J Petrol 2018 03 014zdfvzdfvzdfvfvdv

Accepted Manuscript
A review of petroleum emulsions and recent progress on water-in-crude oil emulsions

stabilized by natural surfactants and solids
Abubakar Abubakar Uma, Ismail Bin Mohd Saaid, Aliyu Adebayo Sulaimon, Rashidah
Bint Mohd Pilus
PII: S0920-4105(18)30198-0
DOI: 10.1016/j.petrol.2018.03.014
Reference: PETROL 4755
To appear in: Journal of Petroleum Science and Engineering
Received Date: 15 April 2017

Revised Date: 15 September 2017
Accepted Date: 2 March 2018
Please cite this article as: Uma, A.A., Saaid, I.B.M., Sulaimon, A.A., Pilus, R.B.M., A review of petroleum
emulsions and recent progress on water-in-crude oil emulsions stabilized by natural surfactants and
solids, Journal of Petroleum Science and Engineering (2018), doi: 10.1016/j.petrol.2018.03.014.
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Journal of Petroleum Sciences and Engineering
1 A Review of Petroleum Emulsions and Recent Progress on Water-

2 in-Crude Oil Emulsions Stabilized by Natural Surfactants and
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3 Solids
4 Abubakar Abubakar Umara, Ismail Bin Mohd Saaid*b, Aliyu Adebayo Sulaimonc,
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5 Rashidah Bint Mohd Pilusd
a,b,c,d
6 Department of Petroleum Engineering, Universiti Teknologi PETRONAS, Bandar Seri Iskandar 32610, Perak Malaysia
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7 Abstract
8 During production of conventional as well as heavy oils, emulsions occur at well bore, in pipelines, and at surface facilities. As
9 the production time of the oil wells increases, there will be an increased coproduction of oil and water in the form of emulsions.
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10 These emulsions are undesirable because they result in high pressure drop due to their high viscosity. They also cause serious
11 corrosion problems due to presence of chlorides dissolved in water. These emulsions must be treated to meet production and
12 transportation requirements, and to maximize the overall profitability of the crude oil production. Apart from the undesirable
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13 emulsions, the petroleum industry is witnessing a surge in the application of emulsions for beneficial processes. Both cases
14 would be discussed in this review. This subject has experienced an extensive research over the years, with highly complicated
15 theories regarding the phenomena involved in its formation (emulsification) and breaking (demulsification). Crude oils,
16 irrespective of their origin, contain certain components or characteristics which tend to make them emulsifiable. These crude oil
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17 components are referred to as emulsifiers, and they vary so widely with the nature of the crude oil. The natural interfacially
18 active components responsible for emulsion stability undoubtedly come from the resin and asphaltenes of the crude oil.
19 However, the presence of other solids like crystalline waxes, clays, corrosion products and mineral scales may lead to the
20 formation of very stable water-in-oil (w/o) emulsions. The nature of these particles controls the type as well as the stability of
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21 emulsions produced. Apart from the natural emulsifiers, chemical enhanced oil recovery (EOR) techniques have been reported
22 to produce stable w/o and o/w emulsions. It is believed that the alkali, surfactant and polymers used in these techniques are
23
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responsible for these stable emulsions. When they form, these emulsions increase pumping costs, heighten the chances of
24 pipeline and equipment erosion, corrosion rate, scaling and lower the produced oil API gravity. These emulsions have to be
25 treated to remove the dispersed water and accompanying inorganic salts in order to meet market specifications, transportation
26 requirement and to reduce corrosion and catalyst poisoning in downstream processing. Despite the huge and concerted efforts
27 by researchers from the academia and the petroleum industry, there are few fundamental and applied investigations into the
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28 roles of native solids in combination to natural emulsifiers on the stabilization of petroleum emulsions. This paper presents a
29 comprehensive overview of the progress made in the field of petroleum emulsions, principally the roles of particles in
30 combination to asphaltene and resin in stabilizing w/o emulsions. The study also charts a way for emulsions studies that could
31 lead to an effective demulsification via thorough characterizations of the solids believed to the enhancers of emulsion stability
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32 in order to tailor demulsifiers based on the characteristics of such emulsifiers.

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34
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35 Keywords: Water-In-Oil Emulsions (W/O); Oil-in-water (O/W); Pickering, Emulsifiers; Demulsifiers; solid particles; Surfactants.
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Abubakar Abubakar Umar et al
36 1. Introduction
37 The process of stabilization of oil and water droplets by solid particles has been acknowledged for over a
38 century. Currently, these particle-stabilized emulsions are largely known as Pickering emulsions. They occur in
39 personal care products, the food industry and have long been used in oil recovery and mineral processes
40 (Bernardini 2015). These are industries where such emulsions are desirable for achieving certain characteristics of
41 the products. In the oil and gas industry however, the formation of emulsion during oil production is a pricy
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42 problem, both in terms of chemicals used and the production lost (Kokal 2005). These emulsions have to be treated
43 to remove the dispersed water and accompanying inorganic salts in order to meet market specifications,
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44 transportation requirement and to reduce corrosion and catalyst poisoning in downstream processing (Kokal and
45 Wingrove 2000). Surfactants with small molecular weight or amphiphilic polymers have long been employed in
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46 certain industries in emulsion stabilization, either by reducing interfacial tension or forming a viscoelastic
47 interfacial film. Although these surfactants have been well understood and are widely in use, they are not the only
48
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potential sources of stabilization of emulsions. Colloidal particles with suitable wettability partially in both the
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49 dispersed and continuous phases can function as Pickering-type stabilizer by forming a physical barrier at droplet
50 interface. This phenomenon is discussed in detail in section 6.2 of this review paper.
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52 Several other researches have shown that asphaltenes are the prime stabilizers of water-in-oil emulsions and that
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53 resins are needed to solvate the asphaltenes (Fingas, Fieldhouse et al. 1999, Fingas and Fieldhouse 2003, Fingas
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54 and Fieldhouse 2004, Fingas 2014). Certain studies however found out that a synergy in stabilization occurs when
55 asphaltenes and fine solids jointly stabilize an emulsion based on a certain fractional area ratio of 2:1 of asphaltenes
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56 to solids (Sztukowski and Yarranton 2005). In a similar work, (Bobra, Fingas et al. 1992) established that waxes
57 cannot act as emulsifiers by themselves, but can stabilize emulsions in combination with asphaltenes or resins.
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58 Thus, according to their findings, a concentration of 0.01g/ml of asphaltenes did not produce a stable w/o emulsion,
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59 but when 0.05g/ml of wax added, stable emulsions were formed. However, an asphaltene concentration of 0.03g/ml
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60 without the presence of wax produced a stable emulsion. These findings were repeated by the authors of this paper,
61 and the results found corroborated this result.
62 2. The Emulsion Problem
63 The problem of separating water from produced crude oil is as old as the oil industry itself. At the beginning of
64 the oil industry, the water separation problem was handled by settling the free water from oil in open tanks or pits
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65 and the sludge (an intermediate phase between clean water and clean oil) was disposed of, ordinarily by burning
66 (Meyer 1964). It was not more than a century ago that attention was drawn to the fact that “sludge” is an emulsion
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67 of crude oil and water, and that substantial amount of merchantable oil can be recovered from the emulsion (API
68 1961). By crude oil emulsions, we are referring to water-in-oil (W/O) emulsions because most emulsions are this
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69 type (Kokal and Wingrove 2000). Although oil-in-water (O/W) emulsions also form and are encountered in the
70 industry, they are generally resolved in the same way W/O emulsions are resolved, except electrostatic treaters
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71 cannot be used on O/W emulsions (Kokal 2005). At the time when crude oil and water are leaving the wellbore of
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72 an oil well, tight w/o emulsions can form due to the turbulence in the choke valve at the wellhead (Janssen, Noïk et
73 al. 2001). The formation of emulsion during crude oil production is a very costly operational problem. It occurs
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74 when hydrocarbon and formation water in the reservoir and in production pipes are extremely mixed under
75 shear/turbulence, and in the presence of surface active agents (Fingas, Fieldhouse et al. 1999, Opawale and
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76 Osisanya 2013) (Ngai and Bon 2014).
77 The continuous phases of these emulsions depend on the water to oil ratio, the natural emulsifier systems contained
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78 in the oil, and the origin of the emulsion. The emulsifiers are complex chemically, and they come in different
79 shapes and sizes. As new oil fields are developed and as production conditions change in older fields, there is a
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80 constant need for new, effective demulsification methods. The emulsion must be separated before the crude oil can
81 be accepted for transportation, to meet the residual salt and water content quality criteria for a delivered crude oil.
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82 The water content must be less than 1% (Fink 2015).

