Accepted Manuscript

Review article

Overview on petroleum emulsions, formation, influence and demulsification

treatment techniques

Murtada Mohammed Abdulredha

PII: S1878-5352(18)30244-2
DOI: https://doi.org/10.1016/j.arabjc.2018.11.014
Reference: ARABJC 2413

To appear in: Arabian Journal of Chemistry

Received Date: 17 May 2018

Accepted Date: 15 November 2018

Please cite this article as: M. Mohammed Abdulredha, Overview on petroleum emulsions, formation, influence and
demulsification treatment techniques, Arabian Journal of Chemistry (2018), doi: https://doi.org/10.1016/j.arabjc.
2018.11.014

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers
we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting proof before it is published in its final form. Please note that during the production process
errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
 Title page

Name of the author: Murtada Mohammed Abdulredha

Title: Overview on petroleum emulsions, formation, influence and demulsification

treatment techniques

Affiliation(s) and address(es) of the author(s): Universiti Putra Malaysia, Jalan Upm,
43400 Serdang, Selangor

Ms. Murtada Mohammed Abdulredha

Department of Chemical and Environmental Engineering,

Faculty of Engineering,
Universiti Putra Malaysia,
43400 UPM,
Serdang Selangor

E-mail address of the first author: murtadaeng94@gmail.com

E-mail address of the corresponding author: aslina@upm.edu.my

1
Abstract
The most challenging aspect in petroleum industry is high produced water accompanying crude oil
extraction. In modern days, environmental attention has become very significant due to large quantity of
produced water. Produced water in crude oil extraction consists of a mixture of several compounds,
including inorganic, organic and other elements. The elements in produced water have a wide
environmental influence and sometimes cause poisonous impact on sounded area. Meanwhile, there are
several techniques to treat produced water. However, a major part of produced water is an emulsion and
this leads to a major problem associated with crude oil treatment and transport. At the same time,
limitations in treatment techniques for produced water have been demanding researchers to investigate on
demulsification techniques for several years. Researchers also noted that there are a lot of elements
influencing emulsion stability and interfacial film, including asphaltenes, resins, solid particles, water and
oil content, PH, etc. However, one of the techniques that has received attention in enhanced oil recovery is
a chemical method by using surface active agents (surfactant).

Keywords: emulsion, produced water, interfacial stability, demulsification mechanism, surfactant

2
 Contents
1. Introduction
1.1. Water Production Sources
1.2. Volume of Generated Water
1.3. Overall Onshore and Offshore Produced Water
1.4. Elements influencing on volume of extraction water
1.5. Gas Generated Water Toxic
1.6. Coal Bed Methane Generated Water

2. Risks of Generated Water

2.1. Poisonous Impact on Environmental Marine Organisms
2.2. Examination of Chronic Toxicity
2.3. Additional Influence Concerns
3. Oily Wastewater
3.1.Emulsion Formation and Stability
3.1.1. Impact of Turbulence on Emulsification.
3.1.2. Impact of Asphaltenes, Resins and other Components on Emulsification
3.1.3. Emulsion Thermodynamic Aspect
3.2. Classification of Emulsion
3.2.1. Water-in-Oil Emulsion
3.2.2. Oil-in-Water Emulsion
3.2.3. Multiple or Complex Emulsion

4. Destabilization Emulsion
4.1. Interfacial Films, Elastic Modulus and Viscous Modulus
4.2. Duration Time and Agitation Speed
4.3. Size and Distribution Impact
4.4. Temperature
4.5. Solids
4.6. Environment Medium
4.7. Spread Phase Salinity
4.8. Water Content and Oil Content

5. Demulsification and Desalination of Oil Recovery Processes

5.1. Measurement of Stability

5.2. Destabilizing Emulsions and Demulsification Methods
5.3. Surface Active Agents
5.4.General Classification of Surface Active Agents
6. Summary
Acknowledgements
References

3
1. Introduction.
A survey of fuel remains is one of the most important activities in recent society because of large fuel-
derived products consumption in several areas. To cover the demand for new reservoirs, the search for new
fields has risen in past years. In Brazil, exploration of new petroleum wells below the sea has opened
several new opportunities, and at the same time it has demanded for technological expansion in exploration
use, treatment and petroleum control, besides its products and wastes that are created by this activity
(Cassella, Dos Reis, Santelli, & Oliveira, 2011).
The light dense hydrocarbons traveled to gap locations and converted some of the water from the formation
to hydrocarbon reservoirs. Consequently, these reservoir rocks will usually contain petroleum hydrocarbons
(liquid and gas) together with water. Resources flow through underground water may rise from above or
below the hydrocarbon region, flowing from inside the hydrocarbon area, or stream from injected fluids
and additives during production activities. This type of water is frequently considered as “connate water” or
“formation water” and becomes produced water when the reservoir is produced as these fluids are carried
to the surface. Produced water can be defined as the water that is raised to the surface with the hydrocarbon
resource and is brought to the surface along with crude oil or natural gas (Veil, Puder, Elcock, & Redweik
Jr, 2004). However, the hydrocarbon compounds are presented as a fluid mixture on the surface. The
combination of mixture usually depends on the nature of hydrocarbons being extracted. The combination
normally contains liquid and gaseous hydrocarbons, dissolved or solid contaminants, water, solid particles
like salts, silt, sand, iron and additives, such as chemical compounds and injected fluids during production
and exploration activities. Furthermore, the process of extraction includes disarmament of water and this
may lead to natural gas migration to other wells. Formation of water from coal bed methane (CBM)
production is also concerned as produced water. There are some similar properties between this type of
produced water and water from oil or conventional gas production, but may be very different in
composition (Veil et al., 2004). Furthermore, most fields of crude oil often have a higher content of water
and fines, while this combination of fines and high water content produced very stable crude oil emulsions.
The increasing in emulsion viscosity due to the large number of small water droplets often leading to
increasing the cost of operation condition (Sellman, Sams, & Mandewalkar, 2013). The emulsion can be
produced due to contact between two immiscible liquids, the presence of emulsifying compounds in crude
oil, for example, asphaltenes as well as turbulence during production activates. While water in oil emulsion
very common in petroleum industry compared with other types of emulsion (de Oliveira, Miranda, de
Carvalho, & Miranda, 2018). Asphaltenes considered as the primary parameter in stabilizing water in oil
emulsion even with low content (Juan Zhang, Tian, Lin, Yang, & Dong, 2016). The issue of separating
water or breaking water in oil emulsion returns to the beginnings of production of crude oil. The emulsion
in the petroleum industry is very undesirable and in the same time, the formation of the emulsion is
ineluctable. The emulsion should be broken into two-phase before transportation and refinery process and
meet the specific standard of water and salt residual, while the content of water should be less than 1%
(Fink, 2015). The process of breaking emulsion into two-phase refers by demulsification terms.
Furthermore, the process of demulsification process is a very intricate process, generally there three basic
methods for demulsification physical, chemical and biological. The efficiency of methods depends on the
capability in minimizing emulsion stability until the separation occurs (Zolfaghari, Fakhru’l-Razi,
Abdullah, Elnashaie, & Pendashteh, 2016). In the petrochemical industries, the emulsion must be broken
into two phase before further refining process. While using chemical additives that know as demulsifers are
the prevalent mechanism in breaking emulsion (Issaka, Nour, & Yunus, 2015). Demulsifers or surfactant
are organic particles that consist of two parts, polar portion that attractive to the water phase (hydrophilic)
and the non-polar portion that attractive to oil phase (hydrophobic). There are basically four sorts of
surfactant nonionic, ionic, amphoteric and polymer surfactant (Cullum, 1994; Salager, 2002; Yu & Xie,
2012).
This overview paper on previous studies and related literature on produce water, emulsion formation,
classification, and emulsion stability as well as demulsification methods.

4
1.1. Water Production Sources
Reservoirs naturally have water in the shape of a denser layer under the hydrocarbon sheet and usually this
water is called formation water or produced water. Sometimes produced water comes from another source
exactly from the surface as injected water for hydrocarbon compounds extraction to achieve high oil
recovery.
Petroleum resources normally contain natural water or formation water mixed with petroleum in oil
reservoirs. Figure 1, gives a general imaginary of reservoir layers, where generally water sits below the
hydrocarbon seams and formation water is slightly acidic. In addition, during the hydrocarbon compounds
extraction, a drop in reservoir pressure. Consequently, water is used to maintain the reservoir pressure by
injecting water into the water layers to enhance oil recovery. Moreover, to inject water, there can be water
penetration from outside the reservoir zone, and thus, to ensure a continuous oil and gas production, the
time when formation water reaches production well begins and production of water besides the
hydrocarbons can be considered. This type of water is recognized as produced water or oilfield brine.
Volume of by-product that is produced during oil and gas recovery operations is a mixture of several
compounds, including injected water, formation water, treating chemicals and hydrocarbons, that are
generally organized as oilfield produced water, natural gas produced water and coal bed methane (CBM)
produced water, depending on the source (Chan, Starinsky, & Katz, 2002; Reynolds & Kiker, 2003;
Strømgren et al., 1995).

Figure 1. Reservoir layers (Igunnu & Chen, 2012).

1.2. Volume of Generated Water

During crude oil and gas extraction, produced water is mostly created through the process. In general, oil
and gas production from subsurface resources is accompanied by water or brine, which is also indicated as
produced water. At the end of the reservoirs age, especially after using secondary or tertiary recovery
methods, the amount of produced water from wells increases and usually exceeds the volume of the
hydrocarbons before when compared with the first production stage. The percentage of water produced

5
from reservoirs basically depends on two factores; location and reservoir age. Generally, the average for
produced water can vary from a few percent in the first production stage to more than 95% in the end of
exploitation. Universal experts approximate that for every barrel of crude oil, three barrels of produced
water are created, which means that more than half of the reservoir production is water (Fakhru’l-Razi et
al., 2009). There are two major ways for produced water removal. The first is by draining water to the sea.
Water that is to be discharged into the sea is treated to achieve a certain quality level that is specified by
local environmental policy. Depending on the spot, the range of 30 to 40 ppm is the highest average oil in
water (OIW) content for drainage (Igunnu & Chen, 2012). The second way for produced water discharge is
by reinjecting and pumping the water into a disposal or a production reservoir. Moreover, the reinjection
way is more preferred than the first way in handling produced water from the subsea production and
processing facilities. At the same time, the process also conducts several hazards, for instance reservoir
souring or harmful formation due to decline in injectivity. Additionally, emulsified oil droplets and
suspended solid particles in the produced water can fill holes in the reservoir and reduce the permeability of
formation. This leads to one fact that high quality is strictly required for reinjection and discharge options
in handling produced water (Paige & Sweeney, 1993). So the treatment methods of produced water can be
divided into three types to ensure processing quality.
1.3. Overall Onshore and Offshore Produced Water
Total extraction of produced water is approximately 250 million barrels per day, while 80 million barrels
per day is for oil and this reverses the contrast between water and oil production. Consequently, water to oil
percentage is about 3:1 and this shows that water production is 70%. The global water extraction has grown
since a decade ago and is still rising. Produced water production is usually matured in the old wells, but for
driven down depends on the methods used for managing and entering of new oil wells into the service (Dal
Ferro & Smith, 2007; Khatib & Verbeek, 2003). Figure 2 gives an estimate of onshore and offshore
produced water extraction since 1990 until 2014.

Onshore water Offshore

300000

250000
BBIS*1000 PER DAY

200000

150000

100000

50000

0
1991

2010

2015
1990

1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009

2011
2012
2013
2014

YEAR

Figure 2. Overall water production of onshore and offshore (Dal Ferro & Smith, 2007).

1.4. Elements Influencing on Volume of Extraction Water

6
(Reynolds & Kiker, 2003) estimated that there are several elements that affect the production volume of
produced water besides the age of wells:

 Drilling well technique: basically there are two types of well, namely horizontal and vertical well, The
horizontal well produced water production is more than that of vertical well, at the same level of
drawdown or become the same production if the horizontal well drawdown is reduced .
 Location of well within homogeneous or heterogeneous reservoirs: the area of wells, especially
homogenous reservoirs, take a part in decreasing the production of water, and at the same time the
increase in production of horizontal reservoirs versus unstimulated vertical wells is related to the
nature of area that is in contact with the wells.
 Diverse sorts of completion: generally there are two factors in these elements that ascertain rules. The
first factor is to avoid drilling towards water area and second is an open hole method which permits
testing of drilling regions. However, the second factor (perforated completion method) gives more
control because the area can be perforated and tested.
 Water separation methods: there are several technologies that are used for treating and lifting water to
reduce cost for wells that produce high amount of saline water.
These technologies include treatment by using gelled polymers to shut-off water, dropping beam pump
lifting costs and the power options help to drop the electrical costs and separation technologies.
 Water flooding and injection to enhance oil recovery: the production rate of oil wells will
progressively drop with time, so use water flooding to maintain a steady production rate. As a result of
water flooding, the water production ratio will become higher at the same time as the water injection
volume increases. In this case, it is essential to treat water with chemical characteristics. This is very
important for produced water treatment, or makeup to enable sealing, clay swelling and brine
incompatibilities.
 Low mechanical integrity: mechanical problems cause a lot of water entries and one of these problems
is casting holes which are caused by wear or corrosion, and splits caused by flows; extreme pressure
can let undesirable fluids to enter and raise water production.
 Underground communications: usually difficulties in underground communications occur near
reservoirs or wellbores. All these difficulties work on rising produced water. Near wellbore problems
are fence failures, completions and route behind casing. Reservoir related challenges are channeling,
coning, cresting across higher permeability areas or fractures and fracturing out of area.

1.5. Gas Generated Water Toxic

During gas extraction, produced water is separated at the same time. However, the construction water and
condensed water that are included in gas process is produced water. The characteristics of produced water
that is extracted during gas production are distinguished by the molecular-weight contents, like
ethylbenzene, toluene, xylene (BTEX) and benzene. All these contents are considered as light aromatic
hydrocarbons compounds as compared to produced water that is produced from oil. In addition, these
compounds make water relatively more toxic. At the same time, many research point out that produced
water from oil platforms is about 10 times less toxic than water extracted from gas/condensate platforms
(Jacobs, Grant, Kwant, Marquenie, & Mentzer, 1992). In addition, the water production volume from
offshore gas fields is lower. Normally, chemical additives that are used during gas extraction consist
hydrogen sulfide, dehydration and elimination compounds. In addition, there is a wide range of chemical
elements that exist during water production from gas platforms. Chemicals include brines solution,
additives and inorganic acids (Stephenson, 1992). The characteristics of produced water from offshore oil
platforms are greatly different from produced water from gas platforms. (Jacobs et al., 1992) researched in
the North Sea and found that pH and chlorides concentrations were 8.1 and 19 g/L, alternately. The pH for
produced water from crude oil wells in the North Sea was 6 to 7.7, while 3.5 to 5.5 was from gas wells,
which was more acidic. Chloride concentration was about 1 to 189 g/L for produced water from gas
production, while produced water from oil wells was 12 to 100 g/L.
1.6. Coal Bed Methane Water Generated

7
Water production from coal bed methane (CBM) varies in three basic point compositions; influence on
environments, production technique from oil and gas and traditional technique of produced water. Water
content in the coal layers leads to a rise in hydrostatic pressure and this helps to adsorb methane on the
crystal surface. One of the methods that is used to remove methane from the crystalline body is by
decreasing the reservoir head in the coal layers. During extraction, water holds methane in the coal layers,
while produced water is created at the same time. In addition, water quantity is the other point of difference
in CBM produced water from oil and gas. produce water in production stage, . The quantity of CBM
produced aqueous phase is high in quantity at the first stage of production and reduces towards the final
stage of production. Simultaneously, when the size of aqueous phase is decreasing in CBM, the quantity of
methane extraction increases. There are two general ways to deal with produced water from CBM; one is
by processing and pulling to the surface or reinjecting. The nature of produced water from CBM vary,
depending on three point of the original depositional environment, i.e., nature of coal, and coal layers
depth, and these properties alter across extraction regions (Jackson & Myers, 2002).
The amount of produced water increases with rise in CBM production, and at the same time, the concern
about produced water influence on the environment is growing, while there are some suspicions related to
the environment effect of these water. Moreover, relevant managers and engineer are keen on
environmental safety. The data of produced water are increasing and there are several states which provide
information about produced water. These sources include institutes and different states ground water
information centers in the USA. The organizations which collect information, confirm the information,
assessing the dependability and reliability of information is done through DOE and the Bureau of Mines,
and the USGS organization. Simultaneously, not all data about the effect of CBM production are totally
understood.

