Fuel 243 (2019) 15–27

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Full Length Article

Experimental investigation of stability of water in oil emulsions at reservoir T

conditions: Effect of ion type, ion concentration, and system pressure
⁎
Yousef Kazemzadeha, Ismail Ismailb, Hosein Rezvanic, Mohammad Sharifia, , Masoud Riazib,d
a
Department of Petroleum Engineering, Amirkabir University of Technology, Tehran Polytechnic, Tehran, Iran
b
Department of Petroleum Engineering, School of Chemical and Petroleum Engineering, Shiraz University, Shiraz, Iran
c
Department of Mining Engineering, Isfahan University of Technology, Isfahan, Iran
d
Enhanced Oil Recovery (EOR) Research Centre, IOR/EOR Research Institute, Shiraz University, Shiraz, Iran

G R A P H I C A L A B S T R A C T

A R T I C LE I N FO A B S T R A C T

Keywords: Different ions present in formation water (FW) and aqueous phases injected into the oil reservoirs can affect the
Emulsion stability formation and stability of water-in-oil (W/O) emulsions. Previous studies regarding this issue devoted attention
Cation to the chemical compounds of the oil and water with a partial focus on different parameters at ambient pressure
Anion and temperature. However, pressure can multilaterally control the formation of emulsification phenomena. One
Asphaltene
important factor of emulsion stability is the asphaltene that is present in the crude oil. These particles are
Interfacial tension
subjected to instability when they encounter a change in chemical composition and pressure, which affects the
formation and stability of the emulsion. In this study, emulsification at various pressures and salinity were
analyzed to determine the role of affecting factors, including asphaltene and various ions in the aqueous phase.
The apparatus used for monitoring the emulsification was a HP-HT Emulsion Analyzer, designed and constructed
by our research group. According to the results, the type and concentration of cations present in the aqueous
phase govern the stability of the emulsion. At low salinities (i.e. up to 10,000 ppm), the emulsion stability
increases and then decreases with increasing salt concentration in the water phase. At high pressures (i.e. from
4000 to 6000 psi), divalent cations form a more stable emulsion in comparison with monovalent ones. In ad-
dition, among divalent cations, Mg2+ introduces a more stable emulsion than that of Ca2+. Based on the results,
the thermodynamic conditions affect the precipitation and deposition of asphaltene. Since dead oil was used in
this research, the emulsion stability decreases with a decreasing asphaltene content at the interface at high
pressures (i.e. 4000–6000 psi). This is due to the considerable reduction in the number of emulsifiers at the
interface. Therefore, at high pressures, pressure increase reduces the emulsion stability. However, at low pres-
sures (i.e. from 14.7 to 4000 psi), the increase in shear energy and asphaltene adsorption at the interface by ions

⁎
Corresponding author.
E-mail address: m_sharifi@aut.ac.ir (M. Sharifi).