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83 2.1. Definitions of Emulsions
84 Emulsions are thermodynamically unstable systems, since they will separate to reduce the interfacial area
85 between the oil phase and the water phase, as a function of time (Sjoblom 2001). Emulsions are metastable systems
86 typically formed in the presence of surfactant molecules, amphiphilic polymers or solid particles. The relative
87 balance of the hydrophilic and lipophilic properties of these emulsifiers is known to be the most important
88 parameter dictating the emulsion type: oil-in-water (O/W) emulsions are preferentially obtained with molecules
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89 which are rather hydrophilic whereas water-in-oil (W/O) emulsions are produced in the presence of hydrophobic
90 molecules (Leal-Calderon and Schmitt 2008).
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92 (Manning and Thompson 1991) defined emulsion as a quasi-stable suspension of fine drops of one liquid in
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93 another liquid. (Roberts 1926) defined emulsion as a system containing two liquid phases, one of which is
94 dispersed as globules in the other. Other researchers defined emulsion as a mixture of two mutually immiscible
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liquids, one of which is dispersed as very small droplets in the other, and is stabilized by an emulsifying agent
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96 (Aziz, Darwish et al. 2002) (Singh, Thomason et al. 2004) (Kokal 2008).
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98 Another definition of oil field emulsions was proposed by (Roberts 1926). According to his work, he maintained
99 that oilfield emulsions vary from extremely unstable types, which should more accurately be called suspensions, to
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100 extremely stable ones. Based on that, he classified emulsions into three classes, according to their behavior in the
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101 hand centrifuge. These are: (a) Emulsions that show only clear oil and; and are better referred to as suspensions,
102 thus if allowed to stand will generally separate into their different phases without any form of treatment. However,
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103 certain unstable emulsions occur which are capable of resolution in the centrifuge, especially when diluted with
104 gasoline, but which will not settle to oil and water without any form of treatment. (b) Emulsions that show the
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105 emulsion phase, with or without water, and a clear oil phase. These are real emulsions and must be treated to
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106 recover the emulsified oil (c) those that may or may not show emulsion and water phases, but which also show
107 cloudy oil after centrifuging.
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109 Something common to all the definitions provided in this review and many others not stated here is the fact these
110 emulsions are thermodynamically unstable and separate into two phases if allowed to sit for a long time (Singh,
111 Thomason et al. 2004). These emulsions, which fall under macro-emulsions (having dispersed phase diameters
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112 greater than 0.1µm) are said to be thermodynamically unstable systems because the contact between the oil and
113 water molecules is unfavourable, and so they will always break down over time. There has been more
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114 comprehensive studies and a lot has been known about the formation and stabilization of oil-in-water emulsions
115 than of the water-in-oil emulsions type (Oliveira and Goncalves 2005). To understand the W/O emulsions, more
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116 information is needed on the materials responsible for their formation and stabilization, and especially how solid
117 particles form or enhance their stabilizations.
118 2.2. Classifications of Emulsions
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119 Decades of far-reaching research work on water-in-oil emulsions (often called “chocolate mousse”) that form
120 after oil spill, (Fingas and Fieldhouse 2009) found that four classes of emulsions form when crude oil mixes with
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121 water. Among the leading studies on classification of crude oil emulsion according to their stability are the works
122 of (Fingas, Fieldhouse et al. 1999, Fingas and Fieldhouse 2003, Fingas 2014, Fingas and Fieldhouse 2014) who
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123 proposed new empirical data and corresponding physical knowledge of emulsion formation. Based on their studies,
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124 the density, viscosity, saturates, asphaltene, resins and fine solids were used to propose an emulsion type
125 classification index which gives either an unstable, entrained, meso-stable or stable water-in-oil class of emulsion.
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126 From the four classes, only stable and meso-stable states can be considered as emulsions. It is assumed that the
127 stability derives from the tough visco-elastic interface, triggered by asphaltenes and resins. Mesostable emulsions
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128 are the emulsions between stable and unstable emulsions. It is thought that meso-stable emulsions lack sufficient
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129 quantities of asphaltenes to render them completely stable. The meso-stable emulsions may degrade to form layers
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130 of stable emulsions. Given the oil and water phases, the type of emulsion formed depends on several factors. As a
131 rule of thumb, when the volume fraction of one phase is very small compared with the other, the phase that has the
132 smaller fraction is the dispersed phase and the other is the continuous phase. When the volume-phase ratio is close
133 to 1 (a 50:50 ratio), then other factors determine the type of emulsion formed (McClements 2008) (Kokal and
134 Wingrove 2000). Although emulsions are defined as stable dispersion of one liquid in another, not every mixture
135 or dispersion of water in oil is an emulsion. For a dispersion to qualify as an emulsion, it has to be a stable
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136 dispersion (Bansbach 1965).
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139
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145
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146
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148 Figure 1 (a) Water-in-Oil Emulsion (b) Oil-in-Water Emulsion (Nalco)
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151 Based on this, (Bansbach 1965) classified emulsions as Tight and Loose. Tight emulsions are those emulsion
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152 characterized by very small sizes of the dispersed phase, while a relatively larger dispersed phase droplet
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153 characterizes loose emulsions. According to (Bobra 1992) (Meyer 1964), the type of emulsifying agent determines
154 the type of emulsion that would form, either w/o or o/w. If the emulsifying agent is more favorably wetted by the
155 oil phase, the contact angle between the oil-water-solid boundaries, Ɵ, is greater than 90o and a w/o emulsion
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156 forms. However, if the water phase more favorably wets the particle, then Ɵ is <90o and an o/w emulsion will
157 form. If the contact angle is much greater or much lesser than 90o, the emulsion will be unstable. According to
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158 (Wang and Alvarado 2011), Stable emulsions form when the contact angle is near 90o As a rule of thumb, the
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159 continuous phase of the emulsion is normally the one in which the particles are preferentially dispersed.
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160 (Fingas, Fieldhouse et al. 1999, Fingas and Fieldhouse 2003, Fingas 2014) classified emulsions into stable,
161 mesostable, entrained and unstable. Each of these emulsion types has unique characteristics and is believed to be
162 non-convertible to other types once formed.
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164 (Kokal 2008, Fink 2015) in separate studies upheld that w/o emulsions form as a result of asphaltene and resin
165 surfactant behaviors in oil of moderate viscosities (50-2000mPa.s) and that oil field emulsions are sometimes
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166 classified based on their degree of kinetic stability as Loose emulsions; those that will separate within a few
167 minutes, medium emulsions; that will separate in approximately ten minutes; and tight emulsions; that will
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168 separate within hours, days, or even weeks, and even then, not completely.
169 Table 1 Some desirable and undesirable emulsions in the petroleum Industry (Schramm 2000).
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Occurrence Usual Type
Undesirable Emulsions
Well-head Emulsions W/O
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Fuel Oil Emulsions (Marine)
W/O
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Oil Flotation Process (Froth) emulsions
W/O and O/W
Oil Sand Flotation Process (Diluted froth)
O/W/O
Oil Spill Mousse Emulsions
W/O
Tanker Bilge Emulsions O/W
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Desirable Emulsions
Heavy oil pipeline emulsions O/W
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Oil Flotation Process froth emulsions O/W

Fuel-oil emulsion (70% heavy oil) O/W
Emulsion Drilling Fluid (Oil-Base Mud) W/O
O/W
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Asphalt Emulsions
Enhanced Oil Recovery in-situ Emulsions O/W
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171
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172 Earlier, (Surfluh 1937) has classified emulsions as temporary and permanent. While a temporary emulsion will
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173 break down into oil and water by settling methods, a permanent emulsion would remain stable until it is treated
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174 effectively. Any method of preventing the formation of emulsions in oil and water mixtures must either reduce the
175 degree of agitation or must employ the use of chemicals to produce physicochemical changes which will aid in
176 emulsion prevention (Becker 1997).
177 (Singh, Thomason et al. 2004) (Becker 1997) classified emulsions based on the size of the dispersed phase.
178 When the dispersed droplets are larger than 0.1 µm, the emulsion is referred to as macro-emulsion. Emulsions of
179 this kind are normally thermodynamically unstable (i.e., the two phases will separate over time because of a
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180 tendency for the emulsion to reduce its interfacial energy by coalescence and separation). Emulsions are called
181 Micro-emulsions when the dispersed phase droplet sizes are less than 0.1µm. Micro emulsions are transparent and
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182 can occur both as water-in-oil, or oil-in-water.
183 Technically speaking, micro-emulsions differ from macro emulsions in several ways (McClements 2008)
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184 (McClements 2015), while there exist a direct oil-water contact at the interface of a macro emulsions, such direct
185 contact is not present in micro emulsions. Also, macro emulsions are cloudy colloidal systems, while micro
186 emulsions are optically transparent (isotropic).
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187 2.3. Crude Oil Emulsions formed during Enhanced Oil Recovery (EOR) Processes
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188 Enhanced Oil Recovery (EOR) technique has always been a subject of interest in the oil and gas industry. Prior to
189 the fall in oil price which started June 2014, the high oil prices and energy demand all over the world has
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190 necessitated the needs for Enhanced Oil Recovery (EOR) methods. Of recent, EOR techniques are getting more
191 attention by many countries since energy crises are getting worse and frightened. One of the reasons for this is due
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192 to the shortage of current oil resources and difficulties in finding new oil fields all over the world. EOR has been
193 classified into five (5) categories, with general intent of reducing the mobility ratio between injected and in-situ
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194 fluids, eliminating or reducing interfacial tension or doing both simultaneously (Sheng 2014, Standnes and
195 Skjevrak 2014, Talebian, Masoudi et al. 2014). Application of EOR technology gives an additional chance to get
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196 out more oil from the reservoir, possibly about another 20 - 40%. These classes are Mobility-control, chemical,
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197 miscible, thermal and other processes such as microbial. Despite the recorded successes, EOR processes are always
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198 accompanied with varying problems. The formation of strong emulsions and excessive formation of silicate scales
199 (Umar and Saaid 2013) especially with the application of high concentration of alkali.
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201 (Li, Lin et al. 2005) studied the effect of alkaline–surfactant–polymer (ASP) flooding using sodium
202 hydroxide as the alkali constituent to enhance oil recovery of an onshore oilfield in Daqing, China. Although it has
203 increased the oil recovery, it has also created a new problem for the industry. Although the crude oil is paraffinic
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204 (contains very little asphaltene), the alkali added formed stable w/o emulsion. The study reveals that the sodium
205 hydroxide solution reacts with fatty acids in the aliphatic fraction of the crude oil and/or with the fatty acids formed
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206 from the slow oxidation of long chain hydrocarbons, and form soap like interfacially active components. These
207 accumulate at the crude oil–water interface and contribute to the stability of the oil/water emulsion.
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209 (Li, Xu et al. 2007) investigated the effects of HPAM on crude oil/water Interfacial properties and the
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stability of petroleum emulsions formed by Gudong crude oil. The investigation was conducted via measurement
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211 of interfacial shear viscosity, interfacial tension, Zeta potential, and emulsion stability. They found out that HPAM
212 has the ability to adsorb at the interface between the oleic phase and water without decreasing the interfacial
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213 tension. Increasing the HPAM concentration however, leads to increase in the interfacial shear viscosity, Zeta
214 potential, and stability of the emulsion.

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215 (Abidin, Puspasari et al. 2012) in a comprehensive review of polymers used in EOR processes believe that
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216 there is an immense optimism that the use of polymer may play a significant role in resolving the current energy
217 crisis since its applications in some EOR fields has shown some successes to recover more than 20% additional oil
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218 from OOIP. However, HPAM one of the most common polymers used in the EOR so far, was found to enhance the
219 stability of o/w emulsions and makes the water treatment difficult (Li, Xu et al. 2007).
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220 (Ahmadi and Shadizadeh 2012) investigated the implication of adsorption equilibrium when different
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221 types of nanosilica and Zyziphus Spina Christi, a novel surfactant, were combined in aqueous solutions for EOR
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222 and reservoir stimulation purposes. The study employed a conductivity technique to evaluate the adsorption of the
223 surfactant and nanosilica in the aqueous phase. Batch experiments were used to understand the effect of adsorbent
224 dose on sorption efficiency as well. The results from this study can help in appropriate selection of surfactants in
225 the design of EOR schemes and reservoir stimulation plans in carbonate reservoirs.
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227 (Li, Lin et al. 2005, Li, Xu et al. 2007) at different times carried out laboratory studies concerning the
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228 chemical nature of the emulsions produced by Da Qing crude oil (paraffinic crude oil- that contains very little
229 asphaltene and very low acid number). In this chemical flood where sodium hydroxide was used as the alkaline
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230 component in the recovery of crude oil, production was enhanced but the recovered oil was accompanied by a
231 severely stabilized water-in-crude-oil emulsion. Certain studies however pointed to the fact that neither the
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232 surfactant nor polymer are responsible for the stabilization of the w/o emulsion.
233 In a series of articles, Ahmadi and co-workers (Ahmadi and Shadizadeh 2012, Ahmadi and Shadizadeh
234
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2013, Ahmadi and Shadizadeh 2013, Ahmadi and Shadizadeh 2015, Ahmadi and Shadizadeh 2016) have
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235 conducted several studies ranging from estimation of adsorption behaviour of surfactants with nanosilica,
236 adsorption of solid surfaces like carbonate reservoirs, adsorption of new plant derived surfactants on quartz among
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237 others. Results from these studies can help in making the right selection of surfactants in the design of chemical
238 EOR schemes and reservoir stimulation plans in carbonate reservoirs. Also, the studies presented economically
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239 viable and environmentally friendly options for use in EOR techniques, particularly chemical flooding. Also, the
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240 studies are very helpful in understanding the mechanism of surfactant loss into sandstone reservoirs.
241 2.4. Some Industry Applications of Emulsions- Desirable Emulsions