2. Risks of Generated Water

Produced water can form several environmental effects, depending on the area that water is produced.
However, discharges into small streams have more influence on the environment than the discharges in
open ocean due to the importance of dilution that occurred after drainage. The influence of water extraction
is related to several factors; the accompanying parts which talk about the potential effects that depend on
the area where production occurred and the type of produced water.

2.1. Poisonous Impact on Marine Environment

Effects are identified as exposure of life to different chemical concentrations . Components that have
influence are quantity of delivered water compounds and solution density. Thus, their potential effect on
sea-going living beings are incorporated in the following points (Georgie, Sell, & Baker, 2001):
 Decrease the release in environment.
 Sudden and longstanding sedimentation.
 Evaporation of light hydrocarbons compounds.
 The interaction between some species in seawater and physical-chemical of produced water have
influence on delivered water segments.
 Adsorption on particulate material.
 Biodegradation of natural mixes to less complex mixes.

Inside the marine condition, it is important to recognize shallow, ineffectively flushed waterfront zones and
the vast sea. For seaside processes, the accepting conditions can incorporate shallow, near shore zones,
bogs and regions. There are many examinations done on destiny and impacts of water that is releaseed into
the waterfront situations of the Gulf of Mexico (Rabalais, McKee, Reed, & Means, 1992). (Rabalais et al.,
1992), approved that released water has pollute impact and hat depend on size and concentration of
regional hydrocarbon. Perceiving the potential for shallow-water impacts, EPA prohibited the releases of
produced water into beach front waters with an eliminate period beginning in 1997. (Rabalais et al., 1992),
noted that profound water and quick streams; thus, give more than satisfactory weakening. Moreover, in

8
spite of the fact that residue contamination is obvious at most studied areas, impacts on the benthic groups
might be restricted or not apparent. For offshore activities, key components cover concentration of
constituents and different features of the constituents, for example, poisoning, bioavailability and shape.
Real destiny and impacts fluctuate with volume and structure of the release and the hydrologic and physical
qualities of the receiving environment (Rabalais et al., 1992). A key concern is the potential for poisonous
consequences for living amphibian due to release water into the water environments, like estuarine and
marine.

2.2. Examination of Chronic Toxicity

Most oil and gas offshore wells are subjected to chronic toxicity examination under EPA organization. The
examination result was positive and showed that there was no poisonous water problems in the USA. In
other countries, especially in North Sea, the researchers focused more on compound interactions effect of
chemical martials and applied new methods to control produced water. For instance, in Norway, there are
numerous programs applied to reduce poisonous discharges into the environment (Johnsen, Frost,
Hjelsvold, & Utvik, 2000; Veil et al., 2004). Furthermore, these methods or programs depend on comparing
the predicted from spirited concentrations of each element, without any concentration, and see the harmful
effects on the environment. There are two basic assessment program models (DREAM) and dose-related
risk applied to estimate the environmental impact factor (EIF). Moreover, this method depends on the
quantitative work to estimate the impact of each extraction. This technique is very viable with Norwegian
due to limited offshore production in the North Sea. At the same time this technique is not very common in
the Gulf of Mexico because it is not workable in such area due to the large offshore extraction. The
examination of chronic toxicity in the Gulf of Mexico provides poor control.

2.3. Additional Influence Concerns

The water production from wells increases with age of wells, and at the same time the production and
treating prior to water from deep offshore platforms will rise. Furthermore, there is limitation in using
common treatment methods of produced water due to the lake in the space and movement on the rigs. This
lead to increase in challenges on which techniques should be applied for treating the produced water and
understanding of compounds in the water, besides how these elements effect on the environment and which
of these compounds will increase. In addition, the acute toxicity of produced water depends on
concentration of compounds water and the inside production area. Chemical additives, antagonistic effects
and synergistic can cause or increase the produced water acute toxicity (Veil et al., 2004).
3. Oily Wastewater
The water extraction from offshore and onshore wells is produced as "free" water or sometimes as an
emulsion. Any two immiscible liquids, like water in oil, can be classified as emulsion (Lim, Wong, Law,
Samyudia, & Dol, 2015). Basically there are three common types of emulsion as follows:

 Water-in-oil (W/O) emulsion

 Oil-in-water (O/W) emulsion
 Multiple emulsion
The common type of emulsion in the petroleum industry, which is water-in-oil emulsion, is emulsion with
water drops diffused in the oil constant phase. Oil-in-water is a contrast of previous type of emulsion.
Multifaceted emulsion or multiple emulsion is water-in-oil-in-water (W/O/W) emulsion added to oil-in-
water-in-oil (O/W/O) emulsion (Khan et al., 2011; Schramm, 1992b). while in each field there are many
applications of these emulsions. In petroleum, food and pharmaceutical the O/W and W/O emulsions are
more common than the multiple emulsion (Garti, 1997; J. S. Lee et al., 2004; Oh et al., 2002; Okochi &
Nakano, 2000), while in each field there are many applications of these emulsions. In petroleum, food and
pharmaceutical the O/W and W/O emulsions are more common than the multiple emulsion (Julio et al.,

9
2015; Schramm, 1992b). Emulsification refers to the emulsions formation process. The water-in-oil
emulsion is a challenge in the petroleum industry and some spill workers call it as “chocolate mousse” or
“mousse” (Fingas & Fieldhouse, 2003). Emulsification is the second challenge facing the oil and gas
industry, after evaporation. This is what most researchers assume due to the impact of emulsion on the
quality of operations and environment (Fingas & Fieldhouse, 2003). Emulsification is commonly used in
upstream petroleum industries, especially in pipeline flow. In addition, the percentage of produced water
increases towards the end life of wells (Lim et al., 2015). Figure 3 shows the general picture of upstream
equipment for crude oil production.
.

Figure 3. Upstream equipment for crude oil production (Z. Wang, Fingas,M.,Yang,C.,Christensen,J.H.,,
2005).
The oil spills or emulsions properties and features are influenced by physical factors, such as oil viscosity,
density and volume of spills (Fingas, 1995; Fingas & Fieldhouse, 2003, 2004). Researchers have reported
that emulsification affects physical properties, where it normally increases the volume, density and
viscosity of spills.
3.1. Emulsion Formation and Stability
One of the most major problems in the petroleum industry, especially mature oil fields, is high water
quantity accompanying crude oil extraction. Besides that, during desalting and steam treatment of crude oil,
water is injected into the process. Generally, there are three important factors that cause emulsion in the
petroleum industry, which are turbulent flows, pressure change in chokes valve and other valves during
crude oil extraction. Emulsions play certain rules in increasing the cost of transportation and pumping of
crude oil, facilitated corrosion and crude oil production equipment processing plant catalysts damage
(Schramm, 1992a; Sjöblom, Mingyuan, Christy, & Gu, 1992; Sjöblom, Mingyuan, Christy, & Rønningsen,
1995). (Schubert & Armbruster, 1989), concluded there are three basics reason to form emulsion, which
are:
 Interaction between two immiscible fluids, for example, oil and water.
 Existence of emulsifying agents inside the crude oil such as asphaltenes and resins.
 Diffusion of one liquid into another due to turbulence flow or mixing energy.

3.1.1. The Impact of Turbulence on Emulsification

Disturbance or mixing energy was the first reason to create emulsion. That was what researchers concluded
in the 1970s (Haegh & Ellingsen, 1977; H. Wang & Huang, 1979). (Schubert & Armbruster, 1989), found
that turbulence in the pipeline flow helped to create emulsion by mixing two fluid-like flow system of
crude oil and water. Besides that, turbulence has an impact on coalescence and break up of emulsions
(Schubert & Armbruster, 1989). Turbulence suppression happens due to contact between emulsion droplets
and other liquids (constant phase). The scientific reason behind the occurrence of turbulence suppression is

10
that kinetic energy of one liquid (single-phased) becomes higher than the other two liquids (two-phased) at
the same liquid flow rate. Furthermore, a portion of the kinetic energy is transferred to emulsions from the
two-phased stream and this makes the kinetic energy of two-phased less than single-phased. At the same
time, when the power or kinetic energy is transferred from single-phased to the particle, the turbulent
strength is declined (Schubert & Armbruster, 1989). Figure 4 clearly shows the stage of water-in-oil
emulsions formation.

Figure 4. Water-in-oil emulsions formation (Hanapi, Ariffin, Aizan, & Siti, 2006).

(Kobayashi et al., 2002), did an experiment on emulsion formulation by using a membrane through
injection of diffused phase into constant phase by the membrane pores. Besides, many researchers had
reported about the impact of velocity flow of single-phased and several types of surfactant on membrane
emulsification characteristics. These studies focused on three point effect of diameter range, surfactants on
membrane emulsification and impact of several types of surfactant on emulsion stability.

3.1.2. The Impact of Asphaltenes, Resins and Other Components on Emulsification

Crude oil comprises of asphaltenes and resins (also called functional molecules). These molecules contain
heteroatoms, such as nitrogen, oxygen and sulfur. This causes acidic and basic traits in petroleum-based
fluids, and thus stabilize water-in-oil emulsions (Subramanian, May, & Firoozabadi, 2017). Alphaltenes are
regarded as having the strongest stability of water-in-oil emulsion, because they contain aromatic and
polycyclic aromatic hydrocarbons, Figure 5, shows the molecular structure for asphaltenes in Tulare crude
oil.

11
 Figure 5. Molecular structure for asphtenes in Tulare crude oil (Varadaraj & Brons, 2012).

Before 40 years ago, researchers, concluded that asphaltenes take an important part in stabilizing of water-
in-oil (W/O) emulsion. These days, the researchers have more understood the emulsification process than
the past (Czarnecki, 2008; Sjöblom et al., 2003). (Canevari, 1982), showed or clear how asphaltene affect
by preventing water droplets from coalescence by making a thick layer on the water surface droplets. In
addition the asphaltene assistedemulsion stability by making high viscoelastic films surrounded the water
droplets while resins reinforced the stability by replacing the asphaltene when the asphaltene connection
decreased for a period of time. Generally, researchers have showed that the composition of crude oil is the
most important factor in an emulsification process cover the type of asphaltene, resin and concentration of
compounds. Aspaltenes cover a wide range of elements. (Graham, May, & Trengove, 2008), classifying the
elements into two types; binding and nonbinding, depending on the effect on emulsification process, where
the elements that have impact on binding other nonbinding. (Czarnecki, 2008), found that after studying
several fractions, each fraction has different compounds, such as sulphur and oxygen. In addition, after the
emulsion is separated into two phases, there are some droplets which is unable to be separated by an
interface. (Varadaraj & Brons, 2012), see there are many types of emulsion like W/O, W/O/W, O/W, etc.
emulsions are inside the portion of rag. Furthermore they noted that the broken emulsion has high
concentration of asphaltenes. There are many studies about emulsion and researchers have reached the fact
that asphaltene has an impact on emulsification process (Gu, Xu, Nandakumar, & Masliyah, 2002;
Kilpatrick & Spiecker, 2001; Yarranton, Hussein, & Masliyah, 2000). Synergistic compounds can be
considered as other factors that help in stabilizing emulsion by forming rigid and elastic films around water
droplets and one of the common synergistic compounds is resins. Mechanism of asphaltenes in working
and matching intermolecular interactions are not totally understood. Research focus generally on emulsion
stabilizing through asphaltenes and neglected to measure the exact stability (Kilpatrick & Spiecker, 2001).
Besides, there are other factors, including inorganic and organic solid particles and waxes, can improve the
stability of emulsions (Sztukowski & Yarranton, 2004). Asphaltenes construction is anonymous and
asphaltenes can be known from the deposition of oil in aromatic hydrocarbons, like pentane and hexane. In
addition, the molecular weight of asphaltene is approximately 750 Daltons and surrounded by other
compounds, such as alkane, S, N, etc. (Groenzin & Mullins, 2007). Another factor, such as time, has side
effects through enhanced the emulsion stability by rising the complex modulus by 2 degrees in time; from
2 hours to 4 hours. This happens due to the impact of the time on crosslinking and aggregation of
asphaltene on the interface film, and thus improves the film strength. The diffusion of asphaltenes on
interface film in W/O emulsion showed the mechanism of emulsion formation. However, what caused
emulsion stability is asphaltenes because asphaltenes are made into rigid, elastic and stable film (Lobato et
al., 2007; L. Y. Zhang, Lopetinsky, Xu, & Masliyah, 2005). Arla and co‐ workers (Arla et al., 2007),
showed that some part of asphaltenes have more effects than the other part, especially the acid fraction in
making W/O emulsion more stable. At the same time, many research (Spiecker & Kilpatrick, 2004; Xiaoli
Yang, Hamza, & Czarnecki, 2004), have approved that, the stability of emulsion basically depends on two-
factor fractions and concentration of asphaltenes.

12
Other studies focused on the impact of resins on W/O emulsion (Fingas & Fieldhouse, 2009). Researcher
have frequently noted on the impact of resins, in which one of them noted that if resins were added at a
ratio of 2:1 (resins:asphaltenes) it will enhance the stability of W/O emulsion twice than without resins
(Kilpatrick & Spiecker, 2001). Another study (Ali & Alqam, 2000), showed that, raising the ratio of
(resins:asphaltenes) in crude oil will enhance the stability of W/O emulsion. (Pereira et al., 2007), showed
that resins can be found in crude oil, depending on the type of resins. The adsorption of resin on iterfical
film depends on several factors, including silica and asphaltenes, however, some resins are more adsorptive
on the same surface. Other studies showed that the important factor which can decide, whether resins
would stabilize asphaltenes or not. is self-interaction. (Silset, Hannisdal, Hemmingsen, & Sjöblom, 2010),
saw that several emulsion stabilities can be explained through the interaction between resins and
asphaltenes atoms. In normal conditions, asphaltenes adsorb resins to enhance the aggregation and
precipitation of asphaltenes. Other studies (Spiecker, Gawrys, Trail, & Kilpatrick, 2003), noted that resins
work on solvated asphaltenes and besides that, they approve that there are interplays between the atoms of
resins and asphaltenes. On the other hand, resins comprise surface active materials, which are aromatic
ring, long-chain carboxylic acid, esters and phenols. Furthermore, resins could also develop an interfacial
film structure of a particular strength. Since the stability of oil-in-water (O/W) emulsion in conjunction
with resins is the strongest, and thus a higher absolute value of zeta potential for oil droplet surface.
Nonetheless, wax comprises small occurrences of interfacial active materials, whereby it only comprises
short-chain cycloalkanes and hydrocarbons, leading to the weakest stability of oil-in-water (O/W) and
water-in-oil (W/O) emulsions developed by wax model oil oil (Juan Zhang et al., 2016). There are less
study on other factors, such as waxes have impact or not on W/O emulsion, at the same time, waxes have
impact on some emulsions like food formulation when waxes are in molten or deformed shape (Binks &
Rocher, 2009).