https://doi.org/10.1016/j.fuel.2019.01.071
Received 28 July 2018; Received in revised form 7 December 2018; Accepted 9 January 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
Y. Kazemzadeh et al.
overcomes the decrease in asphaltene due to its increased solubility. Therefore, at low pressures, pressure in-
crease raises the emulsion stability.
1. Introduction
Emulsion is a two-phase system in which liquid droplets are dis-
persed in another immiscible liquid [1–5]. It is kinetically stable and
thermodynamically unstable, and this instability separates it into two
phases over time [6,7]. In-situ formation of water-in-oil (W/O) emul-
sions in the heavy oil wells is regarded as a significant challenge during
oil production [6,8]. The emulsions increases the viscosity of crude oil
to a higher, abnormal value, which has been observed several times in
heavy and ultra-heavy oil reservoirs [9–11]. The problem is mainly due
to significant amounts of polar carboxylic and naphthenic groups pre-
sent in the crude oil; these groups are considered to be good W/O
emulsion stabilizers [12]. Due to the low interfacial tension (IFT) of
emulsion versus oil, and its high viscosity relative to those of water and
oil, the injection of emulsion results in improved oil production
[13–15]. Moreover, emulsion injection may increase oil production by
decreasing the fingering and early breakthrough during enhanced oil
recovery (EOR) processes [16–20].
The separation of emulsion phases is influenced by the thermo-
dynamics of the system, since the oil/water interface and the Gibbs free
energy of the system are reduced when the oil and water form two
separated phases [2,21]. As a result, the emulsion characteristics, in-
cluding particle size distribution, average particle size, etc. cannot be
maintained over time [17,22]. Therefore, the emulsion stability refers
to the ability of the dispersed phase to maintain its properties within a
specified time interval. The stability of the emulsion is due to the pre-
sence of particles located on the fluid-fluid interface that postpone the
tendency of the two fluids toward phase separation [23]. These parti-
cles usually consist of molecules with polar and nonpolar chemical
groups in their structures, and are known as surface active agents. It is
important to note that the dispersed phase in an emulsion is usually
present as spherical droplets [24].
The formation and stability of emulsion generally depend on the IFT
of W/O and is facilitated by lower IFT values [25–27]. Therefore, the
stability of the emulsion is essentially associated with the oil/water
interfacial film. Acidic components present in the crude oil reduce the
W/O IFT and aid the emulsification process. On the other hand, the
high surface activity of asphaltene particles available in the crude oil
are capable of moving to the interface and increasing the W/O inter-
facial film and the stability of the emulsions [28,29]. In fact, asphaltic
compounds of the crude oil act as natural surface active agents. They
deploy at the interface and form W/O emulsions, which can be further
stabilized by the salts present in the aqueous phase of the emulsions
[30–32]. The possibility of formation of W/O emulsions increases,
when considering the lack of water resources there is a necessity of
using seawater as the injected fluid into the oil reservoirs. Therefore,
experimental investigation of the stability of these emulsions stabilized
with various ions present in the seawater would pave the way for ac-
cessing useful information about the behavior of natural emulsions
formed in the reservoirs [33,34]. Modifying the ion composition of the
injected water usually leads to the improved oil recovery. In the pre-
sence of some specific ions in the aqueous phase, the behavior of the
molecular aggregates is governed by these ions. Actually, counter ions
penetrate into the diffuse layer as well as to the micelle surface of
charge. Specific ion effects play a key role in bulk solutions when there
is a varied IFT or differed solubility of monovalent and divalent salts, in
terms of order of magnitude. Dispersion forces are of great importance
when it comes to determining the interactions at interfaces and be-
tween particles in colloidal systems. Lukanov and Firoozabadi (2014)
studied the specific ion effects and dissolution of salts in water. Based
16
Fuel 243 (2019) 15–27
on their results, when there is a kosmotrope cation, water dipole keeps
out, while in the case of a kosmotrope anion, there is an attraction
between anion and water dipole [35]. Depending on the type of re-
servoir, the method includes at least one of the following variations
[36–40]:
i. Significant reduction in the salinity of the injected water relative to
the reservoir’s formation water (FW), such as seawater or Low-Sal
water
ii. Increasing the concentration of active multivalent ions (including
but not limited to Ca2+, SO42−)
iii. Reducing the concentration of inactive monovalent ions (including
but not limited to Cl−, Na+).
Xubeing Fu (2010) pointed out that emulsions behave as a
Newtonian fluid if the fraction of water is < 40 wt%. However, beyond
that range, the emulsion displays a shear decreasing behavior [41].
Umar et al. (2016) examined the stability and behavior of W/O
emulsions at various water fractions. They concluded that the stability
of emulsion reduces at high water volume fractions (50 vol%), whereas
Newtonian behavior was observed for those at low water volume
fractions [42].
Kumar et al. (2012) declared that an increase in salinity in the
presence of the anionic surfactant in the solution reduces the IFT va-
lues. They found the oil/water IFT as a function of salt concentration
and the type and amount of surface active agents present in the solution
[18]. Jan Czarnecki and Kevin Moran (2005) presented a new me-
chanism regarding the formation of W/O emulsions, based on at least
two types of chemicals. The first is the asphaltene adsorption with a
slow and irreversible process that leads to the formation of a stable film.
The second is the rapid adsorption of low molecular weight materials
such as surfactants. Moreover, their results showed that there are two
different mechanisms regarding emulsion stability at high concentra-
tions and below infinite dilution point, which shows the competition of
asphaltene adsorption at the oil/water interface [43]. Lashkarbolooki
et al. (2016) showed that increasing the concentration of asphaltene
molecules reduces the oil/water IFT. They used a water/crude oil/as-
phaltene system for surface analysis in the presence of asphaltene
molecules. As another part of the study, the presence of asphaltene at
the oil/water interface was investigated. Based on their results, the
presence of asphaltene at the fluid-fluid interface disturbs the balance
of the forces and, as a result, reduces the IFT of the two phases [44].
This IFT reduction sometimes improves the stability of the emulsion. In
line with our research, Cuiying Jian et al. (2016) showed that by in-
creasing the concentration of asphaltene, the hydrogen bond developed
between asphaltene and water molecules reduces the IFT of oil/water
[45].
As previously described, thermodynamic properties such as pres-
sure, asphaltic sediments, and ions present in the water affect the for-
mation and stability of W/O emulsions. Injection of W/O emulsions into
the oil reservoirs can increase the oil production, which is mainly due to
the low emulsion/oil IFT and high emulsion viscosity, as compared to
that of water and oil. That is why the behavior of W/O emulsions in the
presence of various ions was monitored in this research. In previous
studies, the effect of asphaltene and ionic compounds present in the
water phase on the formation and stability of emulsions has been in-
vestigated, although the thermodynamic conditions governing on the
oil reservoirs were disregarded. In contrast, this research studied the
effect of pressure on the stability of asphaltene and the formation and
stability of W/O emulsions. In addition, the role of monovalent and
Y. Kazemzadeh et al. Fuel 243 (2019) 15–27

divalent cations/anions and the concentration of different ions in the Table 2

formation and stability of emulsions have been addressed by a new HP- SARA analysis performed on the dead crude
HT Emulsion Analyzer, designed and constructed by our research oil used in this research
group. Type wt%

2. Materials, devices, and methods Saturates 41

Aromatic 49
Resin 2
2.1. Materials Asphaltene 8

2.1.1. Crude oil

The dead crude oil used in this research was obtained from one of
the Iranian southern oil reservoirs, with a gravity of 21°API. The
compositional and SARA analyses performed on the crude oil are pre-
sented in Tables 1 and 2, respectively. Regarding SARA analysis, the
Colloidal Instability Index (CII) of the crude oil was calculated as 0.94,
indicating that the asphaltene particles in the crude oil are unstable and
on the edge of deposition [46].
The Fourier-Transform Infrared Spectroscopy (FT-IR) of the crude
oil is shown in Fig. 1. As indicated, the peak at 2993 cm−1 is assigned to
ReCOeOH functional group. The peaks at 1365 cm−1 and 970 cm−1
are attributed to S]O and NeO stretches, respectively. The presence of
ReCOeOH, NH2, RSOOR, NeO, and PeO functional groups are evident
from the peak at 1226 cm−1. In addition, the peak at 1026 cm−1 is
indicative of RSOOR and ReCOeOH functional groups. Based on these
results, the crude oil contained both acid and base components. How-
ever, the number of acidic species seems to be greater than that of the
basic species, which is why one can observe more COOH groups than
NH2 in the analysis. It should also be noted that when the oil phase is in
contact with water phase, the altered polarity of the oil components
such as asphaltene could introduce different behaviors in the system,
depending on the components present in the aqueous phase and their
interactions.
2.1.2. Ions
In this research, different salts were utilized to synthesize various
brines that were used as the water phase in water-in-oil emulsions. The
properties of these salts are indicated in Table 3.
2.2. Devices and methods
2.2.1. High pressure-high temperature emulsion formation and stability
analyzer
The HP-HT Emulsion Analyzer apparatus was designed and con-
structed by our research group and consisted of several parts as follows:
• The main cell
• Water inlet valve
• Oil inlet valve
• High-pressure PT-100 thermometer
• High-pressure heater
• High-pressure fluid isolating valves for minimizing the dead volume
in the system
• Pressure gauge
• Magnetic coupling
• Easy to screw and unscrew connections for cleaning
• Electrical panel
• The visual investigating tool of the device, which included:
o The primary interchangeable chamber, as a supporter of high-
pressure optical glasses
o The secondary interchangeable chamber, as a supporter of rock thin
section
o HD digital microscope
o High-pressure inlet and outlet valves.
As indicated in Fig. 2, two different cylinders with separate lines
were used for oil and water injection. After injecting first water, then oil
into the main chamber, the fluids were completely mixed via strong
magnetic coupling with a maximum rotational speed of 4000 RPM. To
prevent a direct influence of the magnetic forces on the oil and de-
position of solid (asphaltene) particles in the crude oil, the magnetic
coupling was designed outside of the chamber. As the engine starts, the
propeller in the fluid chamber begins to rotate as the power is trans-
ferred to its upper rod. During mixing the two phases, the inlet valve
between the main chamber and visual chamber is kept closed to prevent
pressure drop and dead volume in the system. Prior to increasing the
pressure and temperature of the chamber to the desired values, the two
fluids in the main chamber must be completely mixed. Afterwards, one
can open the intermediate valve for the sample to flow from the main
chamber to the visual chamber. To sufficiently illuminate the visual
chamber, a type of SMD LEDs with a power of 36 W was embedded
inside it. In addition, the chamber was elaborately designed to bring a
thin fluid layer into the visual chamber for light to pass through dark
fluids. The visual chamber was also equipped with an HP drain valve
for draining the fluid from the chamber. A pressure safety valve (PSV)
was contrived Installed to avoid extremely high pressures in case of a
rapid rise in temperature. This would ensure the user’s safety during
working with the device. The microscopic imaging technique was used
to monitor the distribution of water droplets dispersed in the emulsion,
and the Image J software was used for the analysis of the pictures. The
repeatability error with mean droplet area calculation was ± 2 µm2.
During image analysis, the outlier data were removed for more accurate
evaluation. Also, in case of observing a different distribution of droplets
at various points, the analysis was repeated for different pictures taken
from various points of the sample. The size of dispersed droplets in the
emulsion increases with an increasing volume of water. As a result, the
thickness of surface film decreases due to the presence of polar com-
ponents of the crude oil. In this situation, the repulsive forces between
droplets decreases and the thin surface film begin to rupture, which is
why the droplets rapidly coalesce and form larger ones. However, low
volume fractions of water do not considerably affect the emulsion be-
havior due to the decreased dispersed water. In this research, the vo-
lume percentage of water was fixed at 30 vol% in all prepared emul-
sions.
2.2.2. Interfacial tensiometer
The setup of IFT measuring is illustrated in Fig. 3. As indicated, the
apparatus is composed of an injection pump, an HD camera, and a
quartz cell. First, the syringe is filled with crude oil and placed on the