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242 Despite the numerous posed to the oil and gas industry by the formation of emulsions during crude oil
243 production, emulsions and other materials like foams, have been used as mobility control or diverting agents in
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244 different EOR processes and many other useful applications in the oil and gas industry, food industry, construction
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245 industry, among others (Islam and Ali 1989, Israelachvili 1994).
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246 (Mendoza, Thomas et al. 1991) studied the effect of injection rate on emulsion flooding for a Canadian and a
247 Venezuelan crude oil. The study was conducted using a porous media consisting of crushed Berea sandstone
248 packed in 5x30cm (diameter x length). The study employed a Lloydminster crude oil 16.4° API and 12o API
249 Morichal crude oils. The brines used for the runs and for the preparations of the emulsions had sodium chloride
250 concentrations of 3.3 and 7.5% by weight, respectively. The emulsions were prepared by adding 0.04% and
251 0.0004% by weight sodium hydroxide with pH = 12 and 10 respectively, to mixtures of crude oil and water. The
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252 study revealed that water driven emulsion flooding may offer a viable alternative to thermal recovery of
253 moderately viscous oils.
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254 (Abdul and Ali 2003) carried out a study to examine the effective techniques that can better water-flood bottom
255 water reservoirs using polymer and emulsion as mobility control and/or blocking agents. In the provinces of
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256 Alberta and Saskatchewan certain light and moderately heavy oil reservoirs have a high-water saturation zone in
257 connection with the oil zone. Using a conventional water-flood to produce from such reservoirs gives poor
258
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performance. This is attributed to insufficient and incomplete sweep of the reservoir by the injected water, which
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259 tend to move to the producing wells via those portions of the reservoir that have higher permeability. This leads to
260 low recovery. In this study, polymer was used to control the movement of water in the oil zone while the emulsion
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261 was used to block the injected water from routing into the bottom water zone. The study found out that when
262 producing from reservoirs with water leg, the use of 10% quality oil-in-water emulsion as a blocking agent and
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263 polymer solution as mobility control agent is the most successful strategy.
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264
265 (Mandal, Samanta et al. 2010) investigated the efficiency of o/w emulsions as a displacement fluid during EOR
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266 process. In the study, they used synthetic emulsions prepared by gear oil, and experiments were conducted using
267 sand pack flooding tests to observe the efficiency of the emulsion as displacing fluid. They found a substantial
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268 additional recovery (more than 20% of original oil in place) over conventional water flooding.
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269 (Ashrafizadeh, Motaee et al. 2012) in a study of emulsification of heavy crude oil by surfactants reported
270 several findings on the application of emulsions in the oil industry. He reported the work of (Kessick and Denis
271 1982) on pipeline transportation of heavy crude oil. According to them, conventional pipelining is not suitable for
272 transporting heavy crudes from the reservoir to the refinery because of the high viscosities involved. This requires
273 alternative transportation techniques. (Saniere, Hénaut et al. 2004) in their study outlined several alternative
274 transportation methods that have been proposed. Among the techniques proposed, transporting such viscous crudes
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275 as concentrated o/w emulsions is believed to be one of the most favorable ones (Poynter and Simon 1970, Marsden
276 and Raghavan 1973, Sifferman 1981).
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277 Water-in-diesel emulsions (WiDE) has been studied and applied as fuel for regular diesel engines for the
278 reductions in the emissions of nitrogen oxides and particulate matters, which are both hazardous to our health, and
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279 reduction in fuel consumption due to better burning efficiency (Lif and Holmberg 2006). This leads to
280 improvement in combustion efficiency when water is emulsified with diesel as a result of the micro-explosions,
281
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which assist atomization of the fuel. Several studies (Lin and Wang 2003, Abu-Zaid 2004, Lif and Holmberg 2006,
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282 Ghannam and Selim 2009, Alahmer, Yamin et al. 2010, Alahmer 2013, Fahd, Wenming et al. 2013, Ithnin, Noge et
283 al. 2014) have been conducted on the viability of diesel emulsion as an alternative fuel. Most of the studies pointed
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284 to the fact that thermal efficiency is increased by using WiDE fuel compared to clean diesel fuel. Most of the
285 studies also agree that WiDE result in improvements in brake power, torque and specific fuel consumption
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286 measurements when the total amount of diesel fuel in the emulsion is compared with that of the neat diesel fuel.
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287 3. The Emulsification Process
288 Crude oil emulsions form when oil and brine come into contact with each other, with the influence of sufficient
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289 mixing, and in the presence of an emulsifying agent or emulsifier. The amount of mixing and the presence of
290 emulsifier are critical for the formation of an emulsion (Kokal and Wingrove 2000, Herrera 2012). Several sources
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291 of mixing are available during the process of crude oil production, a factor frequently referred to as the amount of
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292 shear. These include; Flow through reservoir rock, bottom-hole perforations/pump, flow through tubing; flow lines,
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293 and production headers, valves, fittings, and chokes, surface equipment, gas bubbles released because of phase
294 change etcetera (Fingas 1995, Kokal and Wingrove 2000, Langevin, Poteau et al. 2004) as indicated with letters A
295 to F on Fig. 2.
296 (Fingas, Fieldhouse et al. 1998, Langevin, Poteau et al. 2004, Fingas and Fieldhouse 2009) studied different
297 emulsions and opined that the amount of mixing depends on several near-unavoidable factors. High speed agitation
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298 and shear causes vigorous mixing of oil and water and leads to smaller dispersed droplet sizes that are more stable.
299 This is, however as a result of the increased energy transferred for the break-up process which eventually lead to
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300 small droplets and more stable emulsions. The sources responsible for this agitation may be present between the
301 time at which the oil enters the well and the time when the produced phases are separated at the surface (Jackson,
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302 Harrington et al. 2012). Undoubtedly, certain methods of production contribute to the formation of emulsions.
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303
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304 Figure 2 A schematic diagram of crude oil flow from the reservoir to the storage tanks.
305
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306 Although, there seems to be no universal theory that has been postulated for all emulsions, several theories
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307 have been suggested to explain variations in emulsions formation processes (Lowe 1955).
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308 According to (Clayton 1923, Becher 1988, Schramm 1992, Bhardwaj and Hartland 1994, Binks 2002, Fingas
309 2014, Umar, Saaid et al. 2017), many factors play different roles in the stabilization of emulsions, but the
310 significance of such roles vary even as they combine in a single emulsion. (Clayton 1923) presented various
311 theories for emulsions. We would mention few of such theories here in section 3.1.
312 All crude oils have four main constituents belonging to four broad classes of compounds. These are classified
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313 as alkanes (also called saturates or aliphatics), aromatics, resins, and asphaltenes, SARA components. The
314 lower-molecular-weight compounds in crude oils are generally alkanes and aromatics, while Asphaltenes,
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315 resins, and waxes (which are high-molecular-weight alkanes) account for the higher-molecular-weight
316 compounds. In a complex mixture like petroleum, all these compounds interact in such a way that all
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317 components are maintained in the liquid oil phase. In other words, the lighter components of the oil act as
318 solvents for the higher molecular-weight compounds. As long as this solvency interaction is maintained in the
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319 oil and thermodynamic conditions remain constant, the oil will remain stable. Should this equilibrium state be
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320 changed, a point will be reached where the solvency strength of the oil is insufficient to maintain the heavy
321 components in solution, and as a result, they will precipitate out as solid particles. This is a frequent and
322 problematic occurrence during petroleum production, transportation, and storage (Griffith and Siegmund 1985,
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323 Kawanaka, Leontaritis et al. 1989, Bobra 1991).

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324 3.1. The phase-volume theory.

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325 This theory holds that, if small spheres of the same diameter are packed as closely as possible into a given space,
326 they will occupy 74·048 per cent of the available volume, irrespective of the size of the spheres This fact was
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327 employed by Ostwald as the basis for a theory of emulsion, generally referred today as the "phase-volume theory."
328 According to Ostwald, 2 two types of emulsions are only possible over a certain range of concentration and that an
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329 emulsion of one liquid in another was only possible when the volume concentration of the dispersed liquid was less
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330 than 74 per cent, the double series being possible only over the range of 25·96 percent to 74·04 percent by volume.
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331 1.1. The Hydration Theory of Emulsions

332
333 According to this theory proposed by Fischer (Finkle, Draper et al. 1923), emulsions can only be created if the
334 liquid which would form the continuous phase is all used in the formation of a hydrated compound of the
335 emulsifying agent employed. Thus, substances such as acacia, soap, gelatin, casein, dextrin, and albumens are
336 considered to act as emulsifiers in virtue of their ability to form colloidal hydrated compounds. The emulsifying
337 efficiencies of these substances vary, since their "hydratability" varies qualitatively and quantitatively.
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338 It is postulated by this theory that oil cannot be emulsified in a hydrated colloid until a certain minimum amount of
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339 water is present; correspondingly, too much water presence (exceeding the amount used in hydrating the colloid),
340 makes the formation of stable emulsion impossible. It is reasonably accurate to emphasise the importance of
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341 hydrophilic colloids in forming oil-in-water emulsions, but it is only reasonable to extend this and debate that oil-
342 soluble colloids (hydrophobic colloids) promote the formation of the water-in-oil type of emulsions.
343 3.2. Oriented wedge theory.
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344 This theory has been developed from the work of Langmuir and Harkins (Clayton 1923). It postulates the manner
345 in which emulsions are stabilized. The theory is established upon the perception that the molecules of the
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346 emulsifier orientate themselves in the interface between the dispersed and continuous phases, forming a wedge,
347 whose curvature determines the size of the dispersed phase.

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348 3.3. The Adsorbed Film and Interfacial Tension Theory
349 At present, the Interfacial tension theory is probably the most universally accepted theory of emulsions formations.
350 Several works done by (Quincke 1889); in which he created emulsions from different oils in solutions of NaOH or
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351 gum Arabic. He found out that the interfacial tensions between the oils and these solutions were lower than those
352 between the oils and pure water. Previous works (Langmuir 1917, Clayton 1923) had shown that oils containing
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353 free fatty acids result to better emulsions in dilute solutions of borax or sodium carbonate than those created by
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354 purer oils. (Quincke 1889), commenting on such works, recommended that the simplicity of emulsification differ
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355 with the acidity and viscosity of the oil, the concentration of the alkaline solution, and the solubility in water of the
356 resulting soap. (Clayton 1923) holds that with this theory "emphasis is laid upon the fact that emulsification is
357 influenced by (1) the mass of the emulsifying agent present, (2) the ease with which this agent is adsorbed at the
358 interfacial separating surface, and (3) the nature of the ions adsorbed by the resultant film."
359 4. Mechanism of Emulsification
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360 Emulsification is a process of agitating two or more immiscible liquids, which result in heterogeneous systems,
361 consisting of at least one immiscible liquid intimately dispersed in another in the form of droplets, whose
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362 diameters, generally exceeds 0.1 µm (Baloch and Hameed 2005). The emulsification process comprises of a certain
363 number of diverse chemical and physical processes and mechanisms, with many theories out forth to justify how
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364 different emulsions are stabilized by the emulsifying agents. The emulsification history can begin right inside the
365 reservoir where the crude oil and water comingle and squeezed through constricted pores. When the crude oil is
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366 produced from the well-head to the manifold (as shown in Fig. 2), there is usually a considerable pressure decrease
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367 with a pressure gradient over chokes and valves where the mixing of oil and water can be intense (Sjöblom, Aske
368 et al. 2003).

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369 As earlier discussed in the definitions of emulsions, they are thermodynamically unstable material systems
370 formed by at least two immiscible liquid phases, with one dispersed in the other(s). When such emulsions separate
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371 into their different phases, there is reduction in the free energy of the system as a result of the large decrease in
372 interfacial area. However, the presence of a third component (referred to as a surfactant) in the erstwhile unstable
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373 system makes the spontaneous formation of thermodynamically stable dispersions (Shahidzadeh, Bonn et al. 1999,
374 López-Montilla, Herrera-Morales et al. 2002). Two forms of emulsification processes are encountered and have
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375 been reported in the literature; (a) Spontaneous emulsification and (b) self-emulsification.
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376 4.1. Spontaneous Emulsification
377 On the one hand, also called “True” Spontaneous emulsification, and it ensues when two immiscible liquids are
378 brought together, and they emulsify without the application of any form of external energy. The emulsification
379 may last for few minutes, or several days depending on the nature of liquids involved (Shahidzadeh, Bonn et al.
380 1999).
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381 4.2. Self-Emulsification
382 On the other hand, emulsification in the industry is habitually accomplished with the aid of appropriate surface-
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383 active agents, and is commonly called 'self-emulsification', although the emulsification process is assisted by
384 providing mechanical energy of some form, such as slight shaking, mixing (5) or sonication. In the case of self-
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385 emulsifying systems, the free energy required to form the emulsion is either very low and positive or actually
386 negative (i.e., the formation is thermodynamically spontaneous) (Craig, Barker et al. 1995, Shahidzadeh, Bonn et
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387 al. 1999).
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388 5. Conditions necessary for Emulsion formation
389 All crude oils, whatever their origin contains certain characteristics which would likely make them emulsifiable
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390 (Bansbach 1965). For emulsions to form, three conditions must be satisfied (Smith and Arnold 1992). These
391 conditions are (a) the two liquids forming the emulsion must be immiscible, (b) there must be sufficient agitation to
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392 disperse one liquid as droplets in the other, and (c) the presence of an emulsifying agent (Becher 1988, Bobra,
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393 Fingas et al. 1992, Smith and Arnold 1992, Fingas 2014).
394 According to Hany et al., (Aziz, Darwish et al. 2002), for an emulsion to form, the system must have the
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395 presence of water (brine), crude oil and sufficient agitation. (Becker 1997) documented that the formation of
396 emulsions requires; differences in solubility between the continuous phase and the dispersed phase, the existence of
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397 intermediate agents having partial solubility in both phases and the presence of an energy source or sources,
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398 sufficient enough to mix the phases.