3.1.3. Emulsion Thermodynamic Aspect

The unchanged in emulsion properties for a certain period of time can be defined by term “emulsion
stability”. In the same time, thermodynamically emulsion a considered as an unstable system and emulsion
properties will change slowly as well as there are various phenomena that occur during the change in
emulsion properties including creaming, flocculation, Ostwald ripening, coalescence, etc. However, these
phenomena may occur combined together or individual. The emulsion is a system of two-phase or more
than in most case have media with various densities. The difference density between droplets and
continuous phase determine the movement of droplets. There are two phenomenon related two the
movement of droplets creaming and sedimentation. Creaming phenomenon occurs when the droplets move
up due to the low density of droplets reverse the sedimentation that happens when droplets move down due
to high density. Generally, oil has a density less than the water, consequently, the sedimentation
phenomenon takes place in water in oil emulsion and creaming phenomenon in oil in water emulsion
(Derkach, 2009; Nollet, 2004; Robins, 2000; Robins, Watson, & Wilde, 2002). Single droplets velocity v in
creaming emulsion which is not deformation can be found by Stokes formula (Nollet, 2004).

(1)

Where r, , cont, drop, cont are present droplet radius, gravity acceleration, continuous phase density,
droplet density and continuous phase Newtonian viscosity. Other phenomenon is flocculation which is
droplets are gathering in emulsion to form droplets flocs due to attractive interactions (Gupta, Eral, Hatton,
& Doyle, 2016). While the merging of droplets describe as coalescence phenomenon and the coalescence
occur when the film between two droplets collapses (Marrucci, 1969). While the process of gradual growth
of coalescence droplets into large droplet in emulsion is defined by Ostwald ripening terms as show in
figure 6 which clear the thermodynamic aspect in nanoemulsions.

13
 Figure 6. Thermodynamic phenomenon’s in nanoemulsions (Gupta et al., 2016).

3.2. Classification of Emulsion

There are many classifications for emulsion, the most common is by sorting emulsion into four types
(Fingas & Fieldhouse, 2003; Fingas, Fieldhouse, & Wang, 2003). (Fingas et al., 2003), had classified
emulsion into four basic types, depending on three factors; stability, appearance and rheological
measurements, as shown below.

 Water-in-oil emulsion.
 Mesostable water-in-oil emulsions.
 Entrained water.
 Unstable water-in-oil emulsion.
Other research divided emulsion to three general groups, as follows (S. L. Kokal, 2005).
 Water-in-oil emulsion
 Oil-in-water emulsion
 Multiple emulsion

3.2.1. Water-in-oil Emulsion

In the petroleum industry, water-in-oil emulsion is very common, as shown in Figure 7. At the same time
crude oil cannot be refined and transported, before the water-in-oil is broken into two-phased (Mukherjee
& Kushnick, 1988; Xia, Lu, & Cao, 2004). During the crude oil extraction, there are many contents
accompanying crude oil, such as oily sludge, water and solid content. Concurrently, the percentages for
these compounds are 30-50 wt% oil, 10-12 wt% solid content and 30-50 wt% water. The solid content
works on enhanced emulsion by stabilizing through the adsorbed partials on interfacial film. The oily

14
sludge in crude oil is harmful to human health, so it is important to apply crude oil for recovery in the
sludge disposal (Elektorowicz, Habibi, & Chifrina, 2006; Hu, Li, & Zeng, 2013; Ju Zhang, Li, Thring, Hu,
& Song, 2012). Furthermore, the sludge recovery was reviewed many times (Hu et al., 2013). The stability
of emulsion is affected by several factors including viscosity, water content, density and element content of
crude oil, while the previous factors change, depending on the wells and change the emulsion stability
(Rodionova, Keleşoğlu, & Sjöblom, 2014; Roodbari, Badiei, Soleimani, & Khaniani, 2016). Asphaltenes,
waxes, resins, etc. All can be considered as surface-active materials and these elements are absorbed at the
interfacial film which prevent the water droplets from coalescence. At the same time, N-, O-, S-, SiAOH
and SiAOA bonding works on improving the emulsion stability (McLean & Kilpatrick, 1997; Mukherjee &
Kushnick, 1988; Oren & MacKay, 1977; Poindexter & Marsh, 2009; Thompson, Taylor, & Graham, 1985).
Moreover, asphaltenes and resins are the most effective factors in enhancing the emulsion stability, while
the asphaltenes are soluble in aromatic hydrocarbon, such as toluene but is not soluble in alkanes. In
contrast, resins with asphaltenes is soluble in both aliphatic and aromatic solutions. The reason that made
asphaltenes and resins to enhance the emulsion stability is due to hydrophilic functional groups in their
structure (Xiaogang Yang, Tan, & Bu, 2008). The interfacial films' rigidity depends on what is deposited
on the surface, whether asphaltenic or resins, while asphaltenic will make the interfacial films stronger than
resinous materials. Demulsification method can be used to break emulsion by weakening the interfacial
film or immobile interfacial films, and this helps the droplets to coalescence. In addition, the elasticity and
the emulsion stability are affected by several factors and the most important factors are aromatic degree,
concentration of asphaltene and resin, resin-to-asphaltene percentage and dose of hydrophilic functional
groups in crude oil (McLean & Kilpatrick, 1997; Mohammed, Bailey, Luckham, & Taylor, 1993; Xia et
al., 2004). Resin can work in high concentration with asphaltene as a destabilizing agent due to the P-P and
polar bonding (Graham et al., 2008; Schorling, Kessel, & Rahimian, 1999; Spiecker et al., 2003). The
hydrocarbon phase is different from crude oil in water-in-oil emulsion and synthetic. Normally, nonionic
surfactant can be used for emulsion stabilization (Chistyakov, 2001). There are noteworthy differences
between the oilfield emulsions contents against demulsification and model emulsions, during the crude oil
extraction, there are several inhibitors added like corrosion inhibitor, scale inhibitor, clay stabilizer, etc.
(Zaid, 1987; Zolfaghari et al., 2016).

Figure 7. Optical microscopic image of W/O emulsion; (a) without surfactant and (b) with 200ppm
copolymer (Le Follotec, Pezron, Noik, Dalmazzone, & Metlas-Komunjer, 2010).

15
3.2. 2. Oil-in-water Emulsion

Due to various properties, from non-Newtonian behavior, elasticity and time emulsions have garnered
attention as a very important topic of study for rheological investigations. The term “emulsions” is
characterized by numerous blends of immiscible liquids, of which include polymeric substances. As a rule
of thumb, one denotes mixtures of low molecular weight (e.g., water and oil). The various blends of
emulsions can be widely observed in technological applications from pharmaceuticals, enhanced oil
recovery and food processing, as well as biological systems. Figure 8 shows oil-in-water emulsion, oil-in-
water emulsion (i.e., oil submersed in highly-concentrated emulsions) could form when surfactants of the
block copolymer type are used with volume fractions being higher than 0.96. This type of emulsion could
be brought to balance by utilizing surfactants with a low HLB value. A single Maxwell element could
appropriately represent the emulsion rheological behavior. While the shear varies in linear proportion to the
volume fraction, a proper correlation between shear modulus as well as the ratio of interfacial tension to
radius was not reported (Masalova, Malkin, Slatter, & Wilson, 2003). The difference with models currently
available could be accredited to a strong interfacial tension, which is greater than those of equilibrium
values. The stronger interfacial tension could explain the reason behind the lack of inversion occurrence
within oil-in-water emulsion. The apparent viscosity (which scales as a minus fourth power of continuous
phase volume fraction) within the continuous phase of emulsion relies greatly on volume fraction for the
oil-in-water emulsion studies of current versus previous experiments (Pons, Solans, & Tadros, 1995).

Figure 8. Optical microscope images for O/W emulsion prepared with (A) Eucalyptus globulus and (B)
Citrus limon (Sousa, Santos, Rocha, & Trindade, 2014).
Reducing the aeration of oil-in-water emulsion and density variance, decreases the velocity of oil droplet
(single phase) in water phase (continues phase). Consequently, this makes O/W emulsion more stable
eventually. Moreover, by reducing the density difference between two phases, this well help to prevent oil
droplet as well as air-water surface and oil droplet from coalescence. During aeration, there are four

16
parameters that can be manipulated to decrease the oil droplet in water velocity. This is done to optimize
stabilization of powdered o/w emulsions. These parameters include the density difference between two
phases, water phase viscosity, aeration speed and oil droplet diameter (Murakami, Moriyama, Noguchi,
Yamamoto, & Binks, 2014). Droplet flocculation has a strong correlation with the creaming stability of
monodisperse oil-in-water emulsions. Hydrodynamic effects and particle-particle interactions are
responsible for the increase of droplet flocculation and reduction of droplet concentration. Consequently,
this leads to the increase of creaming velocity, which could be modeled by utilizing equations formulated to
model it in nonflocculated systems. However, for accurate modeling of this phenomenon, the increase of
effective volume fraction due to flocculation should be noted as well. The results of the preceding
phenomenon, studied by (Chanamai & McClements, 2000), bear many crucial implications towards the
formulation of various commercially relevant emulsion-based products. The study was conducted to
produce a stable O/W emulsion by using diesel as oil and sorbitan monooleate as the emulsifier. It was
found that the optimal emulsifier dosage was 0.5% by volume and that lower emulsifier dosages led to
unstable emulsions. The lack of emulsion stability at higher dosages was accredited to rapid coalescence
and concentration. The next finding concluded that the increase of emulsion stability varied inversely with
oil-to-water ratio. The optimal ratio was found to be 1:1 by volume. The third finding showed that higher
stirring intensity resulted in emulsions, which were more stable; thus, the best stirring intensity was found
to be 2500 rpm. Fourth, high temperature was shown to reduce emulsion stability, with the most optimal
emulsifying temperature being 308 0C. Lastly, emulsion stability varied linearly with stirring time until 15
minutes. After this time, the stability varied inversely with stirring time because of the drop-out of
emulsifier within the oil-water interface (Chen & Tao, 2005).

3.2.3. Multiple or complex Emulsion

The term ‘multiple emulsions’ refers to soft materials made by outer droplets (i.e., droplets which are
dispersed) which comprised of smaller droplets inside (i.e., inner droplets). Various applications may be
satisfied by the multi-compartmental feature, comprising tight spaces in continuum, detailed prior by
(Binks & Rocher, 2009). The common terminology for normal, double or multiple emulsions may be
categorized as oil-in-water-in-oil (O/W/O) or water-in-oil-in-water (W/O/W). The various categorizations
are based on the phase sequence of various scales. For this common terminology, the ‘water’ refers to any
polar or aqueous phase and ‘oil’ refers to hydrophobic, or water-insoluble phase (Silva, Rodríguez-Abreu,
& Vilanova, 2016). In modern times, development of double or multiple emulsions comprises tiny water
droplets interspersed amongst bigger oil globules, which are in turn interspersed among aqueous
continuous phases (Bonnet et al., 2010). Even though multiple emulsion systems have been recognized in
modern science, significant attention was paid to these systems only within the last 15 years.
Photomicrograph representations of the water-in-oil-in-water multiple emulsion configuration drop are
shown in Figure 9. The two dispersed phases could clearly be perceived, whereby the small internal
aqueous droplets which are surrounded by a surfactant-stabilizing layer, are interspersed amongst the oil
phases. Consequently, this is interspersed in the outer equeous phase, which is also surrounded by
surfactant layer (Florence & Whitehill, 1982). Water-in-oil-in-water emulsion poses the same advantages
of water-in-oil emulsion while also having a lower viscosity because of the lower viscosity of the aqueous
external phase. This characteristic makes the particular configuration more convenient to control and for
applications like for injection (Florence & Whitehill, 1982).

17
 Figure 9. Photomicrograph of typical w /o/w emulsion (Florence & Whitehill, 1982).
Relatively small reproducibility is found within these unintended preparations which results in low level of
multiple drops and instability. While multiple structures may appear in numerous liquid-liquid interactions,
they are usually so unstable so as to be imperceivable (Florence & Whitehill, 1982).

3.2.3. Pickering Emulsion

High sustained demands for energy with limited crude oil recovery leading to increase the demand for
discovering new resources of energy and enhancement the techniques of crude oil recovery. The rare new
resources of crude oil drive the oil producer to exploitation and enhancement the oil recovery as the only
option to cover the world energy demands (T. Sharma, Kumar, & Sangwai, 2015). Pickering emulsion is
suitable in applying for enhanced oil recovery (EOR) by stabilizing emulsion with nanoparticles (SiO2 and
clay) and oilfield polymer polyacrylamide (PAM) in the presence of surfactant (T. Sharma, Kumar, Chon,
& Sangwai, 2014). Pickering emulsions can be described as the emulsion stabilized by solids molecules
(Zolfaghari et al., 2016). Figure 10 clear Pickering emulsions stabilize by carbonaceous materials.
Pickering emulsion is characterized by environmentally friendly, biologically compatible and more stability
against coalescence, thus Pickering emulsion application opens the door in petroleum, pharmaceuticals,
biomedicine, cosmetics and food industries (J. Tang, Quinlan, & Tam, 2015). Furthermore, Pickering
emulsion formation including the diffusion the solid particles in the continuous phase, so the solid particles
adsorb on water/oil interfacial file to make electrostatic and steric protective layer that prevent droplets
coalescence. While the solid particles adsorption in two immiscible interphases depends on particles
wettability (J. Tang et al., 2015). Pickering emulsions response to external triggers like light intensity,
temperature, pH and other variables. (Dai et al., 2018), investigate the effect of composite zein - propylene
glycol alginate particles (ZPGAPs) on stabilizing oil in water Pickering emulsion. The result shows that
(ZPGAPs) may help in stabilizing oil in water Pickering emulsion. In addition, the ionic strength has a
significant effect on Pickering emulsion stability through changing the range and magnitude of electrostatic
interactions (Dai et al., 2018). (Xie, Wang, Li, Wei, & Yang, 2018), study the influence of particle
concentration, homogenization speed, pH, oil type, size distribution on Pickering emulsion. The result
shows that increasing homogenization speed and particle concentration increase the emulsion stability.
While the pH and oil types show no effect on the stability of the emulsion. (Schröder, Sprakel, Schroën,
Spaen, & Berton-Carabin, 2018), use microfluidic cross-flow device to study the coalescence stability and
formation Pickering emulsions by colloidal lipid particle (CLP). The result show particle coverage plays a
major role in droplets coalescence. CLP has prevented droplets coalescence at high surface coverage and
destabilizing emulsion at low surface coverage. In the petroleum industry, the application of stimuli-
responsive Pickering emulsifiers may be enhanced the crude oil recovery, reduce the operation cost and
reduce the demand for energy-intensive (J. Tang et al., 2015).

