crude oil emulsion. To choose the most
effective parameter of the separation, the properties of brine as well as its pH values
were tested and the results were recorded.

From this study, there are few remarks can be concluded. The conclusions are
as follows:

1. The water separation efficiency is increasing with the increase of the

salinity of the brine. This is mainly due to the presence of electrolyte
disturbs the interfacial film of the droplet and lowers its mechanical
strength.
2. The pH of the brine affects the stability of the emulsion formed in which
the separation is favoring the pH values higher than 7. The polarization of
the polar group changes the charged densities and promoting faster
coalescence.
3. At pH of 3, tight emulsion is formed and takes more forces in order to
separate between those phases
4. There was a similar trend of water separation observed. The trend can be
divided into three stages. At the first stage, a rapid change on the volume
of separate water occurred which indicates that the emulsion is not at a
stable condition. A medium reduction on the volume of separate water
can be recorded at the second stage shows that the emulsion settled was
more stable while at the third stage a very slow change can be observed. It
indicates that the water are almost separated at the bottom from emulsion.
 36

5.2 Recommendations

For further investigation, it is recommended that:

1. The demulsification process should be done in elevated temperature and

pressure, which in theory promotes better separation than standard room
condition.
2. The combination of electric coalescence or microwave heating should be
considered to investigate which of these method is more effective.
3. Different types of crude oil should be used in order to thoroughly investigate
the interactions between NaCl with the crude oil content.
 CHAPTER 5

CONCLUSIONS AND RECOMMENDATIONS

5.1 Conclusions

Asphaltenes, resins and waxes are common solids which are present in the
crude oil. These agents act as a stabilizer which contribute emulsion formation that
can occur during production phase or in flowlines. Stability of an emulsion
characterized as the persistence of the droplets to coalesce and separated due to its
properties and several factors including the presence of particle such as solids.

Oil in the reservoir is produced together with brine water. This is the leading
cause of emulsion formation and crude oil is invaluable if the water content is more
than 0.1%. Hence, crude oils must be treated by using demulsification process. There
are four types of emulsion; W/O, O/W, W/O/W and O/W/O but in the petroleum
industry, the most common emulsion formed is W/O.

Brine composition and its pH value plays an important roles in determining

the optimum condition for demulsification. The brine content varies from one oilfield
 35

to another thus the degree of stability of an emulsion also different when comparing
crude oil from another location.

Bottle test method or jar test method is commonly used in water separation
measurement in the demulsification of crude oil emulsion. To choose the most
effective parameter of the separation, the properties of brine as well as its pH values
were tested and the results were recorded.

From this study, there are few remarks can be concluded. The conclusions are
as follows:

1. The water separation efficiency is increasing with the increase of the

salinity of the brine. This is mainly due to the presence of electrolyte
disturbs the interfacial film of the droplet and lowers its mechanical
strength.
2. The pH of the brine affects the stability of the emulsion formed in which
the separation is favoring the pH values higher than 7. The polarization of
the polar group changes the charged densities and promoting faster
coalescence.
3. At pH of 3, tight emulsion is formed and takes more forces in order to
separate between those phases
4. There was a similar trend of water separation observed. The trend can be
divided into three stages. At the first stage, a rapid change on the volume
of separate water occurred which indicates that the emulsion is not at a
stable condition. A medium reduction on the volume of separate water
can be recorded at the second stage shows that the emulsion settled was
more stable while at the third stage a very slow change can be observed. It
indicates that the water are almost separated at the bottom from emulsion.
 36

5.2 Recommendations

For further investigation, it is recommended that:

1. The demulsification process should be done in elevated temperature and

pressure, which in theory promotes better separation than standard room
condition.
2. The combination of electric coalescence or microwave heating should be
considered to investigate which of these method is more effective.
3. Different types of crude oil should be used in order to thoroughly investigate
the interactions between NaCl with the crude oil content.
 37

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 40

APPENDIX A

DATA OF TEST DONE TO OBTAIN WATER SEPARATION

A) Effect of salinity towards demulsification (% of water separated)

T (min) Water Separated (%)

Salinity (ppm) 0 20 000 40 000

0 0 0 0

5 0 0.8 2.6

10 0.68 4 6.4

15 0.76 13 14

20 0.8 20 30

25 0.84 22 31.2

30 0.848 22.4 32

centrifuge 100 100 100

 41

Emulsion Separation Index

Salinity, ppm ESI.

0 12.991

20000 22.775

40000 27.025
 42

B) Effect of pH value towards demulsification (% of water separated)

Time
0 5 10 15 20 25 30 Centrifuge
pH

3 0 0 0 0 0 0 0 12.5

5 0 0 0 0 0 0 0 25

7 0 0.76 5.2 13.2 19.6 20.2 20.22 25

9 0 40 57.2 60 68 69.6 69.72 25

11 0 68.8 71.6 74 74.8 75.12 75.2 25

Emulsion Separation Index

pH ESI

3 6.25

5 12.5

7 22.3975

9 58.065

11 67.44