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399 5.1. The Emulsifiers
400 Also, of paramount importance are the types of emulsifying agents or simply called emulsifiers. Emulsifiers are
401 associated with the produced crude oil. Since the nature and compositions of crude oils vary so widely, there exists
402 also a great variety of crude oil emulsifiers (Meyer 1964). To formulate concentrated stable emulsions, either oil-
403 in-water or water-in-oil type, a third substance is required apart from the two liquids. This substance is called an
404 emulsifying agent, or simply an emulsifier. The nature of the emulsifying agent determines what type of emulsion
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405 forms (Clayton 1923). Thus, the lastingness (known as stability) of the emulsion is dependent upon the
406 rigorousness of the agitation and upon the emulsifying agents (Surfluh 1937).
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407 (Roberts 1926) hold that the emulsifying agent responsible for the formation of petroleum emulsions is not
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408 categorically known. However, in a sizable number of cases, it is believed to be colloidal asphalt, which includes
409 all asphalts and similar substances which occur in colloidal dispersion in crude oil. Since the nature and
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410 compositions of crude oils vary so widely, there exists also a great variety of crude oil emulsifying agents (Meyer
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411 1964) . These emulsifiers include asphaltic materials, “resinous substances, soluble organic acids, particles in the
412 ocean, particles found in crude oils including waxes and asphaltenes, particles found in sea water including
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413 suspended sediments, dissolved surfactants which accumulate at the water/oil interface including metallic salts,
414 organic acids, organic bases and organometallics, and other tiny particles of solids, including products of corrosion
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415 of the equipment involved or particles of the producing formation, in case of wells completed in unconsolidated
416 sands and sandy shales, are also the emulsifying agents contributing toward stability of the emulsions (Lee 1999).
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417
418 The absence of these emulsifying agents in a crude oil can lead to the formation of a dispersion that will separate
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419 quickly due to rapid coalescence of the dispersed droplets. However, the presence of these emulsifying agents in
420 the crude oil would lead to the formation of a very stable emulsion (Bobra 1992, Smith and Arnold 1992, Kokal
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421 and Wingrove 2000, Gafonova and Yarranton 2001, Janssen, Noïk et al. 2001, Sjoblom 2001, Binks 2002, Kokal
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422 2002, Sjöblom, Aske et al. 2003, Fingas and Fieldhouse 2004, Sjoblom 2005, Müller and Weiss 2007). These
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423 natural emulsifiers form a mechanical film at the oil/water interface. The structural mechanical properties of the
424 natural crude oil emulsifiers in the interfacial layer surrounding the dispersed droplets are believed are very
425 important. This is the layer that provides resistance to coalescence in the final stage of emulsion breaking (Jones,
426 Neustadter et al. 1978). It is worthy of mention here that, understanding the chemical and physical properties of
427 these particles that reside at the interface is no doubt, key to understanding the emulsion breaking techniques. This
428 area is receiving more attention of recent. The authors of this paper intend to expound more on the effects of native
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429 organic and inorganic solids on the stability of petroleum emulsions and how they can be included in emulsions
430 stability prediction models.
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431
432 (Gallup and Star 2004) in a study of Acidic crude oils identified that apart from their tendencies to cause scale
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433 formation in production tubing or in surface installations, acidic crude oils also have high tendencies of forming
434 stable emulsions. The scale is often a mixture of calcium soaps associated with other minerals. Nigeria, on the
435
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Afia field, Indonesia, on the Attaka field, Great Britain, on the Blake field, Norway, on the Heidrun field, Angola,
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436 on the Kuito field, China, on the EDC field, Cameroon, on the Kita and Asoma fields. The acidity of crude by itself
437 is not a sufficient criterion. Some weakly acidic oils in Cameroon or in Indonesia may form stable emulsions while
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438 other highly acidic crudes can be treated with no problem. It is the actual structure of the naphthenic acids that may
439 explain these differences in behaviors, hence the importance of characterizing the naphthenic acids of a crude oil.
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440 5.1.1. Amphiphiles

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441
442 (Myers 1990) defined those substances that have chemical groups leading to surface activity as being amphiphilic
443 (‘‘liking both’’), designating that they have some affinity for two fundamentally immiscible phases. The word
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444 amphiphile was created by Paul Winsor 50 years ago (Paul and Moulik 1997). It emanates from two Greek roots.
445 The prefix ‘amphi’ means "double", "from both sides", "around", as in amphibian. Then the root philos which
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446 expresses affinity, as in "philanthropist" (the friend of man), "hydrophilic" (compatible with water), or
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447 "philosopher" (the friend of wisdom or science) (Salager 2002). Crude oil contains particles such as silica, clay,
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448 iron oxides; that are naturally hydrophilic, but can become oil-wet (hydrophobic) due to extended contact with the
449 crude oil in the absence of water. A decrease in the size of oil-wet particles results in an increase in W/O emulsion
450 stability. Emulsions with particles and asphaltenes combined can be much more stable than those stabilized by
451 asphaltenes alone, provided that enough asphaltenes are present: all the adsorption sites on the particle surface need
452 to be saturated by asphaltenes (Langevin, Poteau et al. 2004).
453 An amphiphilic substance exhibits a double affinity, which can be defined from the physico-chemical point of view
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454 as a polar-apolar division. On the one hand, an amphiphiles has a polar group made up of heteroatoms such as
455 Oxygen (O), Sulphur (S), Phosphorus (P), or Nitrogen (N), incorporated in functional groups such as ether,
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456 alcohol, ester, thiol, acid, sulfate, sulfonate, phosphate, amine, amide etc. Equally, it has an principally apolar
457 group which is a hydrocarbon chain of the alkyl or alkylbenzene type, sometimes with halogen atoms and even a
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458 few non-ionized oxygen atoms (Salager 2002).
459
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460 Asphaltenes and resins are among the natural amphiphiles found in crude oils. In an attempt to determine the
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461 contribution of indigenous amphiphiles (the light, intermediate and the heavy ones) to emulsion stability, Dicharry
462 et al.,(Dicharry, Arla et al. 2006) evaluated and compared emulsion formed by different parts of substances. They
463 found out that the emulsions formed with the light and intermediate fractions separated immediately when the
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464 agitation stopped. However, the most stable emulsions form with the fraction of crude that distilled at temperatures
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465 greater than 520°C. This suggests that the amphiphiles with the highest molecular weight, i.e., resins and
466 asphaltenes, play a major role in the protection of water droplet against coalescence, thus making the emulsion
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467 more stable. According to (Acevedo, Escobar et al. 1999, Yan, Elliott et al. 1999, Gu, Xu et al. 2002), the key role
468 of the heaviest amphiphilic materials in the crude oil is to stabilize the interface, while the lightest ones tend to
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469 lower the emulsion stability. Due to its dual affinity, an amphiphilic molecule does not feel "at home" in any
470 solvent, whether it is polar or non-polar. This is because, there always exist one of the groups which "does not like"
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471 the solvent environment. This is the reason amphiphilic molecules have a very strong tendency to migrate to
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472 interfaces or surfaces and to adjust so that the polar group lies in water and the non-polar group is placed out of it,
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473 and ultimately in oil. Amphiphiles have other properties other than tension lowering and this is why they are often
474 categorized based on their main use such as: soap, foaming agent, detergent, emulsifier, wetting agent, dispersant,
475 bactericide, corrosion inhibitor, antistatic agent, etc. In some cases they are known from the name of the structure
476 they are able to build, i.e. membrane, micro-emulsion, liquid crystal, liposome, vesicle or gel (Salager 2002).
477
478 5.1.2. Asphaltenes, Resins and Waxes as Emulsifiers
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479
480 (Roberts 1926) in a study on treating field emulsions in Mid-continent Field that the emulsifying agent
481 responsible for the formation of petroleum emulsions is not definitely known but, can be attributed to the presence
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482 of colloidal asphalt, that including all asphalts and similar substances which occur in colloidal dispersion in crude
483 oil. Determining the type of an emulsion is very simple. If it is miscible with water, it is an emulsion of oil in
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484 water; if miscible with oil, it is water dispersed in oil. Probably more than 95 percent of all oil field emulsions are
485 of the water in oil type (Wang, Zhang et al. 2004).
486
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(McLean and Kilpatrick 1997) in an attempt to further investigate the effects of crude solvency and specific
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487 resin–asphaltene interactions on emulsion stability, created model emulsions, using model oil formed by dissolving
488 varying amounts of resins and/or asphaltenes in a mixture of heptane and toluene. The resins and asphaltenes used
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489 in this study were isolated from four different types—Arab Berri, Arab Heavy, Alaska North Slope, and San
490 Joaquin Valley. They found out that the prime factors governing the stability of these model emulsions were the
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491 aromaticity of the crude medium, the concentration of asphaltenes, and the availability of solvating resins in the oil
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492 (i.e., the resin/asphaltene or R/A ratio). The model emulsions were the most stable when the crude medium was
493 30–40% toluene and in many cases at small R/A ratios (i.e., R/A ≤1). This immensely supports the theory that
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494 asphaltenes are the most effective in stabilizing emulsions when they are near the point of incipient precipitation.
495 The point of incipient precipitation, according to (Andersen and Speight 1992) is the point at which separation of
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496 asphaltenes from a crude oil becomes apparent.