18
Figure 10. Optical micrographs at different storage times for (a) styrene/water Pickering emulsions and (b)
water/styrene Pickering emulsions (Xie et al., 2018).

4. Destabilization Emulsion
Development of stable emulsion is heavily unwanted in the petroleum industry but, inevitable. This is
because the interfacial active fractions within crude oil are vital to the development and oil emulsion
stability (described as dispersed water droplets resistance towards coalescence). To explain further,
coalescence refers to the united bonding of diversed particles or droplets to form one greater droplet (Chen
& Tao, 2005). Under the perspective of thermodynamics, an emulsion is considered an unstable system due
to the fact that a liquid-liquid system encounters a natural inclination to disperse, thereby reducing its
interfacial area (in other words, its interfacial energy as well). Nevertheless, the majority of emulsions tend
to be stable over time because they possess kinetic stability (Schramm, 1992a). Oil-field produced
emulsions that are categorized depending on their degree of kinetic stability as shown below (Tambe &
Sharma, 1993).

 Loose emulsions: which refers to those that will diverge within a few minutes. The term ‘free
water’ is credited to separated water.
 Medium emulsions: which will separate within tens of minutes.
 Tight emulsions: which will separate, wholly or partially, within hours up to days.
The various types of parameters involved in chemical demulsification, which, if altered may either reduce
or rise the emulsion stability are discussed in the following section.

4.1. Elastic and Viscous Modulus

Emulsion considers as a system consists from immiscible liquid two or more, while the stability of this
system depends on the presence of adsorbed surfactant on the interfacial system (H. M. Lee, Lee, & Park,
1997). The calculations of rheology emulsion depend on interfacial tension because the shear forces on
surfaces influence on deformation and internal circulation of droplets in the emulsion. (H. M. Lee et al.,
1997) , suggest the following formula to find the macroscopic two-phase fluid stress tensor.

(2)

Where m and dij= ∂ui/∂xj are a symbol of continuous phase viscosity and gradient tensor velocity
respectively. In addition, pt, mdt and vrt represent the pressure term, morphology-dependent term and
viscosity ratio term sequentially and can be calculated as the following equation (H. M. Lee et al., 1997).

19
 (3)

(4)

Where is volume fraction of first order. The capillary number for sa pherical droplet in the diluted
emulsion can be calcaulet by the formula (H. M. Lee et al., 1997).

(5)

Where α and γ· represent the interfacial tension and shear rate respectively. Many researchers predicted the
relative viscosity of emulsion r by applying semi empiric models. While relativee viscosity can be
calculetd by following equation (C. B. de Oliveira et al., 2018).

(6)

Where c and e are the viscosity of the continuous phase and emulsions respectively. Non-Newtonian and
Newtonian behavior were applied to predict the viscosity of water in crude oil emulsions. (Rajinder Pal,
1996), investigate the effect of droplet size in oil in water and water in oil emulsions on rheological. It was
concluded that the coarse emulsions are less storage moduli and viscosities compering with fine emulsions.
In the same time, the fine emulsion show low rheological properties and viscosity reduce with the decrease
in low shear stresses.
Crude oil with high percentage of asphaltenes is insoluble in n-heptane and naphthenic acids, besides that,
this type of crude oil it is difficult to handle and refine. This is so because during crude oil production,
produced water commonly emulsifies into the crude oil, and thus lead to water-in-oil emulsion (Varadaraj
& Brons, 2012). There is an inverse relationship between the creaming rate and oil volume, while the
creaming rate and oil volume correlated with viscosity. The creaming rate and oil volume can be calculated
from steady state measurement and power law of fluid model. At the same time, the correlation between
viscosity and creaming rate is linear and this can be observed in high emulsion concentrations. Low shear
measurements (constant stress (creep) and oscillatory measurements) were described as among the most
effective methods of predicting creaming or sedimentation of emulsions (Tadros, 2004). In addition, Table
2 shows the properties of interfacial film between oil and water droplets, the interfacial tension, interface
elastic modulus (€) and emulsion stability at percentage ratio of 2:8 water-in-oil volume for 0.1 wt% of
asphaltenes in crude oil (Varadaraj & Brons, 2012). High amount of water retained was found to correlate
with high emulsion stability. The oil-water interfacial tension (γ) for 50:50 n-hexadecane/toluene solvent
mixture was 33 mN/m. It was observed that types I, II, and III asphaltenes reduced γ to about 20 mN/m.
This decrease in γ was not as much as the reduction of interfacial tension within conventional surfactants.
Thus, n-interfacial activity of these asphaltenes or interfacial tension could not be considered as a reliable
method of measuring interfacial activity of asphaltenes (Varadaraj & Brons, 2012).
Table 1.
Table 1. Properties of asphaltenes at water-in-oil emulsion (Varadaraj & Brons, 2012).

Interfacial property Hamaca Hoosier Tulare Celtic Talco Cold

Lake
E at t = 5 min (mN/m) 11.9 2.4 5.7 2.6 1.3 6.6
E at = 5 h (mN/m) 31 24 38 13 5 22
γ (mN/m) 21 19 21 26 22 23

20
 Emulsion stability (%) 59 41 70 21 10 40

There is no correlation between stability of emulsion and interfacial tension, as shown in Figure 11, due to
the direct surface action of asphaltenes and autonomy of interfacial tension with the type of asphaltene.
Furthermore, this phenomenon shows that traditional models for emulsion stability (with oil-water
interfacial tension (γ) as the primary stabilizing factor) could not entirely explain stability of asphaltene-
stabilized water-in-oil emulsions (Varadaraj & Brons, 2012).

Interfacial Tension γ (mN/m)

30
Interafacial Tension (mM/M)

25

20

15

10

0
0 10 20 30 40 50 60 70 80
Emulsion Stability

Figure 11. Interfacial tension versus emulsion stability (Varadaraj & Brons, 2012).

The definition of emulsion stability is the resistance of dispersed phase droplet against coalescence.
Asphaltenes, the mass percentage of aromatics components, resins, viscous modulus (G″) and elastic
modulus (G′) are the main parameters that effect on emulsion stability (Wong, Lim, & Dol, 2015). Next to
asphaltenes and volatile aromatic compounds, storage or elastic modulus (G′) and loss or viscous modulus
(G″) were shown to affect emulsions stability. It was previously reported that, when the viscous behavior of
the fluid is less than the elastic behavior (G″oG′) of the fluid, the emulsions were comparatively stable,
provided that both of the parameters were independent of the frequency in the linear viscoelasticity region.
Linear viscoelasticity region (LVER) refers to the region where a system does not break down due to
applied stress (Ortiz, Baydak, & Yarranton, 2010). In addition, natural surfactants of crude oil like
asphaltenes affected by the elastic modulus. (Maia Filho, Ramalho, Lucas, & Lucas, 2012), reported the
effect of adsorption of natural surfactant on the water-oil interface. The result present that these surfactants
cause intermolecular interactions which lead to increasing the elastic behavior and work against oil-water
emulsion interface. (Derkach, 2009), concluded that coalescence between droplet dispersed phase decrease
when the increase inelastic behavior.

4.2. Time and Speed Mixing Impact

Time plays a certain rule in destabilizing emulsion. Generally, after period of time, like one week or more,
the water droplets become more reliable because unstable emulsion will be broken (Fingas & Fieldhouse,
2003, 2004). Some factors cannot be considered as affective factors in destabilizing the emulsion. like
water content due to surplus water that can be found in crude oil. Emulsion stability can be improved by
increasing the speed and mixing interval by reducing diameter size of oil water droplets in oil-in-water

21
emulsion and increasing the stability and viscosity due to particle interaction between two phases
(AHMED, NASSAR, ZAKI, & GHARIEB, 1999). The colloidal surface and Brownian movement forces
can be stronger than the hydrodynamic forces in the system where the diameter of dispersed droplets is less
than 1 lm (AHMED et al., 1999).
4.3. Size and Diffusion Droplets
In the petroleum industry, there are two common types of emulsion; water-in-oil and oil-in-water emulsion
Generally, these two types have droplet of size 0.1 lm or larger and sometimes more than 100 ml. However,
the emulsion viscosity is effected by droplet size and distribution of droplets. The distribution of small
droplets in small area produces emulsion with high viscosity and stability (Zolfaghari et al., 2016). What
makes emulsion more stable is that the small droplets need a longer time to coalesce, while an effective
surfactant can enhance the coalescence of water droplets or oil droplets, depending on the type of
demulsifier.
4.4. Temperature
Temperature rising has several impacts on destabilizing emulsion, including reduce the viscosityof
continuous phase, increase the discrepancy between the dispread and continuous phase of emulsion and
rising the quantity of droplets collisions through weakening of interfacial film between two phases
(Mohammed, Bailey, Luckham, & Taylor, 1994). As a consequence, the increasing temperature at the
same time disadvantage, including increased concentration percentage on interface due to reduction in oil
viscosity (Mohammed et al., 1993). Temperature can affect surfactant solubility, whereby the temperature
can have positive or negative impact on solubility, depending on the type of demulsifier. In addition, the
solubility of nonionic surfactants in water decreases with rising temperature, in contrast with anionic
surfactants (Bourrel, Salager, Schechter, & Wade, 1980). Correspondingly, the adsorption of nonionic
surfactant at interfacial film reduces with rising temperature in oil-in-water emulsion, as a result to
destabilizing emulsion (Hirasaki et al., 2010). In contrast, other published work showed that the increased
temperature in extracting water from ASP flooding improved the emulsion stability (Nguyen, Sadeghi, &
Houston, 2012), the reason behind this behavior was due to high salt content in the produced water which
enhanced the adsorption of anionic surfactant at interfacial film.
4.5. Solids Particles
The emulsion stability can be enhanced through soft solids particles, many factors including size,
interactions and wettability of solids particles affect the effectiveness of solids particles. As a result to
diffusing the particles on the surface of interfacial films of W/O emulsion will increase the rigid of
interfacial film and improve the emulsion stability through preventing the coalescence of emulsion
droplets. At the same time, fine solids particles can improve the stability of temperature impact through
change in average and characteristics of interfacial films. Furthermore, the compressibility of interfacial
films can be influenced by solids particles due to the impact of solid particles on solubility of demulsifier
on interfacial films (Levine & Sanford, 1985; Tambe & Sharma, 1993).
4.6. Environment Medium
The pH effectiveness on emulsion stability is related to oil phase, brine characteristics in emulsion and
organic acids in crude oil can be influenced on demulsification process in water-in-oil emulsion. Normally,
surfactants hydrophilicity normally rise with growth in pH value of emulsion. Acidic environment can help
in producing water-in-oil emulsion in contract with basic and medium environments, which is more
suitable to produce oil-in-water emulsion. At the same time, asphaltenic can be more rigid at low pH level
and starts to become weaker with rising pH level. Alkaline environment has influence on asphaltenic and
make mobile/unstable films, while the resinous, in contrast with asphaltenic, became stronger in alkaline
environment and weaker at low or medium pH. In addition, ionization of surfactants at interfacial film of
water or oil phase gave positive or negative charge for single phase droplets at low pH level, the ionization
effect is caused through brine solution due to the interaction of salts atom and surfactant at interfacial film
(Fortuny et al., 2007; Strassner, 1968). The best pH level that helps surfactant to separate with high
efficiency of oil-in-water emulsion at medium or near to medium level (Azim, Abdel-Raouf, Abdel-
Raheim, & Maysour, 2010; Zaki, Abdel-Raouf, & Abdel-Azim, 1996). The act of nonionics surfactant

22
depends on the environment that works in and normally acts like anionics under basic environment or like
cationic in acidic environment (Möbius, Miller, & Fainerman, 2001). Acidic environment is the best
condition to break emulsion and at the same time should avoid the corrosion in treatment equipment.
4.7. Spread Phase Salinity
The salinity in water normally works in reducing the hydrophilicity of surfactant through decrease in the
interactions of water with surfactant at interfacial films (Goldszal & Bourrel, 2000; Martínez-Palou et al.,
2013). It was noted that, increasing the salinity of water-in-oil emulsion by adding NaCl and decrease the
interfacial film tension, at the same time the HLD can be adjusted from negative to zero through increased
salinity system and enhance the surfactant efficiency (Bera, Mandal, & Guha, 2013; Gaonkar, 1992;
Nguyen et al., 2012). In addition, the increase in salinity in water-in-oil emulsion increase the stability of
the system due to the interaction between the native surfactants and aqueous phase (Fortuny et al., 2007).
However (Goldszal & Bourrel, 2000), observed that when water-in-oil emulsion has various and high
concentration of resins with high brine salinity would need more hydrophilic additives to separate the
aqueous phase with high efficiency . Nonionic surfactant tolerance in salinity is more than in anionic
surfactant, while the effect of salinity on stability of emulsion is contradictory (AHMED et al., 1999;
Moradi, Alvarado, & Huzurbazar, 2010; X. Wang, Brandvik, & Alvarado, 2010). At the same time,
aqueous phase in water-in-oil emulsion with divalent cation is more stable than monovalent cation, while
salinity water with divalent cation increases the demulsification efficiency in water-in-oil emulsion more
than monovalent cation (Kuo & Lee, 2009; Perles, Volpe, & Bombard, 2012; Salager, 2000). The optimal
salinity can be defined or occurred when the interfacial film tension between surfactant and brine is the
same between the surfactant and oil, while optimum point happened at lower separation time, surfactant
dose, viscosity, IFT, high coalescence rate and maximum oil recovery (M. Sharma & Shah, 1985).
4.8. Water and Oil Content
There are many factors besides the other impact, such as asphaltene and resin. Basically, in demulsification,
efficiency by using surfactant increases with increasing water content, while reducing the time and
concentration of surfactant dose needs to increase the other the water in oil ratio in specific the percentage
of water in range from 0.3-07 volumetric fraction (Borges, Rondón, Sereno, & Asuaje, 2009). However,
emulsion is broken faster with higher water content than lower content, at the same time emulsion viscous
increases with increasing in water content (Mouraille, Skodvin, Sjöblom, & Peytavy, 1998; Thompson et
al., 1985). In addition, increasing the volume of dispersed phase enhances the separation efficiency and
average of coalescence due to rise in entropy for high collision between the single phase droplets (Menon,
Wasan, & Becher, 1985). (Zaki, 1997), It is observed that, reducing the volume of oil from 90%-60% in
oil-in-water emulsion lead to little separation of water droplets while less 50% will cause broken emulsion
directly. Moreover, increasing the oil content in oil-in-water emulsion can change the type of emulsion
from oil-in-water emulsion to water-in-oil emulsion, which is more stable due to high concentration of oil
in continuous phase (AHMED et al., 1999). Sometimes, the emulsion is formed for transportation purposes
by reducing the viscous of mixture. What is important in this case is pour-point of emulsion to avoided
freezing of mixture at low temperature (Zaki, 1997).

