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Review article

Overview on petroleum emulsions, formation, influence and demulsification treatment techniques

Murtada Mohammed Abdulredha

PII:

S1878-5352(18)30244-2

DOI:

Reference:

ARABJC 2413

To appear in:

Arabian Journal of Chemistry

Received Date:

17 May 2018

Accepted Date:

15 November 2018

Date: 17 May 2018 Accepted Date: 15 November 2018 Please cite this article as: M. Mohammed

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.

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Title page Name of the author: Murtada Mohammed Abdulredha Title: Overview on petroleum emulsions, formation,

Title page

Name of the author: Murtada Mohammed Abdulredha Title: Overview on petroleum emulsions, formation, influence and
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
Abstract The most challenging aspect in petroleum industry is high produced water accompanying crude oil

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).

chemical method by using surface active agents (surfactant). Keywords: emulsion, produced water, interfacial stability,

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

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

Contents

1. Introduction

1.1. Water Production Sources

1.2. Volume of Generated Water

1.3. Overall Onshore and Offshore Produced Water

Water 1.3. Overall Onshore and Offshore Produced Water 1.4. Elements influencing on volume of extraction 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

3.2.

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

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 Size and Distribution Impact Temperature Solids Environment Medium Spread Phase Salinity Water Content and Oil Content

4.3. 4.4. 4.5. 4.6. 4.7. 4.8. 5. 5.1. 5.2. 5.3. 6. Summary
4.3.
4.4.
4.5.
4.6.
4.7.
4.8.
5.
5.1.
5.2.
5.3.
6.
Summary

Demulsification and Desalination of Oil Recovery Processes

Measurement of Stability Destabilizing Emulsions and Demulsification Methods Surface Active Agents

5.4.General Classification of Surface Active Agents

Acknowledgements

References

1. Introduction. A derived products consumption in several areas. To cover the demand for new

1. Introduction.

A

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

its products and wastes that are created by this activity survey of fuel remains is one

survey of fuel remains is one of the most important activities in recent society because of large fuel-

(Cassella, Dos Reis, Santelli, & Oliveira, 2011).

The light dense hydrocarbons traveled to gap locations and converted some of the water from the formation

to

(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

hydrocarbon reservoirs. Consequently, these reservoir rocks will usually contain petroleum hydrocarbons

“formation water” and becomes produced water when the reservoir is produced as these fluids are carried

to

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

the surface. Produced water can be defined as the water that is raised to the surface with the hydrocarbon

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

in
in

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

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.

1.1. Water Production Sources Reservoirs naturally have water in the shape of a denser layer

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).

2002; Reynolds & Kiker, 2003; Strømgren et al., 1995). Figure 1. Reservoir layers (Igunnu & Chen,
2002; Reynolds & Kiker, 2003; Strømgren et al., 1995). Figure 1. Reservoir layers (Igunnu & Chen,
2002; Reynolds & Kiker, 2003; Strømgren et al., 1995). Figure 1. Reservoir layers (Igunnu & Chen,

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

from reservoirs basically depends on two factores; location and reservoir age. Generally, the average for

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.

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.

offshore produced water extraction since 1990 until 2014. Overall Onshore and Offshore Produced Water Onshore water

Overall Onshore and Offshore Produced Water

Onshore water

Offshore

300000 250000 200000 150000 100000 50000 0 YEAR BBIS*1000 PER DAY 1990 1991 1992 1993
300000
250000
200000
150000
100000
50000
0
YEAR
BBIS*1000 PER DAY
1990
1991
1992
1993
1994
1995
1996
1997
1998
1999
2000
2001
2002
2003
2004
2005
2006
2007
2008
2009
2010
2011
2012
2013
2014
2015

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

1.4. Elements Influencing on Volume of Extraction Water

(Reynolds & Kiker, 2003) estimated that there are several elements that affect the production volume

(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 .

same production if the horizontal well drawdown is reduced .  Location of well within homogeneous

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
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

Water production from coal bed methane (CBM) varies in three basic point compositions; influence on

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.

about the effect of CBM production are totally understood. 2. Risks of Generated Water Produced water

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  Decrease the release in environment.  Sudden and
2.1. Poisonous Impact on Marine Environment
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.