Table 1
Compositional analysis of the dead crude oil used in this research.
Components C2 C3 iC4 nC4 iC5 nC5 C6 C7 C8 C9 C10 C11 C12+

Mole % 0.49 0.73 0.47 0.94 0.55 0.55 7.64 6.18 5.44 4.90 4.71 4.14 63.26

17
Y. Kazemzadeh et al.
Fig. 1. FT-IR analysis of the crude oil.
injection pump. The quartz cell is filled with the different solutions,
which are meant to be a surrounding fluid in the quartz cell. The oil
droplet is slowly injected upward through the needle with an injection
volume of 3 µl. The equilibrium IFT was imaged and analyzed by the
software. The repeatability error with IFT measurement was ± 0.3
mN.m.
2.2.3. Phase separation of emulsions
After imaging analysis in the visual chamber, a 40 mL sample was
taken from the main chamber and was used for measuring the IFT be-
tween water and emulsion and also investigating the phase separation
of emulsions based on the centrifugal force needed for complete se-
paration of the two phases. Phase separation is dependent on various
factors, including separation time, RPM, etc. Make it easy for com-
paring all cases, the separation process began at 2000 RPM and in-
creased gradually by adding to 500 RPM until reaching the ultimate
value. In addition, in each experiment, the centrifugation took 5 min
and the water content was measured 3 min after separation.
3. Discussing the results
3.1. The effect of pressure
The thermodynamic conditions of the system govern the mor-
phology of water in oil emulsion. The average droplet diameter of the
dispersed phase (i.e. water) in the continuous phase (i.e. oil) is influ-
enced by the system pressure. The stability of emulsions in this case is
expressed by the frequency of smaller areas. To study the effect of
pressure on the morphology of water droplets, the formation and sta-
bility of the emulsions were compared at different pressures. For this
purpose, crude oil and 10,000 ppm MgCl2 brine were injected sequen-
tially into the main chamber to prepare an oil/water emulsion at a
specific pressure. The emulsification itself was performed by the ro-
tating propeller of the device. The average area of water droplets in the
oil phase in the visual chamber was ultimately calculated using Image J
Table 3
Properties of salts used in this study
Type of Salt Chemical Formula
Magnesium Chloride, Hexahydrate MgCl2·6H2O
Calcium Chloride CaCl2
Magnesium Sulfate, Heptahydrate MgSO4·7H2O
Sodium Sulfate Na2SO4
18
Fuel 243 (2019) 15–27
software. Fig. 4 shows the average area of water droplets formed in the
oil phase at various pressures related to the aqueous phase, containing
10,000 ppm MgCl2 salt.
As shown in Fig. 4, with an increase in pressure up to 4000 psi, the
average area of water droplets in the oil phase decreases, while beyond
4000 psi, the average area increases. The reduction in the area of water
droplets with increasing pressure may be because of two reasons:
i. An increase in shear energy applied by the homogenizer at high
pressure
ii. An increase in asphaltene adsorption onto the ion surfaces due to the
increased pressure.
In this research, emulsification process was performed via a pro-
peller at certain RPMs. The propeller transfers the rotational movement
as a shear energy to both dispersed and continuous phases. In fact,
rotational movement applies bidirectional forces (vertical and hor-
izontal) to the surface of static droplets. The vertical force is shear
energy and is defined as the transferred energy to the droplet to become
smaller and smaller. As the pressure goes up, the shear energy increases
and in turn the energy transferred from propeller to the droplets in-
creases, too [47,48].
Asphaltene particles act as emulsifiers in this system. Regarding the
dead oil used in this research, an increase in pressure improves the
solubility of asphaltene in the oil phase, which in turn reduces the
number of emulsifiers at the interface. This would subsequently reduce
the droplet stability due to the coarsening of the dispersed phase. As a
result, the number of water droplets in the oil phase decreases. That is
why there are two different behaviors in the system as the pressure
increases. Increasing pressure below optimal pressure introduces
smaller water droplets in the oil phase, owing to the predominance of
the increased adsorption and shear energy applied to the system,
compared to the decrease in asphaltene content. Beyond optimal
pressure, the amount of emulsifier (asphaltene) at the oil/water inter-
face significantly reduces with an increased pressure. Therefore, the
Purity (%) Molecular Weight (gr.mol−1)
> 99 203.30
> 99 110.98
> 99 246.48
> 99 142.04
Y. Kazemzadeh et al.
Fig. 2. The schematic view of the HP-HT Emulsion Analyzer apparatus, designed and constructed by our research group.
stability of the emulsion and the average area of the water droplets
decreases and increases, respectively, with the coarsening of water
droplets (Fig. 5).
In case of low concentrations of salts in the aqueous phase, as-
phaltene molecules can play the role of polydentate ligands and create
chelate with present cations. This would intensify asphaltene aggrega-
tion, which itself instabilizes asphaltene. By definition, ligands are
molecules with an electron pair and may be negative or neutral. They
are known as electron pair donors connected to central metal ions
(electron pair acceptors) in complexes. Ligands usually bind with metal
ions and resultantly develop chelate. In other words, at low salt con-
centrations, the movement of asphaltene molecules towards oil/water
interface is governed by available ions in the aqueous phase. Cations
can create chelate when taking contact with asphaltene molecules and
act as a bridge. This would connect several asphaltene molecules to-
gether and increase asphaltene clustering. In previous studies, it was
found that there is an inverse relationship for calcium and magnesium
Fig. 3. Schematic view of pendant drop method for measuring IFT.
19
Fuel 243 (2019) 15–27
ions in the presence of asphaltene. This effect comes directly from the
size of calcium and magnesium. With regard to big asphaltene mole-
cules, the development of calcium cations with asphaltene molecules
for creating a complex is much easier. Therefore, complexes resulting
from the interaction of asphaltene and divalent cations lead to their
adsorption at the oil/water interface.
To ensure the effect of pressure on the emulsions formed with
10,000 ppm MgCl2 brine, the IFT between emulsions formed at dif-
ferent pressures and DW has been measured at 25 °C (Fig. 6).
According to Fig. 6, pressure presents a bilateral effect on the IFT of
emulsion/DW. By increasing the pressure of the emulsion preparation,
the shear energy applied to the water and oil phases breaks down the
water droplets and brings an analogous governing condition on droplets
with a lower average area, as already investigated in food engineering
[49]. This reduction in the average area of droplets increases the
emulsion stability and subsequently reduces the IFT of emulsion/DW.
On the other hand, increasing pressure intensifies the asphaltene
Y. Kazemzadeh et al. Fuel 243 (2019) 15–27