5. Demulsification and Desalination of Oil Recovery Processes

The most important in demulsification process is removing impurities, salt and water from mixture. The
desalination technique depends on the concentration of salt in content and the compatibility of technique
under high concentration of contaminants in produced water. There are several techniques of
demulsification. The most common are electric separation, chemical treatment and membrane filtration.
Demulsification can be defined as the process of separation crude oil into two-phase crude oil and water.
Generally, demulsification method can be assessed in three-point as below (Arthur, Langhus, & Patel,
2005).

 Time or speed of broken emulsion process.

 Efficiency of process in separating crude oil emulsion.

23
  Goodness of removal separated water.
High efficiency of separation with minimum time and best way for disposal water are centrally preferred by
crude oil producers. There are specifications about crude oil before it is sent to refinery or transported in
pipelines, like crude oil should contain less 0.2% water and sediment and less 10PBT of salt, and this
specifications depend on crude oil producer. Generally, the advantage of using EOR methods is to enhance
microscopic displacement efficiency obtained from water flooding. However, EOR techniques are more
expensive than water treatment and this techniques have become economically attractive in huge oilfields
(Muggeridge et al., 2014).
5.1. Measurement of Stability
One of the most important tests that can be applied is the emulsion measurement stability. Measurement
stability refers to the ease in broking emulsion to two-phase and there are several techniques to measure the
emulsion stability (S. Kokal & Alvarez, 2003; R Pal, Yan, Masliyah, & Schramm, 1992). Bottle test can be
considered as one of the most common techniques to measure emulsion stability , while this method,
including mixing surfactant with emulsion, dilution of emulsion and note the separation efficiency with
increase in time. However, there are several techniques of bottle test, normally standard ASTM technique is
used to measure the sediments and water in the system. Emulsion stability is connected with fast broken
emulsion with time and surfactant concentration. For instance, at specific surfactant dose, the emulsion
stability can be fined through the measurement the percentage of water separation at a certain period of
time. In modern days, the new technique is proposed for determining the stability of emulsion
quantitatively (S. Kokal & Wingrove, 2000). This new method is present to determine the complexity of
emulsion. The index in bottle test is used to measure the complexity of emulsion, while the index start from
zero to 100% total separation and this percentage is influenced by several factors, such as temperature, dose
of surfactant and type of surfactant (S. Kokal & Wingrove, 2000).
5.2. Destabilizing Emulsions and Demulsification Methods
The interfacial films that include water droplets are responsible for the emulsion stability. The
emulsion that is broken into interfacial film should be destroyed so that the water droplets can
coalesce. There are several factors that can help in weakening the interfacial film, as shown below.

 Decreasing agitation or shear force.

 Solids disposal.
 Rising temperature.
 Monitoring the emulsifying agents.
 Increasing time duration.
In the petroleum industry, there are different ways to separate or broken emulsion into two-phase oil and
water. In addition, these methods depend on applying one of the methods below (S. Kokal & Alvarez,
2003; R Pal et al., 1992).

 Applying chemical surfactant to emulsion.

 Raising the temperature of the system.
 Passing electrical fields to enhance the water droplets coalescence.
 Enhancing the physical characteristics of the mixture.
There are several ways to demulsificaion of emulsion. (Arthur et al., 2005), A summary of demulsification
techniques is as in Table 2.

24
Table 2
Summary of demulsification technologies (Arthur et al., 2005).
Treatment Produced water applications
Hydroclone
The different methods can be use in treating oil and
Gas floatation
water that was extracted from emulsion before
discharge. Both water from reservoirs and flooding
Corrugated plate can be storaged as feed stocks. They contain grease
separator and oil in this type of water and can be reach to
1000mg/L.
Centrifuge
Adsorption These methods can be used in disarmament oil or
trace at small oil and grease content before membrane
processing.
In addition, natural gas thermogenic and oil
Extraction reservoirs normally contain hydrocarbons liquid such
as trace. Natural gas like CBNG in reservoir may not
contain liquids but during pumping the water can take
Ozone hydrocarbons liquid to the surface.
Rapid spray
evaporation
This different types of technologies can be
distinguished from membrane technologies by less
Freeze–thaw pretreatment and power. Normally the TDS values of
evaporation produced water in range of 10,000 to 1000mg/L. On
the other hand some of these technologies need to
grease and oil contaminants treatments before
operations while other technologies not.
Lime softening
Ion-exchange
Ultrafiltration Both two technologies can be used in filtering
produced water by removal contaminants like soluble
organics, trace oil, microbial, divalent salts, etc. The
selection of membrane can be chose depend on nature
Microfiltration of contaminants.
Constructed wetland
treatment
This technique can be apply to disarmament
inorganics and organics contaminants. On other hand
Reverse osmosis some organic contaminants need pretreatment, at the
same time the energy cost rise with TDS. In addition,
for higher efficiently in removing contaminants the
salts contain should not excess of 10,000mg/L.
Activated sludge It can be applied to filtration of suspended, like
boron, ammonia, trace, etc. In this technique the post
treatment is usually required.
Description
This methods depend on centrifugal force that cause
by pressurized tangential input of influent stream,
and this force is applied for free oil separation
The particles of oil can reach the surface by link to
induced gas bubbles
Separation of free oil from water under gravity
effects enhanced by flocculation on the surface of
corrugated plates
Free oil separation under centrifugal force from
water. The centrifugal force can be generated by
cylinder spinning
Porous media adsorbs contaminants from the influent
stream
Removal of free or dissolved oil soluble in lighter
hydrocarbon solvent
High oxidizers lead to easy soluble of suspended,
high efficiency for pretreatment of soluble
contaminant and easy operation
The treated water can occur by injection water in
high speed at heated air lead to evaporates the water
that can be condensed
Freezing contaminated water to produced water
crystals by using natural cycles temperature to
produced pure water by thawing crystals
Hardness, bicarbonate and carbonate can be extracted
by adding lime
Ion-exchangers help in remove minerals and
dissolved salts by exchanging
ions
Applied pressure on membrane can help in removing
ultraparticles from the water
Membrane removes micro-particles from the water
under the applied pressure
Decomposition and natural oxidation of contaminants
by fauna and flora
Change pressure on contaminated water lead to
squeeze in pure water that was produced from
contaminated water
Degrade contaminants in water by using
microorganisms
Disadvantages
Expensive maintenance, fouling, weak in solid
separation and energy requirement to generation
pressure at inlet input
Large quantity of skim volume, lateness in separation
time and high amount of air generated.
High cost for maintenance, low separation efficiency
for oil fine particles and long retention time
Expensive maintenance and energy demand for
rotating
High retention time, less efficient at higher feed
concentration
Use of solvent, extract handling, regeneration of
solvent
On-site supply of oxidizer, separation of precipitate,
byproduct CO2, etc.
High energy required for heating air, required
handling of solids
Lower conversion efficiency, long operation cycle
Chemical addition, post-treatment necessary
High content of liquid effluent, high efficiency need
post- and pre-treatments
High energy, membrane fouling, low
MW organics, salts, etc
Low efficiency in monovalent salts, viruses, divalent,
etc. High amount of energy is required
Expensive maintenance, pH and temperature effects,
spinning time requirements
Grease, oil and trace have effect on membrane
fouling, flooding pressure requirements
The dimensions of filter too large and oxygen
requirement
Advantages Waste stream
Higher efficiency, compact modules and output for smaller oil particles
Higher efficiency, fixed parts, robust and durable and easy in operation Skim off volume, lumps of oil
Fixed parts, cheaper, robust and resistant, no required for energy and high Suspended particles slurry at the bottom of the separator
efficiency for suspended solid removal
High efficiency in extraction solids contaminants and oil particles, high output and Suspended particles slurry as pretreatment waste
lesser spinning time
Compact packed bed modules, cheaper, efficient Used adsorbent media, regeneration waste
No energy required, easy operation, removes dissolved oil Solvent regeneration waste
Easy operation, efficient for primary treatment of soluble constituents Solids precipitated in slurry form
High quality treated water, higher conversion efficiency Waste in sludge form at the end of evaporation
No energy required, natural process, cheaper
Cheaper, accessible, can be modified Used chemical and precipitated waste
Low energy required, possible continuous regeneration of resin, efficient, mobile Regeneration chemicals
treatment possible
Higher recovery of fresh water, compact modules, viruses and organics, etc.
removal
Concentrate flow during filtration operation, high contain of backwash waste
output during membrane cleaning
Higher recovery of fresh water, compact modules
Cheaper, efficient removal of dissolved and suspended contaminants
Removes monovalent salts, dissolved contaminants, etc., compact modules Concentrated flow during filtration operation, high content of backwash waste
output during membrane cleaning
Cheaper, simple and clean technology Sludge waste at the end of the treatment
25
5.3. Surface Active Agents (Surfactants)
Surface active agents are essential materials and very common in different industries, including
chemical, detergents, paints, etc. In addition, it is critical in the oil and gas industry, especially in oil
recovery processes, at the same time it is also used in environmental protection. Consequently, it is
necessary to understand the physical and chemical characteristics of surfactants, unaccepted
characteristics and phase behavior is vital in the chemical industry. Furthermore, surface active agents
mainly consist of two parts; one is hydrophilic and the other is hydrophobic. Figure 10 shows the two
parts of a surfactant atom. The understanding of surfactant phenomena, including the application of
surfactant and the elements or compounds that form surfactant (Ottewill, 1984). In petroleum
industries, the breaking emulsion through chemical demulsification by apply surfactant or demulsifiers
as chemical additives is important methods. Table 3 represent different types of demulsifiers.

Figure 12. Basic schematic of a surfactant molecule (Shui, van den Berg, & Eijkel, 2009).

26
Table 3

Summary of application surfactant in demulsification emulsion

Surfactant name Sort and characteristic Emulsion preparation Operational conditions Advantages Reference
surfactant
alkyl sulfate Anionic Surfactants Small unilamellar vesicles were prepared by addition of three surfactants the different types of alkyl sulfate were used to (Silvander, Karlsson, &
ultrasonic irradiation of samples containing about 25 in different concentration have solubilization of small unilamellar lecithin Edwards, 1996)
mg lecithin in 5 ml buffer. A Soniprep 150 was used influence . on the turbidity of vesicles
for the irradiation The samples were sonicated for 1 h sonicated lecithin vesicles in
and thereafter diluted with buffer to the desired buffer containing 150 mM NaCl
concentration and filtrated through a 0.2-mm
Sartorius Minsart filter. However, the different type
of alkyl sulfate was used to solubilization of small
unilamellar lecithin vesicles

polyoxyethylene nonylphenols
Fourier transform infrared
(FTIR)
Triton X-100 (polyethylene glycol
octylphenyl ether)
Nonionic Surfactants
Nonionic surfactant. Fourier
transform infrared have trimeric and
it is got in two stage of
polymerization.
The first stage is production Acyl
chloride by reaction thionyl chloride
with fatty acid with using identical
conditions. The second stage is the
extraction of amide surfactant.
Nonionic hydrophilic surfactant
The water and oil are left together, and after that by
using blending mixture for 5 min at 1500 rpm the
emulsion was made and test the stability bt livng the
sample at room temperature around 25℃ for 24 hours
and observation if their water sapreted.
The crude oil from mineral wells was used and heated
to (50 ◦C). Sequentially emulsifier added to the
sample and mixed at 10000 rpm for half hour. Then
water 20wt% concertation where added to the sample.
The sample is collated after 60 min of mixing.
Two type of crude oils and tap water were used to the
preparation of oil-in-water emulsions , the total
volume that was preparation about 500mL.
Surfactants add in different dose
and add to water phase before
emulsification. The entire volume
of samples is 15 mL.
The best operational conditions at
160◦C
And 2.5wt% water content
Using surfactant dose in the range
from (0.3-2.5 wt%) with mixing
speed between 1000 rpm to 2000
rpm for maximum 15 min.
Furthermore, the pH for a solution
(6-7.8), and the temperature of
homogenization (25–90 1C).
The (hydrophilic-lipophilic balance ) of the (Fan, Simon, & Sjöblom,
surfactant very high which is 14.2 and this gave 2009)
surfactant very high performance in
demulsification processing
High performance in emulsification impact on (R. Zhang et al., 2017)
water-in-oil emulsion with 2.5:7.5 ratio. The tests
of trimeric nonionic surfactant showed positive
result that (FTIR) work on enhanced the
characteristics of oil-based drilling fluids.
Generally, the (FTIR) enhanced the rheological
characteristics, thermal stability and API
filtration.
Using to the stabilized oil-in-water emulsion (Abdurahman, Rosli,
Azhari, & Hayder, 2012)

alkyltrimethylammonium Cationic surfactants 100mL of oil-in-water emulsion was produced 70mL Demulsifier concentration equal to The surfactant was used to determine the effect (Hirasaki et al., 2010)
bromide of brine water was added to bottles and mixed with 200ppm with room temperature on water and oil separation
30mL of crude oil from American Petroleum Institute around (25oc-30o c) of produced emulsions resulting from surfactant-
(API) at high speed for 10 min. polymer
floods.