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497 (Sjöblom, Mingyuan et al. 1990b) in a study conducted to compare the destabilization of True petroleum
498 Emulsions from the Norwegian Continental Shelf and Model Systems. It was reported that True water-in-crude oil
499 emulsions are stabilized by a rigid interfacial film in which the surface-active material is accumulated, and that the
500 distinct components of this film seem, at least for the crude oils from the Norwegian continental shelf, to be
501 asphaltenes, waxes and other non-specified polar components. In addition, small wax particles are incorporated in
502 the film. On the other hand, inorganic particles such as clays have not been detected under laboratory conditions.
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503
504 Earlier before the works of Anderson and Speight, (Bridie, Wanders et al. 1980) investigated the roles of wax
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505 and asphaltenes separately and in combination. In the study, a Kuwait 200+ fraction was first deasphaltenized
506 (thirty-fold dilutions with n-pentane) and then dewaxed. The dewaxing involves a six-fold dilution in a methyl
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507 ethyl ketone/dichloromethane mixture 1/1 vol.). The asphaltenes fraction was recovered and kept under nitrogen to
508 prevent oxidation, and an emulsion of synthetic sea water (70% vol.) in the Kuwait 200 + fraction proper (30%
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509 vol.) was prepared. The investigation revealed that, the de-asphaltenized, dewaxed oil did not form a stable
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510 emulsion and had released 93% of its water content after standing for 15 min while the oil plus wax and
511 asphaltenes mixed to the original concentrations gave a stable emulsion.
512
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513 (Kim, Boudh-Hir et al. 1990) investigated the role of asphaltene both in wettability reversal and as a surfactant.
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514 The change in wettability is governed mainly by interfacial properties, with interfacial tension probably being the
515 most important property. When a rock surface comes in contact with crude oil, the surface of the rock can possibly
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516 be modified due to asphaltene adsorption. This could alter the wettability of the rock. Whereas the polar segments
517 of an asphaltene molecule are oriented towards the surface, the non-polar portions are away from it, causing the
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518 surface to be oil-wettable. It is a well-known fact that certain solids that possess dual wettability (i.e. are wetted by
519 both oil and water can play the role of emulsifiers (Sjöblom, Söderlund et al. 1990a, Bobra 1991, Becker 1997, Lee
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520 1999, Vignati, Piazza et al. 2003, Sztukowski and Yarranton 2005, Al-Sahhaf, Fahim et al. 2009). Thus, when
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521 asphaltene adsorbs on such solids (when they come in contact with the crude oil), there is a high possibility of
522 modification of its wettability from dual wettability to single wettability.
523 (Salager 1990) in an investigation of the most effective mechanism for destabilization of W/O or O/W emulsion
524 reported that the removal of the surfactant from the water-oil interface by trapping it in a micro-emulsion is the
525 most effective destabilization mechanism. According to the study, these emulsion stabilizers have a polar part with
526 affinity to water and a nonpolar part with affinity to oil. These substances cannot fulfil this dual affinity, except
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527 when they are located at the water/oil interface, with the polar part immersed in water and the nonpolar part in oil.
528 When they are adsorbed at the interface, they result to a decrease in the free energy of the system. Such include
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529 naphthenic acids, resins, asphaltenes, etc.
530
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531 A physicochemical study by (Bobra 1991) on the emulsification of water-in-oil emulsions reiterated the fact
532 that, the indigenous emulsifying agents are concentrated in the higher boiling fractions (boiling point > 370° C),
533
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and predominantly in the residuum. It is largely accepted that asphaltenes, resins, and waxes play key roles in
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534 emulsification, but specific mechanisms have not been clearly explained. These compounds are believed to be the
535 main constituents of the interfacial films that surround the water droplets contained in the emulsion. These films
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536 have been shown to have high mechanical strength and therefore act as effective physical barriers, which prevent
537 droplet coalescence and in turn gives rise to the stable petroleum emulsions.
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538
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539 (Sztukowski and Yarranton 2005) studied the stability of w/o emulsion with clays. In the study, heptane,
540 toluene, and asphaltenes were used as model fluids and native solids extracted from oilfield operations. They
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541 established that a combination of asphaltene and fine solids (submicron scale) coverage produced the most stable
542 emulsions. They claim that fine solids compete with asphaltenes to adsorb at the interface and that a coverage of
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543 the interface by asphaltenes between 60 to 80% and the remaining area covered by fine solids leads to the highest
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544 stability. Coarser solids (above 1 µm) can indeed stabilize emulsions, but only if they are in sufficiently high
545 concentration.
546
547
548
549
550
551
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552
553
554
555
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556
557
558
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559
560
561 Figure 3 (a) Example of a hypothetical structure of asphaltene, among the many suggested, showing their aromatic character.
562 (b) Asphaltene structure deduced from microscopic and macroscopic analysis, showing their micro- and macro-molecular
563 bonding (Kawanaka, Leontaritis et al. 1989).
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564
565
566
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567
568
569
570
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572
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573
574
575
576
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577
578 Figure 4 Formation of water-in-oil emulsions (Lee 1999).
579
580
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581 (Bobra 1992) studied the emulsification of W/O emulsions, and the effects of wax, resin and asphaltenes. From
582 the studies, it was revealed that waxes cannot act as emulsifying agents by themselves but can act in combination
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583 with resins or asphaltenes to produce stable oil-in-water emulsions. Thus, a concentration of 0.01 g/ml of
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584 asphaltenes did not produce a stable water-in-oil emulsion, but when waxes were added (0.05 g/ml), stable
585 emulsions were formed. An asphaltene concentration of 0.03 g/ml, with no wax added, produced a stable emulsion.
586
587
588 (Bobra 1991) established that resins alone could act as effective emulsifiers, but the most stable emulsions were
589 produced when both asphaltenes and resins were present. It was suggested that waxes could interact with
590 asphaltenes and resins to stabilize emulsions. Stable emulsions are characterized by properties which prevent the
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591 coalescence of their small water droplets (1 to 10 µm), while in unstable emulsions the larger water droplets
592 quickly coalesce as in Fig. 4.
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593
594
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595
596
597
598
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599
600
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601
602
603
604
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605
606
607
608
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609
610
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611
612 Figure 5 (a) Schematic Diagram of dispersed water droplets in oil stabilized by asphaltenes, waxes and surfactants. An unstabilized region is
613 shown where there is formation of an incomplete barrier. Modification by (Umar, Saaid et al. 2016)., from (Daling, Moldestad et al. 2003) (b)
614 Modified from (Lee 1999).
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615
616
617 (Daling, Moldestad et al. 2003) in a review of the major findings from laboratory studies and field trials conducted
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618 on the emulsification of oils spilled at sea, reported that among other factors, the precipitation of stabilizing agents
619 (asphaltenes, photo-oxidized compounds (resins) and in some crude oils precipitated waxes) leads to the formation
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620 of stable W/O emulsions. The precipitated asphaltenes make an elastic ‘‘skin’’ between the water droplets and the
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621 oil (see Fig. 5), leading to an increase in the stability of the emulsion- since the water droplets cannot coalesce and
622 drain so easily from the emulsion and the equilibrium will tend to favour emulsion formation. (Lee 1999) in a an
623 attempt to study the agents that promote and stabilize W/O emulsions reported that particles and surfactants found
624 in crude oil can act as emulsifying agents and thus can promote and stabilize water-in-oil emulsions. If particles
625 and surfactant concentrations are adequately high, then the coalescence of the water drops are prevented, leading to
626 stable emulsions (Fig. 5b).
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627
628
629 Particles found in crude oils include waxes and asphaltenes, while particles found in sea water include suspended
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630 sediments and/or particulates. Dissolved surfactants which accumulate at the water/oil interface include metallic
631 salts, organic acids, organic bases and organometallics. In oceans and during oil spills, particles in the ocean can
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632 enter an oil slick and act as emulsifying agents.
633 (Bobra, Fingas et al. 1992) has advocated that asphaltenes resins and waxes must be in the form of finely divided
634
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submicrometer particles before they can act as emulsifying agents.
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635 According to (Filby and Van Berkel 1987), since the classification of asphaltenes and resins is an operational term,
636 i.e. they are defined based on their solubility in different solvents, there exist no clear difference between the
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637 compounds found in the two fractions. Resin particles are mostly smaller than asphaltene particles and most of the
638 metal porphyrins are in the asphaltene fraction. Asphaltenes tend to have higher-molecular-weight compounds and
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639 to be more polar than resins.

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640
641 (Lee 1995) disputed the fact that a direct correlation exists between the presence/concentration of asphaltene in
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642 certain crude and the stability of the emulsion formed by that crude. In a study involving a Kuwait crude oil with
643 1.4% asphaltenes and TiaJuana crude oil with 3.1% asphaltenes, it was found that the Kuwait crude forms a more
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644 stable emulsion than the TiaJuana crude, despite the fact that the Tiajuna crude contains a higher concentration of
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645 asphaltene.
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646 (Jenkins, Grigson et al. 1991) carried out an empirical laboratory procedure to obtain information about the
647 different tendencies of six North Sea crude oils to form stable and highly viscous water-in-oil emulsions. They
648 found out that one crude (identified as crude A) had 1.6% asphaltenes and formed a very stable emulsion while a
649 second crude (crude B) had 1.03% asphaltenes and did not form stable emulsions. Thus, certain components of the
650 asphaltenes may play a critical role in emulsion formation. The amounts of these emulsifying agents in asphaltenes
651 are likely to vary for asphaltenes from different crude oils. However, several studies have established the
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652 significance of asphaltenes, resins and waxes in promoting and stabilizing w/o emulsions.
653
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654 (Brandvik 1991) in a study found that the stability of a water-in-oil emulsion was positively correlated with the
655 resin, wax and asphaltene content of the original crude oil. Also, in separate studies, (Sjöblom, Söderlund et al.
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656 1990a, Ebeltoft, Børve et al. 1992, Sjöblom, Urdahl et al. 1992, Urdahl, Brekke et al. 1992, Umar, Saaid et al.
657 2017) observed that the exclusion of asphaltenes from crude oils by silica columns produced oils that did not form
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658 water-in-oil emulsions.
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659
660 (Bridie, Wanders et al. 1980) found that after the removal of asphaltenes from Kuwait crude oil, very unstable
661 emulsions were produced. When wax crystals and asphaltenes were added back to the treated oil, a stable water-in-
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662 oil emulsion was formed. Waxes cannot act as emulsifying agents by themselves but can act in combination with
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663 resins or asphaltenes to produce stable oil-in-water emulsions. Thus, a concentration of 0.01 g/ml of asphaltenes
664 did not produce a stable water-in-oil emulsion, but when waxes were added (0.05 g/ml), stable emulsions were
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665 formed (Bobra 1992, Bobra, Fingas et al. 1992).
666
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667 (Oliveira and Goncalves 2005) in a study on the rheology of emulsions held that the presence of W/O emulsions
668 may have a strong impact on the crude oil production, especially in offshore conditions. In such kind of systems,
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669 the temperature of the crude oil varies widely along the flow from the reservoir to the platform storage tanks. For
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670 example, in Campos basin, where most of the Brazilian crude oil is produced, typically the temperature of the oil
28
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671 gradually decreases from 80 ºC at the bottom of the well-bore, located 3,000 m below the seabed, to about 60 ºC at
672 the top of the well-bore, located 1,000 m below the sea level, where the sea water temperature may vary from 4 ºC
673 to 10 ºC. In order to reach the storage tank, the crude oil has to flow for several hundred meters through a pipeline
674 in a cold environment. The contact with the cold seawater imposes a major decrease in the crude oil temperature;
675 hence crude oil arrival temperatures below 30 ºC have been frequently reported in some fields.
676
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677 (McMahon 1992) studied the interfacial action of crude oil emulsions at the interface. He found out that in
678 certain waxy crude oils, the size of the wax crystal has a fundamental role on the stability of W/O emulsions. Data
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679 obtained of the interfacial viscosity and other physical properties of the mixture show that the crystals form a
680 barrier at the W/O interface, which retards the coalescence of colliding water droplets. To associate with the
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681 interface, wax, which is normally hydrophobic, has to acquire some affinity for the water phase, possibly by
682 adsorption of polar asphaltenes and resins from the crude oil. Studies with Octacosane (n-C28H58), a model crude
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683 oil wax, show that limited wax/asphaltene/resin interactions do exist. However, the adsorbed layer does not confer
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684 hydrophilicity to the surface of either Octacosane or real crude oil wax. Therefore, the effect of wax on emulsion
685 stability does not appear to be through action at the interface. Instead, wax may act in the bulk oil phase by
686 inhibiting film thinning between approaching droplets or by scavenging demulsifier. It is the asphaltene and resin
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687 that were found to affect stability via interfacial action. They can adsorb in either dissolved or in solid form and
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688 thereby inhibiting water separation. When wax crystals occur in the continuous phase, they usually act as emulsion
689 stabilizers. However, if they are present in the dispersed phase, such crystals may stick out through the interface,
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690 leading to partial or complete droplet coalescence (Becker 1997, Rousseau 2000).
691
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692 (Mouraille, Skodvin et al. 1998) reported how naturally occurring surfactants in crude oils (mainly asphaltenes
693 and resins) are important for the stabilization of water-in-crude oil emulsions. According to a research reported, the
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694 stability of emulsions at room temperature was mainly due to those surface-active fractions. It is crucial to gain a
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695 better understanding of the mechanisms via which the stabilization processes of water-in-crude oil emulsions
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696 occur, so as to solve the emulsion problem more efficiently. In general, about 2/3rd of the world's crude oil is
697 produced in form of emulsions that must be treated (demulsified) before it can be marketed. These oilfield
698 emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases
699 (Strassner 1968). They are mostly stable and form spontaneously due to the presence of natural surfactants existing
700 in the crude oil phase. It is known that the viscosity of a w/o emulsion is strongly augmented by increasing its
701 water volume fraction and by decreasing the temperature. When w/o emulsions form, oil viscosity changes from a
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702 few hundred mPa.s to about 100,000mPa.s (Selvarajan, Sivakumar et al. 2001, Ge, Yang et al. 2010, Wang and
703 Alvarado 2011, Fingas 2014, Fingas and Fieldhouse 2014).
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704 6. Emulsion Stabilization Mechanisms
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705 There are four principal mechanisms for the stabilization of emulsions (with cases where a combination of
706 mechanisms occurs). Certain emulsions may be weakly stabilized by the presence of adsorbed ions and non-
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707 surface-active salts (a). The presence of colloidal sols partially wetted by both phases of the emulsion may form a
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708 mechanical barrier to drop contact and coalescence (b). Many emulsions are stabilized by adsorbed polymer
709 molecules (c). Along with polymers, adsorbed surfactant molecules represent the most common stabilization
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710 mechanism (d). These are as depicted in Fig. 6 below.
711 6.1.1. Surfactants