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):

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

spite of the fact that residue contamination is obvious at most studied areas, impacts on

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.

into the water environments, like estuarine and marine. 2.2. Examination of Chronic Toxicity Most oil and

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  Water-in-oil (W/O) emulsion  Oil-in-water (O/W) emulsion  Multiple emulsion
3. Oily Wastewater
 Water-in-oil (W/O) emulsion
 Oil-in-water (O/W) emulsion
 Multiple emulsion

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:

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.,

2015; Schramm, 1992b) . Emulsification refers to the emulsions formation process. The water-in-oil emulsion is

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.

.

2005).
2005).
of upstream equipment for crude oil production. . 2005). Figure 3. Upstream equipment for crude oil

Figure 3. Upstream equipment for crude oil production (Z. Wang, Fingas,M.,Yang,C.,Christensen,J.H.,,

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   
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

that kinetic energy of one liquid (single-phased) becomes higher than the other two liquids (two-phased)

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.

clearly shows the stage of water-in-oil emulsions formation. Figure 4. Water-in-oil emulsions formation (Hanapi, Ariffin,
clearly shows the stage of water-in-oil emulsions formation. Figure 4. Water-in-oil emulsions formation (Hanapi, Ariffin,

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

formation (Hanapi, Ariffin, Aizan, & Siti, 2006). (Kobayashi et al., 2002), did an experiment on emulsion

(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.

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

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 coworkers (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.

approved that, the stability of emulsion basically depends on two- factor fractions and concentration of asphaltenes.
Other studies focused on the impact of resins on W/O emulsion (Fingas & Fieldhouse, 2009).

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

& Rocher, 2009). 3.1.3. Emulsion Thermodynamic Aspect The unchanged in emulsion properties for a certain period

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)

can be found by Stokes formula (Nollet, 2004). (1) Where r, , c o n t

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.

Figure 6. Thermodynamic phenomenon’s in nanoemulsions (Gupta et al., 2016). 3.2. Classification of Emulsion 
Figure 6. Thermodynamic phenomenon’s in nanoemulsions (Gupta et al., 2016). 3.2. Classification of Emulsion 
Figure 6. Thermodynamic phenomenon’s in nanoemulsions (Gupta et al., 2016). 3.2. Classification of Emulsion 

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

3.2. Classification of Emulsion  Water-in-oil emulsion.  Mesostable water-in-oil emulsions.  Entrained
3.2. Classification of Emulsion
Water-in-oil emulsion.
Mesostable water-in-oil emulsions.
Entrained water.
Unstable water-in-oil emulsion.
 Water-in-oil emulsion
 Oil-in-water emulsion
 Multiple 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.

Other research divided emulsion to three general groups, as follows (S. L. Kokal, 2005).

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

sludge in crude oil is harmful to human health, so it is important to apply

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 stabilit y, 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).

clay stabilizer, etc. (Zaid, 1987; Zolfaghari et al., 2016). Figure 7. Optical microscopic image of W/O
clay stabilizer, etc. (Zaid, 1987; Zolfaghari et al., 2016). Figure 7. Optical microscopic image of W/O

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).

3.2. 2. Oil-in-water Emulsion Due to various properties, from non-Newtonian behavior, elasticity and time emulsions

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).

previous experiments (Pons, Solans, & Tadros, 1995). A B Figure 8. Optical microscope images for O/W
A B
A
B

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

parameters that can be manipulated to decrease the oil droplet in water velocity. This is

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 0 C. 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).

within the oil-water interface (Chen & Tao, 2005). 3.2.3. Multiple or complex Emulsion The term ‘multiple

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).