Tweens Nonionic surfactant . The surfactant
characterized with HLB range from
11 to 16.7 and high alkenes chains
high molecular weight and content
groups of ester and ketone
Water in oil emulsion was prepared with water The temperature was fixed on 60 No corrosion impact (Roodbari et al., 2016)
content 10% C and the surfactant adding in the
range from 300ppm to 900ppm

27
Poly(ethylene glycol) distearate,
Polyoxyethylene (10) tridecyl
ether, N,N-
Dimethyldodecylamine N –
oxide solution Polyethylene glycol
sorbitan monooleate
Trioctylmethylammonium
chloride (TOMAC), 1-
Hexadecyltrimethylammonium
bromide (CTAB) and
Trioctylmethylammonium
bromide (TOMAB)
PE 6100 and RPE 3110
C10E3, DTPB and SDS
poly(propylene oxide) , Nonionic surfactant mass screening
poly(ethylene oxide) and sodium
dodecyl sulfate (SDS)
chloride (Cl),
bis(trifluoromethanesulphonyl)
andhexafluorophosphate (PF6)
Six dendritic copolymers
nonionic surfactant and amphoteric
surfactant
Ionic surfactant
nonionic surfactant. The low number
of relative solubility number (RSN)
The surfactant from different families
anionic, non-ionic and cationic
was depended for selecting the
demulsifiers
ionic liquids with long alkyl chains (n
= 10, 12 and 14)
Dendritic polyether. The surfactant
was prepared by reaction of ethylene
oxide and propylene oxide with
various proportions
Synthetic water in oil emulsion was prepared with The first three parameters fixed in
water cut 10% and 20% range as following temperature
(50 C◦ -80 C◦), pH (5-9) water cut
(10%-20%) and surfactant
concentration between (0-
1000ppm),
Synthetic water in oil emulsion with different water Dosage for three surfactants
cut between 300 ppm and 2000 ppm,
while the other parameters fixed in
range as show pH (5-9), water cut
(10%-20%) and temperature (50
C◦-80 C◦)
Water in crude oil emulsion with water content 2% Thermochemical dewatering
and 22% for two type of heavy crude oil method was applied, surfactant
was mixed (1:1) and add to the
emulsion with concentration 1%,
while both surfactant dissolved in
benzene and kerosene
Synthetic water in oil emulsion with 60% water pH range from 2 to 13
content
Synthetic water in oil emulsion with water oil ratio Demulsifiers were added at a
(1:1) concentration from 200 μL to
10000 mg/L at 40 C◦
Synthetic water in oil emulsion with water content Three demulsifiers were studied in
20% range 500 ppm to 3500 ppm
during 24 hours
Water in crude oil emulsion with ratio (7:13) Surfactant concentration is 150
respectively. mg/L
N- Dimethyldodecylamine N –oxide solution (Roshan, Ghader, &
have high performance in breaking water in oil Rahimpour, 2018)
emulsion
The result shows that the pH and temperature are (Biniaz, Farsi, &
the most useful variables, while the maximum Rahimpour, 2016)
separation occurs at maximum temperate and pH
near to the natural value
The maximum separation achieved at high
temperature 80 C◦ (Adilbekova, Omarova,
Karakulova, & Musabekov,
2015)
The result indicates that the pH near to neutral (Daaou & Bendedouch,
medium more stable than basic or acidic 2012)
environment cationic and anionic surfactant
much better in separation water than nonionic
surfactant
The result shows the demulsifiers reduced the (Kang et al., 2018)
interfacial viscoelasticity and separation of
water occur and the efficiency depends on
demulsifiers nature.
The demulsifiers achieve high demulsification (Hazrati, Beigi, & Abdouss,
rate (86%-95%) and reduce the inter factual 2018)
tension to range range from 0.7–6.26 mN/m.
The surfactant achieve high demulsification rate (J. Wang, Hu, Li, Li, &
at 150 mg/l after 15 min Yang, 2010)
28
On other hands, hydrophilic-lipophilic balance (HLB) of demulsifier is an important factor that helps in
determining the attraction of demulsifier into water or oil phase. The surfactants with high HLB
number above 10 are hydrophilic and it has high attraction into the water phase. While surfactants have
HLB lower 10 considered as lipophilic surfactant and attraction into the oil phase (Shehzad et al.,
2018). HLB parameter is useful in selection demulsifier as well as the surfactant with HLB between 8
to 11.63 must have food performance in water in oil emulsion (Ojinnaka, Ajienka, Abayeh, Osuji, &
Duru, 2016). According (Griffin, 1949), surfactant with HLB value between 7 to 9 considered as
wetting agents, while the surfactant with HLB (4-6) can be applied as emulsifiers and surfactant with
HLB (13-15) can be applied as detergents. (Fan et al., 2009), investigate the effect of HLB number in
destabilizing water in oil emulsion with the ratio (1:1) by using polyoxyethylene nonylphenols as a
nonionic surfactant. The result shows that the surfactant with HLB 14.2 has high performance in
braking emulsion reverse surfactant with high HLB that has less efficiency which may be due to the
interaction between crude oil components and surfactant and long oxyethyl head groups. (Charchari &
Abdelli, 2014), investigate the influence HLB value of non-ionic surfactants in aqueous solutions on
extraction oil. The result clear that increasing the HLB of surfactant improve the enhanced oil yield.
(Yeşilyurt, Vaziri Hassas, Karakaş, & Boylu, 2017), study the effect of HLB number on water
recovery, dewatering efficiency and flotation performance of hard bituminous coal slimes. It was
concluded that the surfactant has HLB number equal to ten have the highest performance infiltration.
(Xu et al., 2018), study the effect (HLB), surface tension, infrared spectra and wetting time of anionic
surfactants on coal dust wetting ability. It was concluded that reduce the wetting time have no influence
on surface tension, while reducing surface tension leading to decreasing wetting time at low surfactant
dosage. In addition, electrostatic repulsions and hydrophobic play a major role in the adsorption density
as well as the surfactant with a high value of HLB has high ability to bring the coal dust into the bulk
solution. (Hassas, Karakaş, & Çelik, 2014), designed a special set-up to investigate the effect of
surfactants HLB value on dewatering lignite particles. The result clear that the surfactant with HLB
near to 10 has high performance in dewatering the ultrafine lignite, while the surfactants with lower
HLB are suitable for dewatering reagents like hard coals. (Jafarirad, 2017), found that hydrophobic
blocks of amphiphilic agents have a significant effect on surfactant micellar characteristics as well as
the chain lengths of hydrophobic and hydrophilic have an influence on the micellar behavior of
surfactant. Thus, it helps to design surfactant diversity on hydrophilic/lipophilic balance. (M. Zhang &
Wu, 2018), clear the influence of hydrophilic surfactants including Tween 80, IGEPAL CO890,
IGEPAL CO520 and sodium oleate with hydrophilic-lipophilic balance (HLB) range between 10 and
18 on bio-oil separation. The result present that the surfactants hydrophobic groups have a significant
effect on oil separation. (A. Y. Tang, Lee, Wang, & Kan, 2018), investigate the hydrophilic-lipophilic
balance (HLB) based on non-ionic surfactants and the relationships between the levelness of the dyed
samples and K/Sum value, (HLB) and reflectance. It was concluded that increasing HLB value
increases the reflectance percentage and decreases the K/Ssum value as well as the optimum HLB value
leading to high visual appearance a levelness of dyed samples. (Jin, Ugine, Chen, & Streett, 2009),
enhanced the direct dropping method to find the HLB value for Metarhizium anisopliae conidia during
dehydration at various water content stages. The experimental result shows that the HLB value for
Metarhizium anisopliae conidia was 8 and at the optimum value the dehydration percentage did not
change, while the wetting time significantly increased. Finally, it was concluded that the hydrophilic-
lipophilic balance (HLB) value of a surfactant is a crucial factor that helps in selecting surfactant for a
specific application. Actually, The hydrophilic-lipophilic balance (HLB) is a skill that uses for seeing
the tendency of surfactant between water and oil phase as well as HLB value help in development
advanced emulsification method (Yamashita & Sakamoto, 2016).
5.4. General Classification of Surface Active Agents
There are several ways to classify surface active agents and the most common one depends on the
nature of the hydrophilic part. Normally there are three basic types, cationic, anionic and amphoteric.
(Gore et al., 2000), updated a list of existing surfactants. (van Os, Haak, & Rupert, 2012), reported the
physicochemical characteristics of different types of surfactant, including nonionic and cationic.
(Porter, 1994), published a useful book on surfactant. In addition, polymeric surfactant is one type of
surfactant that use to formation emulsions and suspensions their elements, Figure. 11 shows the
common types of surfactant

29
 Rhamnolipid

Bacillus sp
Emulsan
Bio Surfactant Pseudomonas

Alasan

RLichenysinhamnolipid Acinetobacter

Alkyl Ether Sulfate and Alkyl Ethoxy Sulfate

Surfactant Mixtures Cetyl Trimethyl Ammonium Bromide (CTAB)

Alkyl propoxy Sulfate and Alkyl Ethoxy Sulfonates

Coco Alkyl Trimethyl Ammonium Chloride

Stearyl Trimethyl Ammonium Chloride

Cationic
Dodecyl Trimethyl Ammonium Bromide (DTAB)

Ethoxylated Alkyl Amine

Surfactants

Alkyl Ethoxy Carboxylated

Neodol

Neodol Ethoxylate 91-8

Nonionic Alkyl Polyglycoside (APG)

Neodol 67 Propoxylated Sulfate (N67-7POS)

Nonylphenol “N” Ethoxylate

Polyethoxylated Alkyl Phenols

Lauryl betaine

Betaine Citrate
Amphoterics
Sodium hydroxymethylglycinate

Betaines ,Cocoalkyldimethyl

Alkyl (or Alcohol) Ethoxy Sulfate (AES)

Alkyl Aryl Sulfonates

Anionic
Alkyl Sulfate (AS)

Sodium Dodecyl Sulfate (SDS)

Alkoxylated alkyl phenol condensates

Polymeric
Polyalkylene glycol modified polyester
Figure. 13 Shows general types of surfactant.

30
6. Summary
This literature article focused on global water production from the petroleum industry, the source of
water from three basic fields; oil, gas and coal bed methane. Water production from different platforms
consists of several elements and have influence on the environment. In addition, almost the all the
water produced as emulsion shape, and generally emulsion can be found in three general shapes.
Emulsion can be formed through turbulence strength in choke valves or during piping flow. However,
the emulsion stability is related with the interfacial film among the continuous phase and diffusion
phase, the emulsion stability can be enhanced through emulsifying agents, like asphaltenes and resins,
interfacial films, elastic modulus & viscous modulus, duration time and agitation speed and other
factors. However, the emulsion stability can be measured by different methods, and test bottles is one
of these methods.

Acknowledgment
The authors wish to acknowledge Universiti Putra Malaysia for financial support. Gratefully thanks to
Mrs Siti Aslina Hussain and Mr Luqman Chuah Abdullah for their contribution and support.

31
References

Abdurahman, N., Rosli, Y., Azhari, N., & Hayder, B. (2012). Pipeline transportation of viscous
crudes as concentrated oil-in-water emulsions. Journal of Petroleum Science and
Engineering, 90, 139-144.
Adilbekova, A. O., Omarova, K. I., Karakulova, A., & Musabekov, K. B. (2015). Nonionic
surfactants based on polyoxyalkylated copolymers used as demulsifying agents.
Colloids and Surfaces A: Physicochemical and Engineering Aspects, 480, 433-438.
AHMED, N. S., NASSAR, A. M., ZAKI, N. N., & GHARIEB, H. K. (1999). Stability and rheology of
heavy crude oil-in-water emulsion stabilized by an anionic-nonionic surfactant
mixture. Petroleum Science and Technology, 17(5-6), 553-576.
Ali, M., & Alqam, M. (2000). The role of asphaltenes, resins and other solids in the
stabilization of water in oil emulsions and its effects on oil production in Saudi oil
fields. Fuel, 79(11), 1309-1316.
Arla, D., Sinquin, A., Palermo, T., Hurtevent, C., Graciaa, A., & Dicharry, C. (2007). Influence
of pH and water content on the type and stability of acidic crude oil emulsions.
Energy & fuels, 21(3), 1337-1342.
Arthur, J. D., Langhus, B. G., & Patel, C. (2005). Technical summary of oil & gas produced
water treatment technologies. All Consulting, LLC, Tulsa, OK.
Azim, A. A., Abdel-Raouf, M.-S., Abdel-Raheim, A.-R., & Maysour, N.-S. (2010). Sugar-based
ethoxylated amine surfactants as demulsifiers for crude oil emulsions: 2-
demulsification of different types of crudes. Brazilian Journal of Petroleum and Gas,
4(4).
Bera, A., Mandal, A., & Guha, B. (2013). Synergistic effect of surfactant and salt mixture on
interfacial tension reduction between crude oil and water in enhanced oil recovery.
Journal of Chemical & Engineering Data, 59(1), 89-96.
Biniaz, P., Farsi, M., & Rahimpour, M. (2016). Demulsification of water in oil emulsion using
ionic liquids: Statistical modeling and optimization. Fuel, 184, 325-333.
Binks, B. P., & Rocher, A. (2009). Effects of temperature on water-in-oil emulsions stabilised
solely by wax microparticles. Journal of colloid and interface science, 335(1), 94-104.
Bonnet, M., Cansell, M., Placin, F. d. r., David-Briand, E., Anton, M., & Leal-Calderon, F.
(2010). Influence of ionic complexation on release rate profiles from multiple water-
in-oil-in-water (W/O/W) emulsions. Journal of agricultural and food chemistry,
58(13), 7762-7769.
Borges, B., Rondón, M., Sereno, O., & Asuaje, J. (2009). Breaking of water-in-crude-oil
emulsions. 3. Influence of salinity and water− oil ratio on demulsifier action. Energy
& fuels, 23(3), 1568-1574.
Bourrel, M., Salager, J., Schechter, R., & Wade, W. (1980). A correlation for phase behavior
of nonionic surfactants. Journal of colloid and interface science, 75(2), 451-461.
Canevari, G. P. (1982). The formulation of an effective demulsifier for oil spill emulsions.
Marine pollution bulletin, 13(2), 49-54.
Cassella, R. J., Dos Reis, L. G. T., Santelli, R. E., & Oliveira, E. P. (2011). Direct determination
of manganese in produced waters from petroleum exploration by electrothermal
atomic absorption spectrometry using Ir–W as permanent modifier. Talanta, 85(1),
415-419.

32
Chan, L.-H., Starinsky, A., & Katz, A. (2002). The behavior of lithium and its isotopes in oilfield
brines: evidence from the Heletz-Kokhav field, Israel. Geochimica et Cosmochimica
Acta, 66(4), 615-623.
Chanamai, R., & McClements, D. J. (2000). Creaming stability of flocculated monodisperse
oil-in-water emulsions. Journal of colloid and interface science, 225(1), 214-218.
Charchari, S., & Abdelli, M. (2014). Enhanced Extraction by Hydrodistillation of Sage (Salvia
officinalis L.) Essential Oil Using Water Solutions of Non-ionic Surfactants. Journal of
Essential Oil Bearing Plants, 17(6), 1094-1099.
Chen, G., & Tao, D. (2005). An experimental study of stability of oil–water emulsion. Fuel
processing technology, 86(5), 499-508.
Chistyakov, B. (2001). 6. Theory and practical application aspects of surfactants. Studies in
Interface Science, 13, 511-618.
Cullum, D. (1994). Surfactant types; classification, identification, separation Introduction to
Surfactant Analysis (pp. 17-41): Springer.
Czarnecki, J. (2008). Stabilization of water in crude oil emulsions. Part 2. Energy & fuels,
23(3), 1253-1257.
Daaou, M., & Bendedouch, D. (2012). Water pH and surfactant addition effects on the
stability of an Algerian crude oil emulsion. Journal of Saudi Chemical Society, 16(3),
333-337.
Dai, L., Zhan, X., Wei, Y., Sun, C., Mao, L., McClements, D. J., & Gao, Y. (2018). Composite
zein-propylene glycol alginate particles prepared using solvent evaporation:
Characterization and application as Pickering emulsion stabilizers. Food
Hydrocolloids, 85, 281-290.
Dal Ferro, B., & Smith, M. (2007). Global onshore and offshore water production. Oil and Gas
Review, OTC edition.
de Oliveira, C. B., Souza, W., Santana, C. F., Santana, C. C., Dariva, C., Franceschi, E., . . .
Santos, A. F. (2018). Rheological Properties of Water-in-Brazilian Crude Oil
Emulsions: Effect of Water Content, Salinity, and pH. Energy & fuels, 32(8), 8880-
8890.
de Oliveira, M. C. K., Miranda, L. R., de Carvalho, A. B., & Miranda, D. F. S. (2018). Viscosity of
Water-in-Oil Emulsions from Different American Petroleum Institute Gravity
Brazilian Crude Oils. Energy & fuels, 32(3), 2749-2759.
Derkach, S. R. (2009). Rheology of emulsions. Advances in Colloid and Interface Science,
151(1-2), 1-23.
Elektorowicz, M., Habibi, S., & Chifrina, R. (2006). Effect of electrical potential on the electro-
demulsification of oily sludge. Journal of colloid and interface science, 295(2), 535-
541.
Fakhru’l-Razi, A., Pendashteh, A., Abdullah, L. C., Biak, D. R. A., Madaeni, S. S., & Abidin, Z. Z.
(2009). Review of technologies for oil and gas produced water treatment. Journal of
hazardous materials, 170(2-3), 530-551.
Fan . imon . lom, J. (2009). Chemical destabilization of crude oil emulsions:
effect of nonionic surfactants as emulsion inhibitors. Energy & fuels, 23(9), 4575-
4583.
Fingas, M. (1995). Water-in-oil emulsion formation: A review of physics and mathematical
modelling. Spill Science & Technology Bulletin, 2(1), 55-59.
Fingas, M., & Fieldhouse, B. (2003). Studies of the formation process of water-in-oil
emulsions. Marine pollution bulletin, 47(9), 369-396.
Fingas, M., & Fieldhouse, B. (2004). Formation of water-in-oil emulsions and application to
oil spill modelling. Journal of hazardous materials, 107(1), 37-50.