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712
713 Surfactants are amphiphilic molecules comprising of two dissimilar parts: one hydrophilic (water liking) and the
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714 other hydrophobic (water disliking). The hydrophilic part (the head) of the surfactant molecule may be positive,
715 negative, neutral, or Zwitter ionic, and the hydrophobic part (tail) consists of one or more hydrocarbon chains,
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716 usually with 6–22 carbon atoms (Migahed and Al-Sabagh 2009).
717
718 According to (Salager 2002), Surfactants are substances which exhibits some superficial or interfacial activity. It is
C
719 a short form for Surface-Active-Agents. Other languages such as Spanish, French or German do not have the word
AC
720 "surfactant", but however describe these substances based on their characteristics to lower the surface or interfacial
30
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721 tension. For instance, the French would use tensioactif, German would use tenside, while Spanish would call it
722 tensioactivo.
723
724 This would suggest that surface activity is firmly the same to tension lowering, which is not absolutely general,
725 although it is true in many cases. It is worth mentioning that it is not all amphiphiles that display such activity. It is
726 only the amphiphiles with more or less equilibrated hydrophilic and lipophilic tendencies that are likely to migrate
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727 to the surface or interface. It does not happen if the amphiphilic molecule is too hydrophilic or too hydrophobic, in
728 which case it stays in one of the phases.
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729
730
731
732
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733
734
735
736
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737
738
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739
740
741
742
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743
744
745
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746
747
748
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749
750
751
752 Figure 6 Main emulsions stabilization mechanisms (Myers 1990).
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753
754
755 (Li, Guo et al. 2006) carried out a study on the formation of emulsions during chemical flooding (ASP) in Da
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756 Qing and Sheng Li oil fields in China. In the study, partially hydrolyzed polyacrylamide (HPAM) was used as the
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757 polymer, petroleum sulfonate (ORS-41 or TRS) as the surfactant, and sodium hydroxide (NaOH) or sodium
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758 carbonate (Na2CO3) as the alkaline component. Although, the technique yielded an increase in oil recovery of 15 to
759 20% compared with water-flooding, formation of stable w/o and o/w emulsions accompanied it. They found out
760 that the formation and properties of the crude emulsions formed in this technique are exceptionally complicated.
761 These emulsions do not only depend on the properties of the crude oil, the injection water and formation water, the
762 alkali, HPAM, and surfactant used, but also on the properties of the reservoir formed alkali–oil surfactant, the solid
763 particles from the reservoir among others.
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764
765 6.1.1.1. Surfactant Classifications
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766 Surfactants can be classified commercially according to the uses they are put to in different industries. In the Oil
767 and Gas industry for instance, there is an increased used of surfactants in the formation of drilling fluids. In oil-
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768 based drilling fluids, surfactants are used as emulsifiers and wetting agents. In water-based muds however, there is
769 a continually-growing diverse applications that include oil-in-water emulsification in base fluid formulations;
770
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shale-swelling inhibitors to prevent wellbore instabilities, detergency to prevent cuttings sticking to drill bit,
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771 defoaming additives to eliminate unwanted foam in water-based fluids; surfactant-polymer complexes for
772 enhanced properties in fluids for low-pressure reservoirs, etc. (Quintero 2002). Other applications of surfactants in
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773 the oil and gas industry include: Gas/liquid systems; producing oil well and well-head foams, oil flotation process
774 froth, Liquid/liquid systems; emulsion drilling fluids (as explained above), Enhanced oil recovery in situ emulsions
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775 (EOR), Well-head emulsions, Heavy oil pipeline emulsions, Fuel oil emulsions, etc (Schramm, Stasiuk et al. 2003,
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776 Migahed and Al-Sabagh 2009). Classifications of surfactants based on their usage however, is not as important as
777 classifying them based on their dissociation in water (Salager 2002). Thus, based on their dissociation in water,
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778 surfactants can be classified as:
779
780 • Anionic Surfactants
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781
782 These types of Surfactants are dissociated in water in an amphiphilic anion, and a cation, that is commonly an
AC
783 alkaline metal (Na+, K+) or a quaternary ammonium. They are the most universally used surfactants across many
32
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784 industries. They comprise alkylbenzene sulfonates (detergents), (fatty acid) soaps, lauryl sulfate (foaming agent),
785 di-alkyl sulfosuccinate (wetting agent), lignosulfonates (dispersants) etc. 50% of the world surfactants produced
786 are Anionic surfactants (Salager 2002). This moiety carries a negative charge, as in soap: C17H35COO- Na+, sodium
787 stearate (Becher 1988, Schramm, Stasiuk et al. 2003, Migahed and Al-Sabagh 2009).
788
789 • Cationic Surfactants
790
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791 These classes of surfactants are dissociated in water into an amphiphilic cation and an anion, most habitually of
792 the halogen type. These surfactants are in general more expensive than anionics, because of the high pressure
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793 hydrogenation reaction to be carried out during their synthesis. As a consequence, they are only used in cases
794 where there is no cheaper substitute (Salager 2002, Migahed and Al-Sabagh 2009). The charge is positive, as in
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795 quaternary ammonium salts: (C18H37)2N+(CH3)2Cl-, dimethyl dioctadecyl ammonium chloride (Schramm, Stasiuk
796 et al. 2003, Migahed and Al-Sabagh 2009).
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797
798 • Amphoteric or Zwitterionic Surfactants
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799
800 There are situations where a single surfactant molecule exhibit both anionic and cationic dissociations. This
801 surfactant is called an amphoteric or a zwitterionic surfactant. Syhthetic products like betaines or sulfobetaines and
M
802 natural substances likes aminoacids and phospholipids exhibit this behavior (Salager 2002).
803 For these surfactants, solubilization is provided by the presence of positive and negative charge in the molecule, as
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804 in C12H35N+(CH3)2CH2COO-, Ɓ-N-alkyl amino propionic acid (Schramm, Stasiuk et al. 2003, Migahed and Al-
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805 Sabagh 2009).
806
807 • Non-Ionic Surfactants
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808
809 Nonionic Surfactants do not ionize in aqueous solution, because their hydrophilic group is of a non- dissociating
810 type. These comprise of groups like alcohol, phenol, ether, ester, or amide. They come as a close second with about
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811 45% of the overall industrial production (Salager 2002). According to (Migahed and Al-Sabagh 2009), the
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812 solubility is provided by solvation of polyoxy ethylene oxide groups in water, such as C9H19C6H4(OCH2CH2)9OH,
813 nonyl phenol ethoxylate (Schramm, Stasiuk et al. 2003).
814 6.1.1.2. Surfactants Roles in Emulsion Stabilization

815
816 • Surfactant Adsorption at Liquid-Liquid Interface
817
818 The adsorption of surfactants at liquid interfaces can influence emulsion stability by lowering interfacial
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819 tension, increasing surface elasticity, increasing electric double layer repulsion (ionic surfactants), and possibly
820 increasing surface viscosity (Schramm, Stasiuk et al. 2003). Also, surfactant nature can control the arrangement of
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821 the phases in an emulsion, that is, which phase will form the dispersed versus continuous phase. As discussed
822 earlier (under section 3), several experimental predictive methods based on anticipated surfactant positioning at the
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823 interface exist (Schramm 2000, Dingcong 2002, Pasquali, Sacco et al. 2009). These include the Bancroft’s rule, the
824 oriented wedge theory, the hydrophile–lipophile balance (HLB), and the volume balance value (Dingcong 2002).
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825 Among all the methods, the HLB has been the most widely used. The HLB dimensionless scale ranges from 0 to
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826 20 for non-ionic surfactants; a low HLB (<9) refers to a lipophilic surfactant (oil soluble) and a high HLB (>11) to
827 a hydrophilic (water soluble) surfactant. Most ionic surfactants have HLB values greater than 20. Water-in-oil
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828 (W/O) surfactants show HLB values in the range 3–8 while oil-in-water (O/W) emulsifiers possess HLB values of
829 about 8–18 (Schramm 2000, Pasquali, Sacco et al. 2009, Zafeiri, Horridge et al. 2017). Additionally, surfactant
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830 exchanges between the interface and the bulk can drastically lower interfacial visco-elasticities (Powell, Damitz et
831 al. 2017).