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
Figure 9. Photomicrograph of typical w /o/w emulsion (Florence & Whitehill, 1982). Relatively small reproducibility
Figure 9. Photomicrograph of typical w /o/w emulsion (Florence & Whitehill, 1982). Relatively small reproducibility

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).

the crude oil recovery, reduce the operation cost and reduce the demand for energy-intensive (J. Tang
Figure 10. Optical micrographs at different storage times for (a) styrene/water Pickering emulsions and (b)
Figure 10. Optical micrographs at different storage times for (a) styrene/water Pickering emulsions and (b)
Figure 10. Optical micrographs at different storage times for (a) styrene/water Pickering emulsions and (b)

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).

   4.1. Elastic and Viscous Modulus
4.1. Elastic and Viscous Modulus

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.

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 d ij = u i / x j 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).

(3) (4) Where is volume fraction of first order. The capillary number for sa pherical
(3) (4) Where is volume fraction of first order. The capillary number for sa pherical
(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

Emulsion stability (%) 59 41 70 21 10 40 There is no correlation between stability

Emulsion stability (%)

59

41

70

21

10

40

There is no correlation between stability of emulsion and interfacial tension, as shown in Figure
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
25
20
15
10
5
0
0
10
20
30
40
50
60
70
80
Emulsion Stability
Interafacial Tension (mM/M)
60 70 80 Emulsion Stability Interafacial Tension (mM/M) Figure 1 1. Interfacial tension versus 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 beh avior 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

emulsion and increasing the stability and viscosity due to particle interaction between two phases (AHMED,

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.

the adsorption of anionic surfactant at interfacial film. 4.5. Solids Particles 4.6. Environment Medium The emulsion
4.5. Solids Particles 4.6. Environment Medium
4.5. Solids Particles
4.6. Environment Medium

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).

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

depends on the environment that works in and normally acts like anionics under basic environment

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).

avoided freezing of mixture at low temperature (Zaki, 1997). 5. Demulsification and Desalination of Oil Recovery
5.
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.

 Goodness of removal separated water. High efficiency of separation with minimum time and best

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).

and type of surfactant (S. Kokal & Wingrove, 2000). 5.2. Destabilizing Emulsions and Demulsification Methods The

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
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.

Table 2 Summary of demulsification technologies (Arthur et al., 2005).