Fig. 4. The average area of water droplets in the oil phase at various pressures related to the aqueous phase, containing 10,000 ppm MgCl2 salt.

Fig. 5. Schematic view of dominant mechanisms at pressures below and above optimal pressure.

adsorption by the electrically charged ions at the oil/water interface. In
this situation, the increased number of asphaltene particles at the in-
terface results in a more stable emulsion and a lower IFT value. This
situation prevails for pressures up to 4000 psi. The IFT between emul-
sion formed at 4000 psi and DW was measured as 5.43 mN/m. Beyond
4000 psi, the amount of emulsifier decreases due to the increased
pressure. Increasing pressure also amplifies the solubility of asphaltene
in the dead oil. Therefore, the decrease in the number of asphaltene
particles at the interface reduces the stability of the emulsion, which
results in water droplets with a higher mean surface area dispersed in
the oil phase. This increase in the average area of droplets ultimately
increases the IFT of the emulsion/DW. Therefore, one can observe that
the IFT of emulsion/DW increases to 6.31 mN/m for the emulsion
formed at the pressure of 6000 psi.
To re-examine the effect of pressure on the formation and stability
of the emulsion, different samples were taken from emulsions prepared
at different pressures. The samples were evaluated by the RPM needed
for the centrifugal force to separate the phases of emulsions. Fig. 7
shows the required RPM for phase separation of different emulsions
prepared at various pressures.