33
Fingas, M., & Fieldhouse, B. (2009). Studies on crude oil and petroleum product emulsions:
Water resolution and rheology. Colloids and Surfaces A: Physicochemical and
Engineering Aspects, 333(1), 67-81.
Fingas, M., Fieldhouse, B., & Wang, Z. (2003). The long term weathering of water-in-oil
emulsions. Spill Science & Technology Bulletin, 8(2), 137-143.
Fink, J. (2015). Petroleum engineer's guide to oil field chemicals and fluids: Gulf Professional
Publishing.
Florence, A., & Whitehill, D. (1982). The formulation and stability of multiple emulsions.
International Journal of Pharmaceutics, 11(4), 277-308.
Fortuny, M., Oliveira, C. B., Melo, R. L., Nele, M., Coutinho, R. C., & Santos, A. F. (2007).
Effect of salinity, temperature, water content, and pH on the microwave
demulsification of crude oil emulsions. Energy & fuels, 21(3), 1358-1364.
Gaonkar, A. G. (1992). Effects of salt, temperature, and surfactants on the interfacial tension
behavior of a vegetable oil/water system. Journal of colloid and interface science,
149(1), 256-260.
Garti, N. (1997). Progress in stabilization and transport phenomena of double emulsions in
food applications. LWT-Food Science and Technology, 30(3), 222-235.
Georgie, W., Sell, D., & Baker, M. (2001). Establishing Best Practicable Environmental Option
Practice for Produced Water Management in the Gas and Oil Production Facilities.
Paper presented at the SPE/EPA/DOE Exploration and Production Environmental
Conference.
Goldszal, A., & Bourrel, M. (2000). Demulsification of crude oil emulsions: correlation to
microemulsion phase behavior. Industrial & engineering chemistry research, 39(8),
2746-2751.
Gore, R. H., Kopko, R. J., Machleder, W. H., Mathis, W. D., Stevens, B. M., & Sun, Y. (2000).
Pesticide compositions: Google Patents.
Graham, B. F., May, E. F., & Trengove, R. D. (2008). Emulsion inhibiting components in crude
oils. Energy & fuels, 22(2), 1093-1099.
Griffin, W. C. (1949). Classification of surface-active agents by" HLB". J. Soc. Cosmet. Chem.,
1, 311-326.
Groenzin, H., & Mullins, O. C. (2007). Asphaltene molecular size and weight by time-resolved
fluorescence depolarization. Asphaltenes, heavy oils, and petroleomics, 17-62.
Gu, G., Xu, Z., Nandakumar, K., & Masliyah, J. (2002). Influence of water-soluble and water-
insoluble natural surface active components on the stability of water-in-toluene-
diluted bitumen emulsion. Fuel, 81(14), 1859-1869.
Gupta, A., Eral, H. B., Hatton, T. A., & Doyle, P. S. (2016). Nanoemulsions: formation,
properties and applications. Soft Matter, 12(11), 2826-2841.
Haegh, T., & Ellingsen, T. (1977). The effect of breaking waves on oil spills; 1. Emulsification
of crude oil at sea. SINTEF, The Foundation of Scientific and Industrial Research at
the University of Trondheim, Norway, 23.
Hanapi, B., Ariffin, S., Aizan, A., & Siti, I. (2006). Study on demulsifier formulation for treating
Malaysian crude oil emulsion. Internet website: http://eprints. utm.
my/2768/1/74004. pdf.
Hassas B. V. Karakaş F. Çelik M. . (2014). Ultrafine coal dewatering: Relationship
between hydrophilic lipophilic balance (HLB) of surfactants and coal rank.
International Journal of Mineral Processing, 133, 97-104.
Hazrati, N., Beigi, A. A. M., & Abdouss, M. (2018). Demulsification of water in crude oil
emulsion using long chain imidazolium ionic liquids and optimization of parameters.
Fuel, 229, 126-134.

34
Hirasaki, G. J., Miller, C. A., Raney, O. G., Poindexter, M. K., Nguyen, D. T., & Hera, J. (2010).
Separation of produced emulsions from surfactant enhanced oil recovery processes.
Energy & fuels, 25(2), 555-561.
Hu, G., Li, J., & Zeng, G. (2013). Recent development in the treatment of oily sludge from
petroleum industry: a review. Journal of hazardous materials, 261, 470-490.
Igunnu, E. T., & Chen, G. Z. (2012). Produced water treatment technologies. International
Journal of Low-Carbon Technologies, 9(3), 157-177.
Issaka, S. A., Nour, A. H., & Yunus, R. M. (2015). Review on the fundamental aspects of
petroleum oil emulsions and techniques of demulsification. Journal of Petroleum &
Environmental Biotechnology, 6(2), 1.
Jackson, L., & Myers, J. (2002). Alternative use of produced water in aquaculture and
hydroponic systems at naval petroleum reserve No. 3. Paper presented at the
Ground Water Protection Council Produced Water Conference, Colorado Springs,
CO, Oct.
Jacobs, R., Grant, R., Kwant, J., Marquenie, J., & Mentzer, E. (1992). The composition of
produced water from Shell operated oil and gas production in the North Sea
Produced Water (pp. 13-21): Springer.
Jafarirad, S. (2017). Innovative amphiphilic cellulose nanobiostructures: Physicochemical,
spectroscopic, morphological, and hydrophilic/lipophilic properties. Journal of
dispersion science and technology, 38(8), 1187-1195.
Jin, X., Ugine, T. A., Chen, J., & Streett, A. D. (2009). Method for determining the best
hydrophilic-lipophilic balance (HLB) number for a compatible non-ionic surfactant in
formulation development for aerial conidia of Metarhizium anisopliae (Hypocreales:
Clavicipitaceae). Biocontrol science and technology, 19(3), 341-347.
Johnsen, S., Frost, T., Hjelsvold, M., & Utvik, T. R. (2000). The Environmental Impact Factor-a
proposed tool for produced water impact reduction, management and regulation.
Paper presented at the SPE International Conference on Health, Safety and
Environment in Oil and Gas Exploration and Production.
Julio, L. M., Ixtaina, V. Y., Fernández, M. A., Sánchez, R. M. T., Wagner, J. R., Nolasco, S. M., &
Tomás, M. C. (2015). Chia seed oil-in-water emulsions as potential delivery systems
of ω-3 fatty acids. Journal of Food Engineering, 162, 48-55.
Kang, W., Yin, X., Yang, H., Zhao, Y., Huang, Z., Hou, X., . . . Zhang, X. (2018). Demulsification
performance, behavior and mechanism of different demulsifiers on the light crude
oil emulsions. Colloids and Surfaces A: Physicochemical and Engineering Aspects,
545, 197-204.
Khan, B. A., Akhtar, N., Khan, H. M. S., Waseem, K., Mahmood, T., Rasul, A., . . . Khan, H.
(2011). Basics of pharmaceutical emulsions: A review. African Journal of Pharmacy
and Pharmacology, 5(25), 2715-2725.
Khatib, Z., & Verbeek, P. (2003). Water to value-produced water management for
sustainable field development of mature and green fields. Journal of Petroleum
Technology, 55(01), 26-28.
Kilpatrick, P., & Spiecker, P. (2001). Asphaltene Emulsions. InEncyclopedic Handbook of
Emulsion Technology, ed. J. Sjoblom, Chap. 30,707: New York: Marcel Dekker.
Kobayashi, I., Yasuno, M., Iwamoto, S., Shono, A., Satoh, K., & Nakajima, M. (2002).
Microscopic observation of emulsion droplet formation from a polycarbonate
membrane. Colloids and Surfaces A: Physicochemical and Engineering Aspects,
207(1), 185-196.
Kokal, S., & Alvarez, C. (2003). Reducing pressure drop in offshore pipelines by controlling the
viscosities of pressurized emulsions. Paper presented at the Middle East Oil Show.
Kokal, S., & Wingrove, M. (2000). Emulsion separation index: From laboratory to field case
studies. Paper presented at the SPE Annual Technical Conference and Exhibition.

35
Kokal, S. L. (2005). Crude oil emulsions: A state-of-the-art review. SPE Production & Facilities,
20(01), 5-13.
Kuo, C.-H., & Lee, C.-L. (2009). Treatment of a cutting oil emulsion by microwave irradiation.
Separation Science and Technology, 44(8), 1799-1815.
Le Follotec, A., Pezron, I., Noik, C., Dalmazzone, C., & Metlas-Komunjer, L. (2010). Triblock
copolymers as destabilizers of water-in-crude oil emulsions. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 365(1-3), 162-170.
Lee, H. M., Lee, J. W., & Park, O. O. (1997). Rheology and dynamics of water-in-oil emulsions
under steady and dynamic shear flow. Journal of colloid and interface science,
185(2), 297-305.
Lee, J. S., Kim, J. W., Han, S. H., Chang, I. S., Kang, H. H., Lee, O. S., . . . Suh, K. D. (2004). The
sta ilization of L‐ascor ic acid in aqueous solution and water‐in‐oil‐in‐water dou le
emulsion by controlling pH and electrolyte concentration. International Journal of
Cosmetic Science, 26(4), 217-217.
Levine, S., & Sanford, E. (1985). Stabilisation of emulsion droplets by fine powders. The
Canadian Journal of Chemical Engineering, 63(2), 258-268.
Lim, J., Wong, S., Law, M., Samyudia, Y., & Dol, S. (2015). A review on the effects of
emulsions on flow behaviours and common factors affecting the stability of
emulsions. Journal of Applied Sciences, 15, 167-172.
Lobato, M., Pedrosa, J., Hortal, A., Martinez-Haya, B., Lebron-Aguilar, R., & Lago, S. (2007).
Characterization and Langmuir film properties of asphaltenes extracted from
Arabian light crude oil. Colloids and Surfaces A: Physicochemical and Engineering
Aspects, 298(1), 72-79.
Maia Filho, D. C., Ramalho, J. B., Lucas, G. M., & Lucas, E. F. (2012). Aging of water-in-crude
oil emulsions: Effect on rheological parameters. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 405, 73-78.
Marrucci, G. (1969). A theory of coalescence. Chemical engineering science, 24(6), 975-985.
Martínez-Palou, R., Cerón-Camacho, R., Chávez, B., Vallejo, A. A., Villanueva-Negrete, D.,
Castellanos, J., . . . Aburto, J. (2013). Demulsification of heavy crude oil-in-water
emulsions: A comparative study between microwave and thermal heating. Fuel, 113,
407-414.
Masalova, I., Malkin, A. Y., Slatter, P., & Wilson, K. (2003). The rheological characterization
and pipeline flow of high concentration water-in-oil emulsions. Journal of non-
newtonian fluid mechanics, 112(2), 101-114.
McLean, J. D., & Kilpatrick, P. K. (1997). Effects of asphaltene solvency on stability of water-
in-crude-oil emulsions. Journal of colloid and interface science, 189(2), 242-253.
Menon, V., Wasan, D., & Becher, P. (1985). Encyclopedia of Emulsion Technology, vol. 2:
Marcel Dekker, Inc., New York & Basel.
Möbius, D., Miller, R., & Fainerman, V. B. (2001). Surfactants: chemistry, interfacial
properties, applications (Vol. 13): Elsevier.
Mohammed, R., Bailey, A., Luckham, P., & Taylor, S. (1993). Dewatering of crude oil
emulsions 2. Interfacial properties of the asphaltic constituents of crude oil. Colloids
and Surfaces A: Physicochemical and Engineering Aspects, 80(2-3), 237-242.
Mohammed, R., Bailey, A., Luckham, P., & Taylor, S. (1994). Dewatering of crude oil
emulsions 3. Emulsion resolution by chemical means. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 83(3), 261-271.
Moradi, M., Alvarado, V., & Huzurbazar, S. (2010). Effect of salinity on water-in-crude oil
emulsion: evaluation through drop-size distribution proxy. Energy & fuels, 25(1),
260-268.

36
Mouraille, O., Skodvin, T., Sjöblom, J., & Peytavy, J.-L. (1998). Stability of water-in-crude oil
emulsions: role played by the state of solvation of asphaltenes and by waxes. Journal
of dispersion science and technology, 19(2-3), 339-367.
Muggeridge, A., Cockin, A., Webb, K., Frampton, H., Collins, I., Moulds, T., & Salino, P. (2014).
Recovery rates, enhanced oil recovery and technological limits. Phil. Trans. R. Soc. A,
372(2006), 20120320.
Mukherjee, S., & Kushnick, A. P. (1988). Effect of demulsifiers on interfacial properties
governing crude oil demulsification: ACS Publications.
Murakami, R., Moriyama, H., Noguchi, T., Yamamoto, M., & Binks, B. P. (2014). Effects of the
density difference between water and oil on stabilization of powdered oil-in-water
emulsions. Langmuir, 30(2), 496-500.
Nguyen, D., Sadeghi, N., & Houston, C. (2012). Chemical interactions and demulsifier
characteristics for enhanced oil recovery applications. Energy & fuels, 26(5), 2742-
2750.
Nollet, L. M. (2004). Handbook of Food Analysis: Volume 3 Methods, Instruments and
Applications: CRC Press.
Oh, C., Chung, S.-C., Shin, S.-i., Kim, Y. C., Im, S.-S., & Oh, S.-G. (2002). Distribution of
macropores in silica particles prepared by using multiple emulsions. Journal of
colloid and interface science, 254(1), 79-86.
Ojinnaka, C., Ajienka, J., Abayeh, O., Osuji, L., & Duru, R. (2016). Formulation of best-fit
hydrophile/lipophile balance-dielectric permittivity demulsifiers for treatment of
crude oil emulsions. Egyptian Journal of Petroleum, 25(4), 565-574.
Okochi, H., & Nakano, M. (2000). Preparation and evaluation of w/o/w type emulsions
containing vancomycin. Advanced drug delivery reviews, 45(1), 5-26.
Oren, J. J., & MacKay, G. D. M. (1977). Electrolyte and pH effect on emulsion stability of
water-in-petroleum oils. Fuel, 56(4), 382-384.
Ortiz, D., Baydak, E., & Yarranton, H. (2010). Effect of surfactants on interfacial films and
stability of water-in-oil emulsions stabilized by asphaltenes. Journal of colloid and
interface science, 351(2), 542-555.
Ottewill, R. (1984). In Surfactants; Tadros, Th. F., Ed: Academic Press: London.
Paige, R., & Sweeney, F. (1993). Produced Water-Reinjection: Understanding the Problems.
Paper presented at the Water Management Offshore Conference.
Pal, R. (1996). Effect of droplet size on the rheology of emulsions. AIChE Journal, 42(11),
3181-3190.
Pal, R., Yan, Y., Masliyah, J., & Schramm, L. (1992). Emulsions: fundamentals and applications
in the petroleum industry. Advances in Chemistry Series, 231, 295-312.
Pereira, J. C., López, I., Salas, R., Silva, F., Fernández, C., Urbina, C., & López, J. C. (2007).
Resins: the molecules responsible for the stability/instability phenomena of
asphaltenes. Energy & fuels, 21(3), 1317-1321.
Perles, C. E., Volpe, P. L. O. f., & Bombard, A. n. J. (2012). Study of the cation and salinity
effect on electrocoalescence of water/crude oil emulsions. Energy & fuels, 26(11),
6914-6924.
Poindexter, M. K., & Marsh, S. C. (2009). Inorganic solid content governs water-in-crude oil
emulsion stability predictions. Energy & fuels, 23(3), 1258-1268.
Pons, R., Solans, C., & Tadros, T. F. (1995). Rheological behavior of highly concentrated oil-in-
water (o/w) emulsions. Langmuir, 11(6), 1966-1971.
Porter, M. (1994). Handbook of Surfactants Blackie Academic and Professional: Glasgow, UK.
Rabalais, N., McKee, B., Reed, D., & Means, J. (1992). Fate and effects of produced water
discharges in coastal Louisiana, Gulf of Mexico, USA Produced Water (pp. 355-369):
Springer.