of demulsification technologies (Arthur et al., 2005). Treatment Produced water applications Description
Treatment Produced water applications Description Disadvantages Advantages Waste stream Hydroclone This methods
Treatment
Produced water applications
Description
Disadvantages
Advantages
Waste stream
Hydroclone
This methods depend on centrifugal force that cause
by pressurized tangential input of influent stream,
and this force is applied for free oil separation
Expensive maintenance, fouling, weak in solid
separation and energy requirement to generation
pressure at inlet input
Higher efficiency, compact modules and output for smaller oil particles
The particles of oil can reach the surface by link to
induced gas bubbles
Large quantity of skim volume, lateness in separation
time and high amount of air generated.
Higher efficiency, fixed parts, robust and durable and easy in operation
Skim off volume, lumps of oil
Gas floatation
Corrugated plate
separator
The different methods can be use in treating oil and
water that was extracted from emulsion before
discharge. Both water from reservoirs and flooding
can be storaged as feed stocks. They contain grease
and oil in this type of water and can be reach to
Separation of free oil from water under gravity
effects enhanced by flocculation on the surface of
corrugated plates
High cost for maintenance, low separation efficiency
for oil fine particles and long retention time
Fixed parts, cheaper, robust and resistant, no required for energy and high
efficiency for suspended solid removal
Suspended particles slurry at the bottom of the separator
1000mg/L.
Centrifuge
Free oil separation under centrifugal force from
water. The centrifugal force can be generated by
cylinder spinning
Expensive maintenance and energy demand for
rotating
High efficiency in extraction solids contaminants and oil particles, high output and
lesser spinning time
Suspended particles slurry as pretreatment waste
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
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
hydrocarbons liquid to the surface.
Porous media adsorbs contaminants from the influent
stream
High retention time, less efficient at higher feed
concentration
Compact packed bed modules, cheaper, efficient
Used adsorbent media, regeneration waste
Removal of free or dissolved oil soluble in lighter
hydrocarbon solvent
Use of solvent, extract handling, regeneration of
solvent
No energy required, easy operation, removes dissolved oil
Solvent regeneration waste
Extraction
Ozone
High oxidizers lead to easy soluble of suspended,
high efficiency for pretreatment of soluble
contaminant and easy operation
On-site supply of oxidizer, separation of precipitate,
byproduct CO 2 , etc.
Easy operation, efficient for primary treatment of soluble constituents
Solids precipitated in slurry form
Rapid spray
The treated water can occur by injection water in
high speed at heated air lead to evaporates the water
that can be condensed
Waste in sludge form at the end of evaporation
evaporation
High energy required for heating air, required
handling of solids
High quality treated water, higher conversion efficiency
Freeze–thaw
This different types of technologies can be
distinguished from membrane technologies by less
pretreatment and power. Normally the TDS values of
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.
Freezing contaminated water to produced water
crystals by using natural cycles temperature to
produced pure water by thawing crystals
Lower conversion efficiency, long operation cycle
No energy required, natural process, cheaper
evaporation
Lime softening
Hardness, bicarbonate and carbonate can be extracted
Chemical addition, post-treatment necessary
Cheaper, accessible, can be modified
Used chemical and precipitated waste
by adding lime
Ion-exchange
Ion-exchangers help in remove minerals and
dissolved salts by exchanging
ions
High content of liquid effluent, high efficiency need
post- and pre-treatments
Low energy required, possible continuous regeneration of resin, efficient, mobile
treatment possible
Regeneration chemicals
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
of contaminants.
Applied pressure on membrane can help in removing
ultraparticles from the water
High energy, membrane fouling, low
MW organics, salts, etc
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
Membrane removes micro-particles from the water
under the applied pressure
Low efficiency in monovalent salts, viruses, divalent,
etc. High amount of energy is required
Higher recovery of fresh water, compact modules
Microfiltration
Constructed wetland
Cheaper, efficient removal of dissolved and suspended contaminants
treatment
Decomposition and natural oxidation of contaminants
by fauna and flora
Expensive maintenance, pH and temperature effects,
spinning time requirements
Concentrated flow during filtration operation, high content of backwash waste
output during membrane cleaning
Reverse osmosis
This technique can be apply to disarmament
inorganics and organics contaminants. On other hand
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.
Change pressure on contaminated water lead to
squeeze in pure water that was produced from
contaminated water
Grease, oil and trace have effect on membrane
fouling, flooding pressure requirements
Removes monovalent salts, dissolved contaminants, etc., compact modules
Activated sludge
It can be applied to filtration of suspended, like
boron, ammonia, trace, etc. In this technique the post
treatment is usually required.
Degrade contaminants in water by using
microorganisms
The dimensions of filter too large and oxygen
requirement
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

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.

methods. Table 3 represent different types of demulsifiers. Figure 12. Basic schematic of a surfactant molecule
methods. Table 3 represent different types of demulsifiers. Figure 12. Basic schematic of a surfactant molecule
methods. Table 3 represent different types of demulsifiers. Figure 12. Basic schematic of a surfactant molecule

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

Table 3 Summary of application surfactant in demulsification emulsion Surfactant name Sort and characteristic Emulsion