20
Y. Kazemzadeh et al.
Fig. 6. Ambient IFT values of emulsion/DW with the pressure of emulsion preparation (aqueous phase of the emulsion is 10,000 ppm MgCl2 brine).
As shown in Fig. 7, increasing the pressure of emulsion preparation
up to 4000 psi increases the required RPM for phase separation of
emulsions up to 11,000 RPM. In fact, an intensification of the required
energy for phase separation is the indication of the formation of stable
emulsions with smaller droplets. At 6000 psi, the required RPM for
phase separation once again decreases. As previously discussed, this
decrease in separation RPM at higher pressures than at the optimal
pressure is due to the reduced stability.
3.2. The effect of ion concentration
In this research, different concentrations of organic salts have been
studied to monitor their behaviors, including their solubility in water
and their ability to release ions. With increasing salt concentration,
more anions and cations are released into the solution. Each salt has the
highest number of free ions at a particular concentration, which is
known as the optimum concentration. Beyond this concentration, the
salt crystals are dissolved into water as a molecular form [44]. During
the formation of emulsions, ions released into the water phase during
dissolution interact with polar components of oil, including asphaltene.
However, molecular dissolution of salts in the water phase reduces the
Fig. 7. RPM required for phase separation of emulsions formed at various pressures at 25 °C (aqueous phase of the emulsion is 10,000 ppm MgCl2 brine).
21
Fuel 243 (2019) 15–27
number of free ions in the solution, and as a result, the ions’ ability to
adsorb asphaltene as well as the frequency of water droplets in the oil
phase decreases. The stability of emulsions is expressed by considering
the frequency of water droplets with smaller areas. According to the
results obtained from the distribution of water droplets related to each
salt, one can observe an optimum concentration for which the fre-
quency of droplets for each salt is at a maximum. In other words, the
stability of the emulsion increases with salinity below a specific con-
centration; beyond this concentration, the stability decreases. Fig. 8
shows the average area of water droplets in the oil phase in the pre-
sence of MgCl2 salt in its aqueous phase at different concentrations. The
thermodynamic conditions of emulsion preparation are 25 °C and
4000 psi.
As shown in Fig. 8, an increase in the MgCl2 concentration below
the optimum concentration partially reduces the average area of water
droplets. Increasing stability at low concentrations indicates the dom-
inance of a salting-in effect by which the solubility of a substance
containing hydrophilic and hydrophobic compounds is improved with
an increase in ionic strength of the solution. This effect is usually ob-
served in aqueous solutions with a low ionic strength. The solubility of
the compounds here is a function of the properties of the substance, pH,
Y. Kazemzadeh et al.
Fig. 8. The average area of water droplets in the oil phase for the aqueous phase containing MgCl2 salt. The pressure and temperature of the emulsion preparation
were 4000 psi and 25 °C, respectively.
temperature, salt concentration, and salt type present in the solution.
The salting-in effect can be described by the Debye-Huckel theory [36].
Based on this theory, the charged compounds are surrounded by the
oppositely charged ions. In fact, this phenomenon reduces the electro-
static free energy of these materials and increases the activity of the
solvent medium to dissolve these compounds. Increasing the con-
centration of ions in the aqueous phase leads to the formation of more
water droplets in the oil phase as stability also increases. With an in-
crease in the free ions in the system, the ability of polar components of
the crude oil (asphaltene) for the formation of a more stable emulsion is
improved by deployment of the polar components at the oil/water in-
terface [37]. Regarding the decreased deployment of the asphaltene
particles at the interface with the increase in pressure, the number of
asphaltene particles at the interface at high pressures is of great im-
portance. Thus, the stability of the emulsion increases with an increase
in the salt concentration to 10,000 ppm.
It should be kept in mind that if the ion concentration in the solvent
is high, the solvation of the ions decreases and as a result, the salting-
out effect occurs. With this, the solubility of the compound reduces,
leading to considerable deposition. The salting-out effect is based on the
reaction between the molecules of electrolytes and nonelectrolytes. In
Fig. 9. The average area of water droplets in the oil phase at different concentrations of salts in the water phase of emulsions prepared at 4000 psi and 25 °C.
22
Fuel 243 (2019) 15–27
other words, with increasing ion concentration at high salt concentra-
tions, the polar components of nonelectrolytes are less soluble in the
electrolytes.
If these materials are in contact with water, the hydrophobic com-
pounds form a hydrophobic region in the water, while the hydrophilic
compounds react with water molecules. These reactions are mainly
responsible for the development of the hydrogen-bonded compounds
surrounded by water molecules. If the substance holds enough hydro-
philic compounds on its surface, it will dissolve in water. Increasing salt
concentration in the water phase results in the adsorption of some
molecules onto the ions [50]. This would reduce the number of mole-
cules available for charged hydrophilic compounds. Consequently, the
strength and reactivity of the molecules of the substance would be
higher than that between the hydrophilic parts of the substance and
water. As a result, the molecules of the substance accumulate as the
hydrophobic reactions occur in the system. Therefore, increasing the
salt concentration beyond a specific concentration (i.e. 10,000 ppm)
decreases asphaltene deployment at the oil/water interface due to the
salting-out effect and subsequent reduction in available charged ions,
which ultimately weakens the stability of the emulsions. In oil re-
servoirs, the salting-out effect increases the tendency of organic
Y. Kazemzadeh et al.
compounds toward the oil phase or the solid surface with increasing
salinity. By contrast, the solubility of organic polar components of the
crude oil in the water phase improves with an increase in salinity due to
the salting-in effect. With this effect, organic polar components in the
water form hydrophilic structures under the influence of hydrogen
bonding when contacting water [51,52]. Inorganic ions such as Ca2+,
Mg2+, and Na+ tend to break up such organic structures formed around
water molecules to reduce their solubility in the water phase. These
ions are consequently known as structure breakers. The ability of such
ions to break down the structures depends on their hydration energy. As
a result, divalent ions have a much greater effect on the solubility of
organic compounds in the water. As noted earlier, the increased ten-
dency of organic components towards the oil phase or the solid surface
owing to the salting-out effect would reduce the asphaltene deployment
at the oil/water interface and hence decrease the emulsion stability.