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832
833 • Surfactants and Wettability Alteration
834
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835 Certain surfactants adsorb at a solid surface and by so doing, reduce interfacial tension and alters the ability of
836 water or oil to wet the solid surface. When the adsorbed surfactant positioning is in such a way that its hydrophobic
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837 (water disliking) tail groups point away from the surface or along the surface, that will lead to a decrease in water-
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838 wetting and an increase in oil-wetting. Similarly, if the positioning is with the polar head group away from the
34
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839 surface, there will be a resultant increase in water-wetting. An example of surfactant-induced wettability alteration
840 can be found in the treatment of swelling clays, such as montmorillonite, with a cationic surfactant, such as
841 dimethyl di(hydrogenated tallow) ammonium (Schramm 2000, Schramm, Stasiuk et al. 2003).
842 6.2. Roles of Solids in w/o Emulsion Stabilizations (Pickering)
843 The subject of Pickering emulsions was first investigated by (Ramsden 1903)(Proc. Roy. Soc., 1903, 72, 156).
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844 However, (Pickering 1907) was independently working on emulsification of solids, and only got to know about the
845 work of Ramsden after he has completed his work. Thus, the credit on Pickering emulsion is mostly given to
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846 Pickering. An accumulation of continuous research in the past one century led to the recognition of distinctive
847 characteristics of Pickering emulsifiers compared with conventional emulsifiers, such as, irreversible interfacial
SC
848 adsorption, exceptional stability against coalescence and Oswald ripening , the capability to stabilize emulsions
849 with enormous droplet size (up to several millimetres) or high internal phase, irregular rheological properties, etc.
U
850 (Dickinson 2012, Rayner, Marku et al. 2014, Xiao, Li et al. 2015).
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851
852 According to (Pickering 1907), the mixture of any insoluble liquid in water, where the water is broken up into
M
853 minute globules, like when it is forced through a syringe, the globules would remain emulsified permanently if the
854 water contains emulsifying agents. On mixing lime with paraffin and water, a kind of emulsion formed, which
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855 either upsurges or descends in the excess of liquid, according to the proportions used.
856 However, describing the behaviour of the many substances that results to these different emulsions types would be
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857 a tedious and unprofitable task. Thus, it is sufficient to briefly classify as those which give true emulsions, those
858 which give inadequate emulsions or quasi-emulsions, and those which do not emulsify at all.
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859 This study established the fact that solids which are not adequately fine-grained to emulsify will, in most cases,
860 when present in significant amounts, form quasi-emulsions. Lime for instance forms a quasi-emulsion. Other
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861 substances, including many recently formed precipitates, and, probably, all crystalline solids seem to be incapable
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862 of forming even quasi-emulsions. This was the earliest documented results on Pickering emulsions, and this
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863 opened doors to further researches. (Clayton 1923) reported how finely-divided solids in certain instances can
864 promote emulsification of o/w or w/o emulsions. He found out that a North African argillaceous earth promptly
865 emulsified oils in water and could be used as a replacement for soap.
866 (Alexander 1921) reported that emulsification is influenced by the size of the particles of the emulsifier, and that
867 the size of the emulsion droplets varied directly with the size of the particles of the emulsifying agent. He also
868 identified the ideal condition that for emulsions of oil in water the finely-divided solid emulsifying agent must be
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869 more readily wetted by water than by oil while that of w/o should be more wetted by oil than water.
870 (Briggs 1921) in a study of emulsions by finely divided solids showed that certain finely-divided solids, when
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871 used together, might exert opposing emulsifying effects. For instance, adding 0·8g of carbon black (CB), an
872 amount sufficient to disperse 25 c.c. of water in 15 c.c. kerosene, to 0·1g of silica (350 mesh), no emulsion was
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873 possibly formed. However, kerosene can be emulsified in a water suspension of silica, but if sufficient CB is
874 present, no emulsion is formed. Similarly, 1 part of mercuric iodide in 20 parts of silica will prevent the latter from
875 emulsifying 25 c.c. of kerosene in 25 c.c. of water.
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876 (Mukerjee and Srivastava 1956) reported the action of colloidal clay as efficient emulsifying agents. According
877 to their findings, colloidal clay is capable of promoting the emulsification of o/w or of w/o emulsions. Such results
M
878 however had to be subjected to further investigation because as at that moment, what was understood was that a
879 given emulsifying agent only promotes one type of emulsion with any two given liquids to be emulsified. (Al-
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880 Sahhaf, Fahim et al. 2009) while studying the factors that control emulsion stability in Burgan Oilfield Kuwait
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881 reported that colloidal particles partially wetted by both the water and oil phases are capable of effectively
882 stabilizing emulsions.

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883
884 In separate studies, (Binks 2002, Binks, Clint et al. 2005, Binks and Rocher 2009) also established that colloidal
C
885 particles such as wax crystals can originate by direct solidification at the droplet interface, or previously formed
AC
886 crystals can migrate and attach themselves to the interface. Colloidal particles like wax, silica, clay, iron oxide and
36
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887 polymer lattices can provide kinetic stability to the dispersed phase of many oil-continuous emulsions via either the
888 presence of a particle network and/or interfacially-adsorbed colloids. The degree to which solids increases
889 emulsion stability depends on several factors such as particle size, shape and morphology, density, concentration,
890 and surface coverage, and wettability.
891
892 (Gelot, Friesen et al. 1984) investigated the effect of different combinations of finely divided solids and surface-
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893 active agents on the stability of a w/o emulsion. In the study, they investigated the emulsification of w/o by the
894 clays (Ca−bentonite and Ca−kaolinite), as well as carbon black. The study revealed that by adding the surfactant
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895 sodium dodecyl sulfate (SDS), the stability of the emulsion can be enhanced, and the wettability of the particles
896 changed. Thus, the principles that developed from this work and preceding works was that surface modification of
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897 solid particles by adsorption of surface-active materials can modify the wettability of the particles and the stability
898 of the emulsions enhanced. (Finkle, Draper et al. 1923) are seemingly the pioneer researchers to link the three-
899
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phase contact angle, (see Fig. 7 and 8) with the type of emulsion (O/W) or (W/O) stabilized by the solid particles.
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900 According to them, the better-wetting liquid constitutes the continuous phase. (Reinders 1913) articulated three
901 important parameters that are some strong possibilities for the interfacial tension in a solid-liquid-liquid system;
M
902 γ12, γ13, γ23, where 1 and 2 denote the two liquids and 3 the solid. These possibilities are:
903 1. γ23>γ12+γ13, particle wetted completely by liquid 1;

D
904 2. γ13>γ12+γ23, particle wetted completely by liquid 2;

TE
905 3. γ12>γ13+γ23, or γij>γik+γjk for all i≠j≠k, particle wetted partially by both liquids.
906 Only in case (3) will the particle tend to situate itself at the liquid-liquid interface.
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907
908 (Thompson, Taylor et al. 1985) demonstrated how wax particles and associated solids have considerable
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909 influence on the emulsion stability of waxy North Sea crude. They found out that isolating the indigenous particles
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910 from this oil inhibited oil’s tendency to form stable emulsions. (Bobra, Fingas et al. 1992) established that for
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911 solids to act emulsifying agents, the particles must be very small compared to the droplet size of the emulsified
912 phase. They must accumulate at the interface and they must be “wetted” by both the oil and water phases.
913 (Monson 1969) in a study on chemical resolution of emulsions stated that depending on the specific characteristics
914 as geological age, chemical composition and other impurities, a wide range of materials can stabilize crude oil
915 emulsions. These include materials include finely-divided solids or mechanical stabilizers such as drilling mud
916 (Colloidal clay), produced sand, iron sulphide from pipe corrosion, precipitated minerals due to scale formation,
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917 asphaltenes in the crude oil.
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918 6.2.1. Pickering Stabilization Mechanism
919
920 Several studies have been dedicated to the clarification of the mechanisms behind particle stabilization by
SC
921 focusing on the influence of particle size, hydrophobicity, surface roughness and shape (Ngai and Bon 2014). The
922 phenomenon that solid particles can reside at the interface of droplets, thereby giving them some resistance against
923
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coalescence or fusion, or Ostwald ripening, is known as Pickering stabilization (Bernardini 2015) (Ngai and Bon
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924 2014). (Binks and Lumsdon 2000) reviewed some experimental findings concerning the stabilization of emulsions
925 by solid particles. They further described the preparation and properties of w/o emulsions stabilized by nanometer-
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926 sized hydrophobic silica particles alone.
927
D
928 (Binks and Lumsdon 2000) reported, based on the works of (Abend, Bonnke et al. 1998, Lagaly, Reese et al. 1999,
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929 Neuhäusler, Abend et al. 1999), at least two mechanisms by which colloidal particles stabilize emulsions
930 depending on the system. In the first mechanism, the particles are expected to adsorb at the oil/water interface and
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931 stay there forming a dense monolayer or multilayer film around the dispersed droplets, thus hindering coalescence.
932 In the second, increased stabilization ensues when the particle-particle interactions are such that a three-
C
933 dimensional network of particles forms in the continuous phase surrounding the dispersed droplets. This has been
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38
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934 cited mainly in clay-containing systems in which the emulsion oil drops become captured and largely immobilized
935 in the array of clay platelets in water.
936
937 (Kilpatrick 2012) suggested that the mechanism by which w/o emulsions are stabilized by inorganic solid particles
938 seems to be principally via the enhancement of asphaltene and/or resin or crude oil acid-stabilized emulsions by an
939 adsorption process of surface-modifying components in the crude oil to the particles that render them interfacially
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940 active. There seems to be a limit to the surface coverage of inorganic particles that can effectively stabilize
941 micrometer-sized droplets, with particles in the tens to hundreds of nanometer size scale being most effective.
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942 Figure 9 shows a schematic of surfactant molecule and a colloidal particle at oil-water interface. Surfactants are
943 amphiphilic molecules and they have a natural tendency to move to the oil-water interface. They decrease the oil-
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944 water interfacial tension; and by so doing minimizing the energy required for emulsion formation. The adsorbed
945 surfactant molecules at the interface act as electrostatic or steric barriers against droplet coalescence thereby
946
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increasing the emulsion stability. Hydrophilic-Lipophilic balance (HLB) of the surfactant molecules dictate the
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947 nature of the emulsion formed; either O/W or W/O (Ramsden 1903, Pickering 1907, Clayton 1923, Binks 2002).
948
M
949 Finely divided insoluble solid particles constitute an important class of emulsifying agents (Al-Sahhaf, Fahim et al.
950 2009) and behave in various ways like surfactant molecules, particularly if adsorbed to a fluid/fluid interface. Just
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951 as the water or oil-liking tendency of a surfactant is quantified in terms of the hydrophile-lipophile balance HLB
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952 number, so can that of a spherical particle be described in terms of its wettability via contact angle. Important
953 differences exist, however, between the two types of surface-active material, due in part to the fact that particles
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954 are strongly held at interfaces (Binks 2002).
955 According to (Myers 1990), there are three conditions a solid must satisfy before it can play the role of an emulsion
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956 stabilizer: (1) Particle size; In field operations, it is found that the stabilizer particles must be smaller than the
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957 emulsion droplets, (2) the state of stabilizer particle dispersion; (i.e. in a state of incipient flocculation -that is, they
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958 should have partial colloidal stability in both liquids, otherwise their tendency to ‘‘reside’’ at the oil–water
959 interface will not be sufficiently strong for them to act as stabilizers, and (3) the comparative wettability of the
960 particles by each liquid component of the emulsion system; the solid must exhibit a significant contact angle at the
961 three-phase (oil–water–solid) contact line, usually as measured through the aqueous phase.
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962 .
963
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964 Figure 7 (Left)Distribution of solid particles at water/oil interface (Bobra 1991). (Right) Particles positioning at oil/water interface (Binks
965 2002).
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966
967
968 For maximum efficiency, the stabilizer usually should be preferentially wetted by the continuous phase (but not
M
969 excessively so). (Gelot, Friesen et al. 1984, Tambe and Sharma 1993, Yan, Elliott et al. 1999, Aveyard, Binks et al.
970 2003) in separate studies establish that the extent to which solids increases emulsion stability depends on several
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971 factors. Among these factors are particle size, shape of particles and morphology, particles density, concentration,
972 surface coverage, and wettability.