Table 3 Summary of application surfactant in demulsification emulsion

Surfactant name Sort and characteristic Emulsion preparation Operational conditions Advantages Reference surfactant
Surfactant name
Sort and characteristic
Emulsion preparation
Operational conditions
Advantages
Reference
surfactant
alkyl sulfate
Anionic Surfactants
Small unilamellar vesicles were prepared by
ultrasonic irradiation of samples containing about 25
mg lecithin in 5 ml buffer. A Soniprep 150 was used
for the irradiation The samples were sonicated for 1 h
and thereafter diluted with buffer to the desired
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
addition of three surfactants
in different concentration have
influence . on the turbidity of
sonicated lecithin vesicles in
buffer containing 150 mM NaCl
the different types of alkyl sulfate were used to
solubilization of small unilamellar lecithin
vesicles
(Silvander, Karlsson, &
Edwards, 1996)
polyoxyethylene nonylphenols
Nonionic Surfactants
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.
Surfactants add in different dose
and add to water phase before
The (hydrophilic-lipophilic balance ) of the
surfactant very high which is 14.2 and this gave
surfactant very high performance in
(Fan, Simon, & Sjöblom,
2009)
emulsification. The entire volume
of
samples is 15 mL.
demulsification processing
Fourier transform infrared
(FTIR)
Nonionic surfactant. Fourier
transform infrared have trimeric and
The best operational conditions at
(R. Zhang et al., 2017)
160
◦ C
it
is
got
in
two
stage
of
And 2.5wt% water content
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.
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.
High performance in emulsification impact on
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.
Triton X-100 (polyethylene glycol
octylphenyl ether)
Nonionic hydrophilic surfactant
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.
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).
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
of brine water was added to bottles and mixed with
30mL of crude oil from American Petroleum Institute
(API) at high speed for 10 min.
Demulsifier concentration equal to
200ppm with room temperature
around (25 o c-30 o c)
The surfactant was used to determine the effect
(Hirasaki et al., 2010)
bromide
on
water
and
oil
separation
of produced emulsions resulting from surfactant-
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 nonionic surfactant and amphoteric surfactant
Poly(ethylene glycol) distearate, Polyoxyethylene (10) tridecyl nonionic surfactant and amphoteric surfactant
Poly(ethylene glycol) distearate,
Polyoxyethylene (10) tridecyl
nonionic surfactant and amphoteric
surfactant
Synthetic water in oil emulsion was prepared with
water cut 10% and 20%
(Roshan, Ghader, &
Rahimpour, 2018)
ether,
N,N-
N- Dimethyldodecylamine N –oxide solution
have high performance in breaking water in oil
emulsion
Dimethyldodecylamine N –
oxide solution Polyethylene glycol
The first three parameters fixed in
range as following temperature
(50 C ◦ -80 C ◦ ), pH (5-9) water cut
(10%-20%) and surfactant
concentration between (0-
sorbitan monooleate
1000ppm),
Trioctylmethylammonium
Ionic surfactant
chloride
(TOMAC),
1-
Synthetic water in oil emulsion with different water
cut
Hexadecyltrimethylammonium
bromide
(CTAB)
and
Trioctylmethylammonium
bromide (TOMAB)
Dosage for three surfactants
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 ◦ )
The result shows that the pH and temperature are
the most useful variables, while the maximum
separation occurs at maximum temperate and pH
near to the natural value
(Biniaz, Farsi, &
Rahimpour, 2016)
PE 6100 and RPE 3110
nonionic surfactant. The low number
of relative solubility number (RSN)
Water in crude oil emulsion with water content 2%
and 22% for two type of heavy crude oil
Thermochemical dewatering
method was applied, surfactant
was mixed (1:1) and add to the
emulsion with concentration 1%,
while both surfactant dissolved in
benzene and kerosene
The maximum separation achieved at high
temperature 80 C◦
(Adilbekova, Omarova,
Karakulova, & Musabekov,
2015)
C10E3, DTPB and SDS
The surfactant from different families
anionic, non-ionic and cationic
Synthetic
water in
oil emulsion
with 60%
water
pH range from 2 to 13
(Daaou & Bendedouch,
content
The result indicates that the pH near to neutral
medium more stable than basic or acidic
environment cationic and anionic surfactant
much better in separation water than nonionic
surfactant
2012)
poly(propylene oxide) ,
poly(ethylene oxide) and sodium
dodecyl sulfate (SDS)
Nonionic surfactant mass screening
was depended for selecting the
demulsifiers
Synthetic water in oil emulsion with water oil ratio
(1:1)
Demulsifiers were added at a
concentration from 200 μL to
10000 mg/L at 40 C◦
The result shows the demulsifiers reduced the
interfacial viscoelasticity and separation of
water occur and the efficiency depends on
demulsifiers nature.
(Kang et al., 2018)
chloride
(Cl),
Synthetic water in oil emulsion with water content
bis(trifluoromethanesulphonyl)
ionic liquids with long alkyl chains (n
= 10, 12 and 14)
Three demulsifiers were studied in
range 500 ppm to 3500 ppm
during 24 hours
The demulsifiers achieve high demulsification
rate (86%-95%) and reduce the inter factual
tension to range range from 0.7–6.26 mN/m.
(Hazrati, Beigi, & Abdouss,
20%
2018)
andhexafluorophosphate (PF6)
Six dendritic copolymers
Dendritic polyether. The surfactant
was prepared by reaction of ethylene
oxide and propylene oxide with
various proportions
Water
in
crude
oil
emulsion
with
ratio
(7:13)
Surfactant
concentration
is
150
respectively.
mg/L
The surfactant achieve high demulsification rate
at 150 mg/l after 15 min
(J. Wang, Hu, Li, Li, &
Yang, 2010)
28
On other hands, hydrophilic-lipophilic balance (HLB) of demulsifier is an important factor that helps in