37
Reynolds, R. R., & Kiker, R. D. (2003). Produced Water and Associated Issues. Oklahoma
Geological Survey.
Robins, M. M. (2000). Emulsions—creaming phenomena. Current Opinion in Colloid &
Interface Science, 5(5-6), 265-272.
Robins, M. M., Watson, A. D., & Wilde, P. J. (2002). Emulsions—creaming and rheology.
Current Opinion in Colloid & Interface Science, 7(5-6), 419-425.
Rodionova G. Keleşoğlu . lom J. (2014). AC field induced desta ilization of water-
in-oil emulsions based on North Sea acidic crude oil. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 448, 60-66.
Roodbari, N. H., Badiei, A., Soleimani, E., & Khaniani, Y. (2016). Tweens demulsification
effects on heavy crude oil/water emulsion. Arabian Journal of Chemistry, 9, S806-
S811.
Roshan, N., Ghader, S., & Rahimpour, M. R. (2018). Application of the response surface
methodology for modeling demulsification of crude oil emulsion using a demulsifier.
Journal of dispersion science and technology, 39(5), 700-710.
Salager, J.-L. (2000). Formulation concepts for the emulsion maker. Pharmaceutical
Emulsions and Suspensions, 105, 19-72.
Salager, J.-L. (2002). Surfactants types and uses. FIRP booklet(E300A).
Schorling, P.-C., Kessel, D., & Rahimian, I. (1999). Influence of the crude oil resin/asphaltene
ratio on the stability of oil/water emulsions. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 152(1), 95-102.
Schramm, L. L. (1992a). Emulsions: fundamentals and applications in the petroleum industry.
Advances in Chemistry Series, 321.
Schramm, L. L. (1992b). Fundamentals and applications in the petroleum industry.
Schröder, A., Sprakel, J., Schroën, K., Spaen, J. N., & Berton-Carabin, C. C. (2018).
Coalescence stability of Pickering emulsions produced with lipid particles: A
microfluidic study. Journal of Food Engineering, 234, 63-72.
Schubert, H., & Armbruster, H. (1989). Principles of formation and stability of emulsions.
Chemie Ingenieur Technik, 61(9), 701-711.
Sellman, E., Sams, G. W., & Mandewalkar, S. (2013). Improved Dehydration and Desalting of
Mature Crude Oil Fields. Paper presented at the SPE Middle East Oil and Gas Show
and Conference.
Sharma, M., & Shah, D. (1985). Macro-and microemulsions in enhanced oil recovery: ACS
Publications.
Sharma, T., Kumar, G. S., Chon, B. H., & Sangwai, J. S. (2014). Viscosity of the oil-in-water
Pickering emulsion stabilized by surfactant-polymer and nanoparticle-surfactant-
polymer system. Korea-Australia Rheology Journal, 26(4), 377-387.
Sharma, T., Kumar, G. S., & Sangwai, J. S. (2015). Comparative effectiveness of production
performance of Pickering emulsion stabilized by nanoparticle–surfactant–
polymerover surfactant–polymer (SP) flooding for enhanced oil recoveryfor
Brownfield reservoir. Journal of Petroleum Science and Engineering, 129, 221-232.
Shehzad, F., Hussein, I. A., Kamal, M. S., Ahmad, W., Sultan, A. S., & Nasser, M. S. (2018).
Polymeric surfactants and emerging alternatives used in the demulsification of
produced water: A review. Polymer Reviews, 58(1), 63-101.
Shui, L., van den Berg, A., & Eijkel, J. C. (2009). Interfacial tension controlled W/O and O/W
2-phase flows in microchannel. Lab on a Chip, 9(6), 795-801.
Silset, A., Hannisdal, A., Hemmingsen, P. V., & Sjöblom, J. (2010). Emulsions of heavy crude
oils. II. Viscous responses and their influence on emulsion stability measurements.
Journal of dispersion science and technology, 31(10), 1432-1445.

38
Silva, B. F., Rodríguez-Abreu, C., & Vilanova, N. (2016). Recent advances in multiple
emulsions and their application as templates. Current Opinion in Colloid & Interface
Science, 25, 98-108.
Silvander, M., Karlsson, G., & Edwards, K. (1996). Vesicle solubilization by alkyl sulfate
surfactants: a cryo-TEM study of the vesicle to micelle transition. Journal of colloid
and interface science, 179(1), 104-113.
Sjöblom, J., Aske, N., Auflem, I. H., Brandal, Ø., Havre, T. E., Sæther, Ø., . . . Kallevik, H.
(2003). Our current understanding of water-in-crude oil emulsions.: Recent
characterization techniques and high pressure performance. Advances in Colloid and
Interface Science, 100, 399-473.
Sjöblom, J., Mingyuan, L., Christy, A. A., & Gu, T. (1992). Water-in-crude-oil emulsions from
the Norwegian continental shelf 7. Interfacial pressure and emulsion stability.
Colloids and Surfaces, 66(1), 55-62.
Sjöblom, J., Mingyuan, L., Christy, A. A., & Rønningsen, H. P. (1995). Water-in-crude oil
emulsions from the Norwegian continental shelf 10. Ageing of the interfacially active
components and the influence on the emulsion stability. Colloids and Surfaces A:
Physicochemical and Engineering Aspects, 96(3), 261-272.
Sousa, F., Santos, M., Rocha, S., & Trindade, T. (2014). Encapsulation of essential oils in SiO2
microcapsules and release behaviour of volatile compounds. Journal of
microencapsulation, 31(7), 627-635.
Spiecker, P. M., Gawrys, K. L., Trail, C. B., & Kilpatrick, P. K. (2003). Effects of petroleum
resins on asphaltene aggregation and water-in-oil emulsion formation. Colloids and
Surfaces A: Physicochemical and Engineering Aspects, 220(1), 9-27.
Spiecker, P. M., & Kilpatrick, P. K. (2004). Interfacial rheology of petroleum asphaltenes at
the oil− water interface. Langmuir, 20(10), 4022-4032.
Stephenson, M. (1992). A survey of produced water studies Produced water (pp. 1-11):
Springer.
Strassner, J. (1968). Effect of pH on interfacial films and stability of crude oil-water
emulsions. Journal of Petroleum Technology, 20(03), 303-312.
Strømgren, T., Sørstrøm, S., Schou, L., Kaarstad, I., Aunaas, T., Brakstad, O., & Johansen, Ø.
(1995). Acute toxic effects of produced water in relation to chemical composition
and dispersion. Marine Environmental Research, 40(2), 147-169.
Subramanian, D., May, N., & Firoozabadi, A. (2017). Functional Molecules and the Stability of
Water-in-Crude Oil Emulsions. Energy & fuels, 31(9), 8967-8977.
Sztukowski, D. M., & Yarranton, H. W. (2004). Characterization and interfacial behavior of oil
sands solids implicated in emulsion stability. Journal of dispersion science and
technology, 25(3), 299-310.
Tadros, T. (2004). Application of rheology for assessment and prediction of the long-term
physical stability of emulsions. Advances in Colloid and Interface Science, 108, 227-
258.
Tambe, D. E., & Sharma, M. M. (1993). Factors controlling the stability of colloid-stabilized
emulsions: I. An experimental investigation. Journal of colloid and interface science,
157(1), 244-253.
Tang, A. Y., Lee, C., Wang, Y., & Kan, C. (2018). Effect of Hydrophilic-lipophilic Balance (HLB)
Values of PEG-based Non-ionic Surfactant on Reverse Micellar Dyeing of Cotton
Fibre with Reactive Dyes in Non-aqueous Medium. Fibers and Polymers, 19(4), 894-
904.
Tang, J., Quinlan, P. J., & Tam, K. C. (2015). Stimuli-responsive Pickering emulsions: recent
advances and potential applications. Soft Matter, 11(18), 3512-3529.
Thompson, D., Taylor, A., & Graham, D. (1985). Emulsification and demulsification related to
crude oil production. Colloids and Surfaces, 15, 175-189.

39
van Os, N. M., Haak, J. R., & Rupert, L. A. M. (2012). Physico-chemical properties of selected
anionic, cationic and nonionic surfactants: Elsevier.
Varadaraj, R., & Brons, C. (2012). Molecular origins of crude oil interfacial activity. Part 4: oil–
water interface elasticity and crude oil asphaltene films. Energy & fuels, 26(12),
7164-7169.
Veil, J. A., Puder, M. G., Elcock, D., & Redweik Jr, R. J. (2004). A white paper describing
produced water from production of crude oil, natural gas, and coal bed methane.
Retrieved from
Wang, H., & Huang, C. (1979). The effect of turbulence on oil emulsification. Paper presented
at the Workshop on Physical Behavior of Oil in the Marine Environment.
Wang, J., Hu, F.-L., Li, C.-Q., Li, J., & Yang, Y. (2010). Synthesis of dendritic polyether
surfactants for demulsification. Separation and Purification Technology, 73(3), 349-
354.
Wang, X., Brandvik, A., & Alvarado, V. (2010). Probing interfacial water-in-crude oil emulsion
stability controls using electrorheology. Energy & fuels, 24(12), 6359-6365.
Wang, Z., Fingas,M.,Yang,C.,Christensen,J.H.,. (2005). CrudeOilandRefined Product
Fingerprinting: Principles,inEnvironmentalForensics.
Wong, S., Lim, J., & Dol, S. (2015). Crude oil emulsion: a review on formation, classification
and stability of water-in-oil emulsions. Journal of Petroleum Science and Engineering,
135, 498-504.
Xia, L., Lu, S., & Cao, G. (2004). Stability and demulsification of emulsions stabilized by
asphaltenes or resins. Journal of colloid and interface science, 271(2), 504-506.
Xie, X., Wang, Y., Li, X., Wei, X., & Yang, S. (2018). Pickering emulsions stabilized by
amphiphilic carbonaceous materials derived from wheat straw. Colloids and Surfaces
A: Physicochemical and Engineering Aspects, 558, 65-72.
Xu, C., Wang, D., Wang, H., Ma, L., Zhu, X., Zhu, Y., . . . Liu, F. (2018). Experimental
investigation of coal dust wetting ability of anionic surfactants with different
structures. Process Safety and Environmental Protection.
Yamashita, Y., & Sakamoto, K. (2016). Hydrophilic–Lipophilic Balance (HLB): Classical
Indexation and Novel Indexation of Surfactant. Encyclopedia of Biocolloid and
Biointerface Science 2V Set, 570-574.
Yang, X., Hamza, H., & Czarnecki, J. (2004). Investigation of subfractions of Athabasca
asphaltenes and their role in emulsion stability. Energy & fuels, 18(3), 770-777.
Yang, X., Tan, W., & Bu, Y. (2008). Demulsification of asphaltenes and resins stabilized
emulsions via the freeze/thaw method. Energy & fuels, 23(1), 481-486.
Yarranton, H. W., Hussein, H., & Masliyah, J. H. (2000). Water-in-hydrocarbon emulsions
stabilized by asphaltenes at low concentrations. Journal of colloid and interface
science, 228(1), 52-63.
eşilyurt Z. Vaziri Hassas B. Karakaş F. Boylu F. (2017). Ultrafine coal flotation and
dewatering: Selecting the surfactants of proper hydrophilic–lipophilic balance (HLB).
International Journal of Coal Preparation and Utilization, 1-17.
Yu, W., & Xie, H. (2012). A review on nanofluids: preparation, stability mechanisms, and
applications. Journal of nanomaterials, 2012, 1.
Zaid, N. H. (1987). Dispersed oil soluble corrosion inhibitor and water soluble phosphonate
scale inhibitor composition: Google Patents.
Zaki, N. N. (1997). Surfactant stabilized crude oil-in-water emulsions for pipeline
transportation of viscous crude oils. Colloids and Surfaces A: Physicochemical and
Engineering Aspects, 125(1), 19-25.
Zaki, N. N., Abdel-Raouf, M. E., & Abdel-Azim, A.-A. (1996). Propylene oxide-ethylene oxide
block copolymers as demulsifiers for water-in-oil emulsions, I. Effect of molecular

40
 weight and hydrophilic-lipophylic balance on the demulsification efficiency.
Monatshefte für Chemie/Chemical Monthly, 127(6-7), 621-629.
Zhang, J., Li, J., Thring, R. W., Hu, X., & Song, X. (2012). Oil recovery from refinery oily sludge
via ultrasound and freeze/thaw. Journal of hazardous materials, 203, 195-203.
Zhang, J., Tian, D., Lin, M., Yang, Z., & Dong, Z. (2016). Effect of resins, waxes and
asphaltenes on water-oil interfacial properties and emulsion stability. Colloids and
Surfaces A: Physicochemical and Engineering Aspects, 507, 1-6.
Zhang, L. Y., Lopetinsky, R., Xu, Z., & Masliyah, J. H. (2005). Asphaltene monolayers at a
toluene/water interface. Energy & fuels, 19(4), 1330-1336.
Zhang, M., & Wu, H. (2018). Separation of Bio-oil by Hydrophilic Surfactants. Energy & fuels,
32(3), 3559-3565.
Zhang, R., Huo, J., Peng, Z., Feng, Q., Zhang, J., & Wang, J. (2017). Emulsification properties
of comb-shaped trimeric nonionic surfactant for high temperature drilling fluids
based on water in oil. Colloids and Surfaces A: Physicochemical and Engineering
Aspects, 520, 855-863.
Zolfaghari R. Fakhru’l-Razi, A., Abdullah, L. C., Elnashaie, S. S., & Pendashteh, A. (2016).
Demulsification techniques of water-in-oil and oil-in-water emulsions in petroleum
industry. Separation and Purification Technology, 170, 377-407.

41
42