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973 (Rousseau 2000) reviewed the effects of fat crystals in food emulsion formation and its stability. The study of
974 colloidal particles in food emulsions, particularly the role of fat crystals, is a more recent phenomenon, being first
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975 examined in 1960s (Lucassen-Reynders and Tempel 1963). In quiet a number of emulsified foods (e.g. ice crystals
976 in ice cream, egg yolk particles in mayonnaise and fat particles in whipping cream) solid particles are necessary for
C
977 making them stable (Darling 1982). The role played by colloidal particles in the stabilization of emulsion is
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978 receiving much attention, yet, the knowledge base is relatively scarce (Rousseau 2000). Some factors that are
40
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979 intimately related by inter-particle interactions and significantly affect fat crystal stabilization of emulsions ate
980 explained below.
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U SC
981
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982 Figure 8 Adsorption and contact angles of fat crystals at the interface of an oil-in-water emulsion (Rousseau 2000).
983
984
985 The significant factors that determine the influence of fat crystals on emulsion stabilization are: (1) the wettability
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986 of the crystals at the interface (Friberg, Larsson et al. 2003); (2) interfacial film rheology and (Lucassen-Reynders
987 1993); (3) polymorphism and morphology of the particle (particle structure) (Ogden and Rosenthal 1998); and (4)
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988 location of fat crystals [(in the dispersed (O/W emulsion) or continuous phase (W/O emulsion)] (Darling 1982). All
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989 of these factors are intimately related via inter-particle interactions (Wesdorp, Human et al. 1992).
990 (Mackay, McLean et al. 1973, Edwards and Wasan 1991) proposed that, the ability of an emulsion to oppose
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991 coalescence will largely be determined by the properties of the interface. A highly viscous and rigid interfacial film
992 will retard the rate of film drainage and resist rupture thereby promotion.
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993 (Wang and Alvarado 2011) in a research demonstrated how particle suspension contributes to emulsion stability. In
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994 the study, Kaolinite and silica particle dispersions were characterized as functions of brine salinity using a
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995 reference water phase, as the reservoir brine, diluted with distilled water to obtain 10 and 100 times lower Total
996 Dissolved Solid (TDS) brine. Scanning Electron Microscope (SEM) and X-ray Diffraction (XRD) were employed
997 in examining the morphology and composition of the clays. The emulsions used in the studies were prepared by
998 mixing a crude oil with brine, with and without dispersed particles to investigate emulsion stability. The stability
999 was measured through the conventional bottle tests and optical microscopy. Results from the experiments show
1000 that both silica and kaolinite promote emulsion stability. Also, around 1 µm in size of kaolinite stabilizes emulsions
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1001 more than does larger clay particles. A total reversal to this was observed with regards silica particles. Silica
1002 particles of bigger sizes (around 5 µm) produced more stable emulsions than smaller silica particles do.
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1003 (Sztukowski and Yarranton 2005) inspected the role of solids in the stability of oil filed emulsions. They found that
1004 emulsion stabilized by fine solids and asphaltenes were most stable at a 2:1 fraction area ratio of asphaltene to
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1005 solids. There is a strong correlation between asphaltene content and emulsion tightness.
1006
1007
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(Binks and Rocher 2009) in a study on the effects of temperature on water-in-oil emulsions stabilized by wax
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1008 microparticles claimed that micro-wax particles alone can stabilize emulsions. According to the authors, since wax
1009 particles are hydrophobic at the oil–water interface; such emulsions are water-in-oil. They found out that the
M
1010 stability of these emulsions at different temperatures to both sedimentation and coalescence depends significantly
1011 on whether particles are adsorbed to dispersed drop interfaces or they are not, prior to the temperature change.
D
1012 However, if the drops are formed at room temperature, increasing the temperature of the emulsion consequently
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1013 leads to increase in the degree of coalescence as particles melt and cannot provide an obstruction to drop blending;
1014 the temperatures over which this occurs are in the same range as that of the melting range of the particles alone.
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1015
1016 (Sharma, Velmurugan et al. 2015) conducted an EOR study, where oil-in-water Pickering emulsion stabilized by
1017 Nanoparticles was used in Combination with Polymer Flood. In this work, oil-in-water Pickering emulsion systems
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1018 stabilized using nanoparticles, surfactant, and polymer were formulated and their efficiency tested for enhanced oil
AC
1019 recovery with and without a conventional polymer flood. For the flooding experiments conducted, Berea core
42
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1020 samples at 13.6 MPa and temperatures of 313 and 353 K were used. The study found out that a combination of 0.5
1021 PV polymer flood with 0.5 PV Pickering emulsion was efficient and have yielded an additional 1–6% oil recovery
1022 as compared to 0.5 PV Pickering emulsion flooding alone.
1023
1024
1025
1026
1027
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1028
1029
1030
1031
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1032
1033
1034
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1035
1036 Figure 9 Schematic representation of (a) surfactant molecule (b) colloidal particle at oil-water interface (Katepalli 2014).
1037
1038
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1039 (Yan, Gray et al. 2001) investigated the stability of w/o emulsions stabilized by fine solids with different
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1040 hydrophobicities. They used model organic solvents like light mineral oil (Bayol-35), decane and toluene. The fine
1041 solids used in the study include hydrophilic and hydrophobic colloidal silica; kaolinite clay particles treated with
M
1042 asphaltenes, hydrophobic polystyrene latex microspheres, as well as fumed silica dry powders treated with
1043 silanization. Experimental results showed that hydrophilic colloidal silica could only produce o/w emulsion that is
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1044 stable for a very short period of time. Using hydrophobic particles (either colloidal silica or polystyrene latex
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1045 microspheres) that were suspended in the aqueous phase prior to emulsification produced only o/w emulsions.
1046 However, when such hydrophobic particles were suspended in organic phase prior to emulsification, stable w/o
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1047 emulsions were formed, with dispersed water droplets as small as 2 mm when the solids were 12 nm in diameter.
1048 They found out that the stability of the produced emulsions studied depended on the hydrophobicity of the
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1049 particles, and only particles with intermediate hydrophobicity produced very stable w/o emulsions.
1050 Although vast literatures on factors that affect emulsion stability exist, there is a shortage of work on inorganic
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1051 and organic solids stabilized water-in-oil emulsion despite their importance (Al-Sahhaf, Fahim et al. 2009). The
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1052 authors believe that this extensive literature review would open more doors to those in the academia and the
1053 industry, especially that want to explore deeper into the issues of petroleum emulsions.
1054 7. Conclusions
1055 The formation of emulsions in the oil and gas industry is as old as the industry itself. These produced emulsions
1056 have posed serious operational and economic problems to the industry, justifying the economic and technical
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1057 reasons for the resolution of these unwanted emulsions. Resolving emulsions require a detailed understanding and
1058 thorough research into not just the consequence of its formation, but the factors that prompt its formation and those
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1059 that enhance its stabilization. Numerous studies have been conducted by researchers from the Industry and
1060 academia, and several factors have been experimented with respect to their roles in producing stable petroleum
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1061 emulsions. Despite the vast literatures available, there is still a significant shortage of studies that deeply examine
1062 the roles of inorganic solids in stabilizing water-in-crude oil emulsions. From this review study, we found out that
U
1063 the concept of study adopted by most of the researchers that studied solids stabilized emulsions involve (1) Using
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1064 processed solids in the study (2) preparing emulsions in the laboratory, rather than using field emulsions, and (3)
1065 inadequate knowledge on the properties of the solids – in the case of the few studies that have used field emulsions.
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1066 To the best knowledge of the authors of this work, there is no study that holistically made use of solids from a field
1067 emulsion and explicitly characterized those solids, while examining their roles in stabilizing emulsions. Hence the
D
1068 authors of this work focus on native solids from field emulsions (both organic and inorganic), holistically
1069 understand their properties and roles in stabilizing petroleum emulsions and predict the type of emulsion that the
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1070 presence of these solids may form. It is believed that understanding the compositions, behaviors and properties of
1071 these solids (that reside at the o/w interface) is fundamental in understanding the nature, severity and type of
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1072 petroleum emulsions, as well as a key in developing cost-effective demulsification strategy. From the details of the
1073 papers reviewed by the authors of this paper, they believe that tackling the issue of undesirable emulsions,
C
1074 especially, requires a closer investigation into the problem. Due to the peculiarity of every oilfield emulsions
AC
1075 (because of the varying factors responsible for its formation), containing the behavior of these complex mixtures is
44
ACCEPTED MANUSCRIPT
1076 no easy task. Perhaps the best way to visualize such complex emulsions is to identify the physical and chemical
1077 properties of not just the organic emulsifiers, but also of the inorganic solids which we believe are very significant
1078 in making the emulsion more difficult to treat. As mentioned, emulsion treatment has always been more of an art
1079 than science, with many such chemicals selected based on trial and error. This we believe should be replaced with
1080 a more scientific approach to the problem, where the demulsifiers are tailored based on the exact properties of the
1081 emulsifying agents. Hence, it is important to understand the nature of the solids that stabilize the emulsions at a
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1082 molecular, microscopic and macroscopic level. Also, to obtain an adequate prediction model that can predict the
1083 nature and severity of petroleum emulsions, the solids that are produced together with the crude oil should be
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1084 included in the prediction model. The authors of this paper have conducted series of laboratory studies as part of
1085 an extensive study that would go a long way in tackling the problem of emulsion treatment in the oil and gas
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1086 industry.
1087 Acknowledgements
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AN
1088 The authors wish to acknowledge Universiti Teknologi PETRONAS, Malaysia for providing us with state-of-the-
1089 art equipment for this study. Also, Deleum Chemicals Sdn Bhd Malaysia, PETRONAS Research Sdn Bhd (PRSB)
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1090 Malaysia, Vision Petroleum Sdn Bhd, Malaysia for providing us with production data and field emulsions.
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1091
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Highlights
 The formation and stabilization of petroleum emulsions remain a serious problem in the
oil and gas industry.
 Increase in solids concentrations lead to an increase in the emulsion stability.
 The irreversible adsorption of solids has a major consequence on the long-term stability
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 Solids sizes play significant roles in improving emulsion stability.
 The stability of these emulsions in the oil industry has been a fundamental issue that
necessitates continuous research.
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 This paper provides details of the petroleum emulsions in the oil and gas industry.
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A review of petroleum emulsions and recent progress on water-in-crude oil emulsions

To appear in: Journal of Petroleum Science and Engineering

Received Date: 15 April 2017

Journal of Petroleum Sciences and Engineering

1 A Review of Petroleum Emulsions and Recent Progress on Water-

32 in order to tailor demulsifiers based on the characteristics of such emulsifiers.

61 and the results found corroborated this result.

62 2. The Emulsion Problem

76 Osisanya 2013) (Ngai and Bon 2014).

82 The water content must be less than 1% (Fink 2015).

83 2.1. Definitions of Emulsions

90 molecules (Leal-Calderon and Schmitt 2008).

107 cloudy oil after centrifuging.

117 particles form or enhance their stabilizations.

118 2.2. Classifications of Emulsions

162 non-convertible to other types once formed.

Oil Flotation Process froth emulsions O/W

176 emulsion prevention (Becker 1997).

186 emulsions are optically transparent (isotropic).

214 potential, and stability of the emulsion.

241 2.4. Some Industry Applications of Emulsions- Desirable Emulsions

253 moderately viscous oils.

276 and Raghavan 1973, Sifferman 1981).

287 3. The Emulsification Process

323 Kawanaka, Leontaritis et al. 1989, Bobra 1991).

324 3.1. The phase-volume theory.

331 1.1. The Hydration Theory of Emulsions

343 3.2. Oriented wedge theory.

347 whose curvature determines the size of the dispersed phase.

348 3.3. The Adsorbed Film and Interfacial Tension Theory

359 4. Mechanism of Emulsification

368 et al. 2003).

376 4.1. Spontaneous Emulsification

398 sufficient enough to mix the phases.

399 5.1. The Emulsifiers

430 stability prediction models.

440 5.1.1. Amphiphiles

452 to be saturated by asphaltenes (Langevin, Poteau et al. 2004).

478 5.1.2. Asphaltenes, Resins and Waxes as Emulsifiers

485 of the water in oil type (Wang, Zhang et al. 2004).

496 asphaltenes from a crude oil becomes apparent.

511 asphaltenes mixed to the original concentrations gave a stable emulsion.

522 modification of its wettability from dual wettability to single wettability.

563 bonding (Kawanaka, Leontaritis et al. 1989).

592 quickly coalesce as in Fig. 4.

626 stable emulsions (Fig. 5b).

639 to be more polar than resins.

665 formed (Bobra 1992, Bobra, Fingas et al. 1992).

703 Alvarado 2011, Fingas 2014, Fingas and Fieldhouse 2014).

710 mechanism (d). These are as depicted in Fig. 6 below.

711 6.1.1. Surfactants

728 which case it stays in one of the phases.

763 particles from the reservoir among others.

765 6.1.1.1. Surfactant Classifications

778 surfactants can be classified as:

796 et al. 2003, Migahed and Al-Sabagh 2009).

805 Sabagh 2009).

813 nonyl phenol ethoxylate (Schramm, Stasiuk et al. 2003).

814 6.1.1.2. Surfactants Roles in Emulsion Stabilization

831 al. 2017).

842 6.2. Roles of Solids in w/o Emulsion Stabilizations (Pickering)

875 emulsifying 25 c.c. of kerosene in 25 c.c. of water.