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/S sum 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

surfactant

common

that use to formation emulsions and suspensions their elements, Figure. 11 shows the surfactant common types
that use to formation emulsions and suspensions their elements, Figure. 11 shows the surfactant common types

types

of

Rhamnolipid Bacillus sp Emulsan Bio Surfactant Pseudomonas Alasan RLichenysinhamnolipid Acinetobacter Alkyl Ether
Rhamnolipid Bacillus sp Emulsan Bio Surfactant Pseudomonas Alasan RLichenysinhamnolipid Acinetobacter Alkyl Ether
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.

6. Summary This literature article focused on global water production from the petroleum industry, the

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.

different methods, and test bottles is one of these methods. Acknowledgment The authors wish to acknowledge

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.

support. Gratefully thanks to Mrs Siti Aslina Hussain and Mr Luqman Chuah Abdullah for their contribution
References Abdurahman, N., Rosli, Y., Azhari, N., & Hayder, B. (2012). Pipeline transportation of viscous

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,

types of crudes. Brazilian Journal of Petroleum and Gas, 4(4). Bera, A., Mandal, A., & Guha,
4(4).
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 IrW as permanent modifier. Talanta, 85(1),

415-419.

Chan, L.-H., Starinsky, A., & Katz, A. (2002). The behavior of lithium and its isotopes

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 oilwater 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.

Journal of Saudi Chemical Society, 16 (3), 333-337. Dai, L., Zhan, X., Wei, Y., Sun, C.,

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. 541. Fan . imon .
8890.
541.
Fan . imon .

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-

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.

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.

Fingas, M., & Fieldhouse, B. (2009). Studies on crude oil and petroleum product emulsions: Water

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),

Industrial & engineering chemistry research, 39 (8), 2746-2751. Gore, R. H., Kopko, R. J., Machleder, W.

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.

diluted bitumen emulsion. Fuel, 81 (14), 1859-1869. Çelik M. Gupta, A., Eral, H. B., Hatton, T.

Çelik M.

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.

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

. (2014). Ultrafine coal dewatering: Relationship

emulsion using long chain imidazolium ionic liquids and optimization of parameters. Fuel, 229, 126-134.

Hirasaki, G. J., Miller, C. A., Raney, O. G., Poindexter, M. K., Nguyen, D. T.,

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:

for aerial conidia of Metarhizium anisopliae (Hypocreales: Clavicipitaceae). Biocontrol science and technology, 19

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.

and Environment in Oil and Gas Exploration and Production. Julio, L. M., Ixtaina, V. Y., Fernández,

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.