3.3. Effect of ion type on the formation and stability of the emulsions
To investigate the effect of the type and concentration of salts
present in the water phase on the formation and stability of the emul-
sions, four salts including MgCl2, CaCl2, MgSO4, and Na2SO4 were
added to the water phase to monitor the emulsion behaviors.
As highlighted in Fig. 9, at low concentrations, all prepared emul-
sions are stable with increasing concentrations from 1000 to
10,000 ppm. While from 10,000 up to 50,000 ppm, the stability de-
creases with increasing salt concentration. As noted, the stability im-
provement at low salt concentrations comes from the salting-in effect
and the decrease in stability at high salt concentrations is due to the
salting-out effect. Comparing all salts at different concentrations in-
dicates that the maximum and minimum emulsion stabilities are related
to emulsions containing MgCl2 and Na2SO4 brine, respectively. The
average droplet area in the emulsion containing MgCl2 brine varies
from 48.2 to 63.4 µm2, while for the emulsion containing Na2SO4 brine,
the average droplet area varies from 66.62 to 83.12 µm2.
The solubility of salts consists of three steps: (1) separation of solute
molecules, (2) separation of water molecules, and (3) spreading and
diffusion of solute molecules into the water phase (hydration of solute
molecules). The ions of the dissolved substance are adsorbed by polar
water molecules, i.e., negative ions are attracted by positive poles and
positive ions have a tendency toward negative poles [53]. This ion-
dipole attraction causes the ions to separate from the crystals and
spread into the water. The salt dissolution occurs when the hydration
energy provides the required energy for breaking the crystal network.
Fig. 10. IFT values of DW/emulsion measured for different concentrations of salts in the water phase of an emulsion.
23
Fuel 243 (2019) 15–27
The ionic bond is a type of chemical bond that forms between oppo-
sitely charged ions. It is proportional to the charge and has an inverse
relationship with radius. Surface charge density represents the ratio of
ion charge to ion surface. By increasing the surface charge of an ion, the
enthalpy of hydration also increases, which leads to the hydration of
ions. If the ions have the same charges, then the smaller the ion radius,
the better the ion hydration. As a result, hydration reaches its maximum
number of ions with high charge densities that breaks down the hy-
drogen bond and releases free anions and cations. Asphaltene is a polar
molecule with a negative charge, which may interact with released
cations resulting from the dissolution of salt crystals in water. On the
other hand, if asphaltene contains polar functional groups such as OH−
and S, it reacts with a cation with greater charge density. The inter-
action of asphaltene with ions in the water phase causes a more stable
emulsion, which results in droplets with a lower average area. Among
the ions investigated in this research, the divalent cations (Mg2+ and
Ca2+) introduced droplets with a lower average area at different con-
centrations, which is mainly due to the cation-asphaltene interactions
[36]. For the same reason, comparing optimum concentrations of MgCl2
and CaCl2 shows that the cation valence does not affect the charge
density. According to the Mendeleev’s periodic table of chemical ele-
ments, the atomic radius of Mg2+ is less than that of Ca2+, which
means that its charge density is greater. As a result, Mg2+ has a greater
tendency towards the adsorption of polar asphaltene molecules.
Therefore, the efficiency of MgCl2 in IFT reduction and emulsion sta-
bility is relatively higher.
The effect of mono- and di-valent anions on the formation and
stability of emulsions was studied through the addition of MgSO4 and
MgCl2 salts to the aqueous phase. Divalent sulfates anions are bigger in
size in comparison with chlorides; this transports lower asphaltene into
the aqueous phase. On the other hand, the presence of heteroatoms like
O2−, S2−, and N2− (with the same charge value with sulfate) in the
structure of asphaltene molecule restricts the presence of asphaltene in
the aqueous phase, which reduces asphaltene reactions with cations.
This indeed reduces the deployment of asphaltene at the oil/water in-
terface and in turn the emulsion stability. With the same argumenta-
tion, Lashkarbolooki et al. (2014) concluded that the development of
asphaltene complex by magnesium ions in the presence of sulfate an-
ions is more restricted, as compared to chlorides. They explained this
phenomenon by anion charge and size, declaring that if the anion
charge increases, the emulsion stability decreases as the stabilizer (as-
phaltene) at the oil/water interface decreases.
The emulsion/DW IFT values measured for prepared emulsions
Y. Kazemzadeh et al.
containing different brines are presented in Fig. 10.
As shown in Fig. 10, the IFT decreases with increasing salt con-
centration in the water phase of the emulsion at low concentrations.
However, beyond 10,000 ppm, there is an ascending trend observed for
IFT values with concentration. The IFT of emulsion/DW related to the
MgCl2 brine in the water phase of the emulsion varies between 4.08 and
12.76 mN/m, while it changes from 8.1 to 18.68 mN/m for the emul-
sion water phase containing Na2SO4 brine.
Brines used as the aqueous phase of emulsions were different in pH.
The pH of the MgSO4 solution was 5.6, which indicates an acidic con-
dition. Actually, MgSO4 can be dissolved in water as follows:
MgSO4 → Mg 2 +− + SO42 −
As the hydrogen bonds between water molecules break down, the
solution will contain H+ and OH−. Mg2+ is a weak base and SO42- is a
strong acid. Since the conjugate ion of a weak acid is a strong base and
the conjugate ion of a strong acid is a weak base, Mg2+ (weak base)
reacts with OH− and produces Mg(OH)2. Therefore, the concentration
of H+ in the environment goes up, which results in an acidic condition.
As noted earlier, the crude oil used in this research contained more
acidic than basic species, with more CO2H than NH2 groups. With the
contact of oil with water, the polarity alteration of crude oil compo-
nents results in different behaviors based on components in the aqueous
phase and the subsequent reactions. In case of MgSO4 salt in the aqu-
eous phase, oil takes a contact with the MgSO4 solution with acidic pH
and high H+. This increases the asphaltene polarity with a gentle slope
through the reactions of oil components with NH2. As asphaltene moves
towards the oil/water interface, it acts as a bridge between two phases
and reduces the oil/water IFT; therefore, water droplets are dispersed in
the oil phase. In this condition, an oil film is created around water
droplets and emanates them from coalescence by applying repulsion
between droplets, ending up with stabilization of emulsions.
When a basic brine is in contact with oil, it reacts with acidic oil
Fig. 11. Schematic view of asphaltene adsorption by Mg2+ cation at low and high pressures and its role in the stability of the emulsions.
24
Fuel 243 (2019) 15–27
components and the IFT decreases considerably because of OH– de-
velopment of the system, which finally disperses water phase in the oil
phase. Owing to the strong polarity of asphaltene, it is dissolved in the