Zhang, X. (2018). Demulsification

Kang, W., Yin, X., Yang, H., Zhao, Y., Huang, Z., Hou, X.,

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, H.

Khan, B. A., Akhtar, N., Khan, H. M. S., Waseem, K., Mahmood, T., Rasul, A.,

(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.

Kokal, S. L. (2005). Crude oil emulsions: A state-of-the-art review. SPE Production & Facilities, 20

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:

Suh, K. D. (2004). The
Suh, K. D. (2004). The

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.,

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:

Castellanos, J., 407-414.
Castellanos, J.,
407-414.

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.,

Aburto, J. (2013). Demulsification of heavy crude oil-in-water

emulsions: A comparative study between microwave and thermal heating. Fuel, 113,

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.

Mouraille, O., Skodvin, T., Sjöblom, J., & Peytavy, J.-L. (1998). Stability of water-in-crude oil emulsions:

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-

recovery applications. Energy & fuels, 26 (5), 2742- 2750. Nollet, L. M. (2004). Handbook of Food

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.
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.

Reynolds, R. R., & Kiker, R. D. (2003). Produced Water and Associated Issues. Oklahoma Geological

Reynolds, R. R., & Kiker, R. D. (2003). Produced Water and Associated Issues. Oklahoma Geological Survey. Robins, M. M. (2000). Emulsionscreaming phenomena. Current Opinion in Colloid & Interface Science, 5(5-6), 265-272. Robins, M. M., Watson, A. D., & Wilde, P. J. (2002). Emulsionscreaming and rheology. Current Opinion in Colloid & Interface Science, 7(5-6), 419-425.

Rodionova G. Keleşoğlu .

Science, 7 (5-6), 419-425. Rodionova G. Keleşoğlu . lom J. (2014). AC field induced desta ilization

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 nanoparticlesurfactantpolymerover surfactantpolymer (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

P. V., & Sjöblom, J. (2010). Emulsions of heavy crude oils. II. Viscous responses and their

oils. II. Viscous responses and their influence on emulsion stability measurements. Journal of dispersion science and technology, 31(10), 1432-1445.

Silva, B. F., Rodríguez-Abreu, C., & Vilanova, N. (2016). Recent advances in multiple emulsions and

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.

Kallevik, H.
Kallevik, H.

Sjöblom, J., Aske, N., Auflem, I. H., Brandal, Ø., Havre, T. E., Sæther, Ø.,

(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):

258.
258.

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-

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.

van Os, N. M., Haak, J. R., & Rupert, L. A. M. (2012). Physico-chemical properties

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: oilwater 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.

Separation and Purification Technology, 73 (3), 349- 354. Wang, X., Brandvik, A., & Alvarado, V. (2010).

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.

Liu, F. (2018). Experimental

Aspects, 558 , 65-72. Liu, F. (2018). Experimental Xu, C., Wang, D., Wang, H., Ma, L.,

Xu, C., Wang, D., Wang, H., Ma, L., Zhu, X., Zhu, Y.,

investigation of coal dust wetting ability of anionic surfactants with different structures. Process Safety and Environmental Protection. Yamashita, Y., & Sakamoto, K. (2016). HydrophilicLipophilic 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.

Boylu F. (2017). Ultrafine coal flotation and

eşilyurt Z. Vaziri Hassas B. Karakaş F.

dewatering: Selecting the surfactants of proper hydrophiliclipophilic 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

weight and hydrophilic-lipophylic balance on the demulsification efficiency. Monatshefte für Chemie/Chemical Monthly,

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.

water-in-oil and oil-in-water emulsions in petroleum industry. Separation and Purification Technology, 170 , 377-407. 41
water-in-oil and oil-in-water emulsions in petroleum industry. Separation and Purification Technology, 170 , 377-407. 41
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