aqueous phase and its ability to move toward oil/water interface de-
creases. Strong ionization of oil polar components in a basic solution
intensifies the reaction of asphaltene with the aqueous phase. That is
why the performance of asphaltene as a bridge between oil and water
decreases and the film formed around the droplets is not stable.
The amount of asphaltene adsorption at the oil/water interface is
greater at higher pressures compared to other pressures, since the
pressure increase amplifies the adsorption. The performance of divalent
cations of Mg2+ in the asphaltene adsorption, IFT reduction, and sta-
bility improvement at low and high pressures is schematically illu-
strated in Fig. 11.
Fig. 11 shows that the increase in the number of asphaltene particles
at the oil/water interface results in smaller water droplets. As the
pressure increases, the molar volume of asphaltene (Vas) decreases and
the amount of adsorbate for interaction with cation Mg2+ increases. An
increase in the asphaltene adsorption at the oil/water interface pro-
motes the stability of the emulsions.
Fig. 12 compares the required RPM for separating the two phases of
the emulsions prepared at 4000 psi and 25 °C. The figure depicts RPMs
for different concentrations of salts in the water phase of the emulsions.
As shown in Fig. 12, two distinctive behaviors at two concentration
intervals are observed for all salts as added to the water phase of the
emulsion. At low concentrations, an increase in free cations promotes
the stability of the emulsion and the required RPM for phase separation.
However, at high concentrations, the required RPM has been reduced
due to the decreased stability of W/O emulsions.
The intermolecular forces involved in the interaction between par-
ticles include attractive (i.e. van der Waals) and repulsive (i.e. elec-
trical) forces. These forces are of greater importance than hydration
forces. When an emulsion is formed at the oil/water interface, an
Y. Kazemzadeh et al.
Fig. 12. Required RPMs for phase separation of emulsions prepared at 25 °C and 4000 psi in the presence of different salt concentrations in the emulsion water phase.
electrical layer is developed due to the presence of free cations and
anions [44]. Salt crystals establish electrical charges when dissolved in
water, which increases the ionic strength of the water phase. These ions
adsorb onto the emulsion droplets and develop electrical charges during
the formation of water in oil emulsions, developing a second electrically
charged layer with electrostatic repulsion. The tension of the second
layer depends on two factors: (1) electrolyte concentration and (2)
electrolyte capacity [50]. Low capacity and concentration extend the
second layer. In other words, increasing electrolyte concentration re-
duces the expansion and repulsion of the second electrically charged
layer. The emulsion stability depends on the repulsive forces that exist
between droplets [16]. The greater the charge density of an ion, the
lower the length of the electrical layer. Comparison of different ions
reveals that divalent cations present a higher charge density than
monovalent ones. This would develop a surface film around water
droplets containing electrically charged asphaltene particles. In this
situation, the existing ions tend to adsorb asphaltene at the oil/water
interface. Moving asphaltene to the fluid/fluid interface reduces the IFT
and promotes the emulsion stability. Inorganic ions can break the
structure of water network formed around the organic molecules and
thereby reduce the solubility of organic molecules in the water phase.
Fig. 13. Schematic view of the emulsion formation and stability by Mg2+ and Ca2+ cations.
25
Fuel 243 (2019) 15–27
Therefore, organic ions are known as structure breakers. Low salinity
accelerates the movement of surface active agents of the crude oil from
the oil bulk to the oil/water interface. Regarding the salting-in effect,
monovalent ions introduce a further improved stability at lower sali-
nities than divalent ions. The distance between the droplets is higher
because of the repulsive electrical force, which prevents them from
coagulating. This is why emulsions prepared by monovalent ions shown
in Fig. 12 require lower RPM for phase separation.
Comparing Figs. 9 and 10 shows that the stability of the emulsions
in the presence of MgCl2 and CaCl2 salts in the water phase is higher
than that of other salts. Since both salts are composed of the chloride
anion with divalent cations, their performance in the formation and
stability of the emulsions at the optimum conditions (i.e. 25 °C and
4000 psi) is different.
Breaking the hydrogen bonds existing between water molecules
creates H+ and OH− ions in the water phase. Mg2+ and Ca2+ are the
cations of a weak base and Cl− is the anion of a strong acid. Since the
conjugate ion of a weak acid is a strong base and the conjugate ion of a
strong acid is a weak base, Mg2+ and Ca2+ react with OH− and pro-
duce Mg(OH)2 and Ca(OH)2. As a result, H+ concentration increases in
the water phase, which makes it acidic.
Y. Kazemzadeh et al.
The crude oil used in this research contains acidic and basic com-
ponents with more acidic species than basic species. Therefore, one can
observe more COOH groups than NH2 groups. When the oil phase
makes contact with the water phase, the altered polarity of oil com-
ponents such as asphaltene leads to the different behaviors depending
on the components present in the aqueous phase and the consequent
reactions. With the contact of the oil phase with MgCl2 and CaCl2
brines, an acidic pH is developed in the system with the releasing of H+
which results in the gently increased polarity of the asphaltene due to
the interaction with NH2 compounds. As asphaltene particles move
toward the oil/water interface, they form a bridge between the two
phases which reduces the oil/water IFT and leads to the dispersion of
water droplets in the oil phase. As a result, a surface film around water
droplets is formed that creates repulsive forces between droplets and
prevents them from approaching each other. This ultimately results in
the stable emulsions.
The hydration efficiency is improved with the increase in the so-
lubility of the salt crystals and their ability to release anions and ca-
tions. This would promote the interactions of the ions with the polar
asphaltene molecules in the crude oil.
Fig. 13 shows the effect of Mg2+ and Ca2+ cations on the asphaltene
adsorption at the oil/water interface and the formation and stability of
emulsions. Concerning the lower atomic radius of Mg2+ cations in
comparison with Ca2+, their charge density and tendency toward as-
phaltene adsorption is higher. Therefore, magnesium chloride is more
efficient in the IFT reduction, and therefore improves the emulsion
stability. As illustrated in Fig. 13, the asphaltene adsorption onto the
divalent cations is higher due to the increased molar volume of as-
phaltene with increasing pressure. As a result, the emulsion stabiliza-
tion is higher at high pressures (i.e. 4000 psi).
4. Conclusion
According to the obtained results from the analyses carried out on
the average droplet area, emulsion/DW IFT, and the required RPM for
phase separation of the emulsions, the following conclusions can be
drawn:
• The asphaltene adsorption at the oil/water interface increases with
an increase in pressure up to 4000 psi in the emulsion water phase
containing 10,000 ppm MgCl2. This improved adsorption emanates
from the reduced molar volume of asphaltene due to the increased
pressure and improved asphaltene solubility. Therefore, increasing
pressure up to 4000 psi decreases the average area of water droplets
in the oil phase and improves the stability of the emulsions.
• Among different salts investigated in this research, those with di-
valent cations were more efficient in increasing the stability of water
in oil emulsions due to their higher charge density. Among divalent
cations, Mg2+ cation presented a higher charge density than Ca2+
cation due to its lower ion radius, with a better performance in as-
phaltene adsorption and emulsion stability.
• Increasing salt concentration in the water phase of the emulsions at
low concentrations from 1000 to 10,000 ppm promotes the stability
of the emulsions due to the salting-in effect. At higher salt con-
centrations, however, the stability of the emulsions decreases with
the increase in the average diameter of the droplets due to the
salting-out effect.
• According to the results, the efficiency of salts in the formation and
stability of the emulsions at the high pressure of 4000 psi (i.e. op-
timum pressure) followed this ascending order:
MgCl 2 > CaCl2 > MgSO4 > Na2SO4
The IFT of different emulsions/DW indicated that emulsions with a
lower average droplet area present lower IFT values and more stable
emulsions.
The required RPM for phase separation of emulsions is higher for
26
Fuel 243 (2019) 15–27
those emulsions with high stability.
Acknowledgement
Authors also sincerely thank Miss. Zahra Etemadan and Miss.
Sepideh Palizdan for their collaboration in this work.
References
[1] Mu L, Li S, Ma Q-L, Zhang K, Sun C-Y, Chen G-J, et al. Experimental and modeling
investigation of kinetics of methane gas hydrate formation in water-in-oil emulsion.
Fluid Phase Equilib 2014;362:28–34.
[2] Wong S, Lim J, Dol S. Crude oil emulsion: a review on formation, classification and
stability of water-in-oil emulsions. J Petrol Sci Eng 2015;135:498–504.
[3] Mashhadi S, Javadian H, Tyagi I, Agarwal S, Gupta VK. The effect of Na2SO4
concentration in aqueous phase on the phase inversion temperature of lemon oil in
water nano-emulsions. J Mol Liq 2016;215:454–60.
[4] Moradi M, Kazempour M, French JT, Alvarado V. Dynamic flow response of crude
oil-in-water emulsion during flow through porous media. Fuel 2014;135:38–45.
[5] Kazemzadeh Y, Sharifi M, Riazi M. Mutual effects of Fe3O4/Chitosan nanocompo-
site and different ions in water for stability of w/o emulsions at low-high salinities.
Energy Fuels 2018.
[6] Kumar A, Mandal A. Characterization of rock-fluid and fluid-fluid interactions in
presence of a family of synthesized zwitterionic surfactants for application in en-
hanced oil recovery. Colloids Surf, A 2018;549:1–12.
[7] Kazemzadeh Y, Sharifi M, Riazi M, Rezvani H, Tabaei M. Potential effects of metal
oxide/SiO2 nanocomposites in EOR processes at different pressures. Colloids Surf, A
2018;559:372–84.
[8] Rezvani H, Riazi M, Tabaei M, Kazemzadeh Y, Sharifi M. Experimental investigation
of interfacial properties in the EOR mechanisms by the novel synthesized
Fe3O4@Chitosan nanocomposites. Colloids Surf, A 2018;544:15–27.
[9] Griffith N, Ahmad Y, Daigle H, Huh C. Nanoparticle-stabilized natural gas liquid-in-
water emulsions for residual oil recovery. SPE improved oil recovery conference.
Society of Petroleum Engineers; 2016.
[10] Feng C, Kong Y, Jiang G, Yang J, Pu C, Zhang Y. Wettability modification of rock
cores by fluorinated copolymer emulsion for the enhancement of gas and oil re-
covery. Appl Surf Sci 2012;258(18):7075–81.
[11] Mironova MV, Ilyin SO. Effect of silica and clay minerals on rheology of heavy
crude oil emulsions. Fuel 2018;232:290–8.
[12] Zhang T, Davidson D, Bryant SL, Huh C. Nanoparticle-stabilized emulsions for ap-
plications in enhanced oil recovery. SPE improved oil recovery symposium. Society
of Petroleum Engineers; 2010.
[13] Maaref S, Ayatollahi S. The effect of brine salinity on water-in-oil emulsion stability
through droplet size distribution analysis: a case study. J Dispersion Sci Technol
2018;39(5):721–33.
[14] Mandal A, Samanta A, Bera A, Ojha K. Characterization of oil− water emulsion and
its use in enhanced oil recovery. Ind Eng Chem Res 2010;49(24):12756–61.
[15] Rezvani H, Khalilnezhad A, Ganji P, Kazemzadeh Y. How ZrO2 nanoparticles im-
prove the oil recovery by affecting the interfacial phenomena in the reservoir
conditions? J Mol Liq 2018;252:158–68.
[16] Maaref S, Ayatollahi S, Rezaei N, Masihi M. The effect of dispersed phase salinity on
water-in-oil emulsion flow performance: a micromodel study. Ind Eng Chem Res
2017;56(15):4549–61.
[17] Kokal SL. Crude oil emulsions: a state-of-the-art review. SPE Prod Facil
2005;20(01):5–13.
[18] Kumar R, Dao E, Mohanty K. Heavy-oil recovery by in-situ emulsion formation. SPE
J 2012;17(02):326–34.
[19] Kazemzadeh Y, Shojaei S, Riazi M, Sharifi M. Review on application of nano-
particles for EOR purposes; a critical of the opportunities and challenges. Chin J
Chem Eng 2018.
[20] Bera A, Kumar T, Ojha K, Mandal A. Screening of microemulsion properties for
application in enhanced oil recovery. Fuel 2014;121:198–207.
[21] Carneiro GF, Silva RC, Barbosa LL, Freitas JC, Sad CM, Tose LV, et al.
Characterisation and selection of demulsifiers for water-in-crude oil emulsions
using low-field 1H NMR and ESI–FT-ICR MS. Fuel 2015;140:762–9.
[22] Aman ZM, Paris CB, May EF, Johns ML, Lindo-Atichati D. High-pressure visual
experimental studies of oil-in-water dispersion droplet size. Chem Eng Sci
2015;127:392–400.
[23] Perazzo A, Tomaiuolo G, Preziosi V, Guido S. Emulsions in porous media: from
single droplet behavior to applications for oil recovery. Adv Colloid Interface Sci
2018.
[24] Silva F, Tavares F, Cardoso M. Thermodynamic stability of water-in-oil emulsions.
Braz J Petrol Gas 2013;7(1).
[25] Al-Yaari M, Hussein I, Al-Sarkhi A, Abbad M, Chang F. Effect of water salinity on
surfactant-stabilized water–oil emulsions flow characteristics. Exp Therm Fluid Sci
2015;64:54–61.
[26] Kumar N, Gaur T, Mandal A. Characterization of SPN Pickering emulsions for ap-
plication in enhanced oil recovery. J Ind Eng Chem 2017;54:304–15.
[27] Kumar N, Mandal A. Thermodynamic and physicochemical properties evaluation
for formation and characterization of oil-in-water nanoemulsion. J Mol Liq 2018.
[28] Qiao P, Harbottle D, Tchoukov P, Masliyah J, Sjoblom J, Liu Q, et al. Fractionation
of asphaltenes in understanding their role in petroleum emulsion stability and
fouling. Energy Fuels 2017;31(4):3330–7.
Y. Kazemzadeh et al.
[29] McLean JD, Kilpatrick PK. Effects of asphaltene solvency on stability of water-in-
crude-oil emulsions. J Colloid Interface Sci 1997;189(2):242–53.
[30] Spiecker PM, Gawrys KL, Trail CB, Kilpatrick PK. Effects of petroleum resins on
asphaltene aggregation and water-in-oil emulsion formation. Colloids Surf, A
2003;220(1–3):9–27.
[31] Gafonova OV, Yarranton HW. The stabilization of water-in-hydrocarbon emulsions
by asphaltenes and resins. J Colloid Interface Sci 2001;241(2):469–78.
[32] da Silva M, Sad CM, Pereira LB, Corona RR, Bassane JF, dos Santos FD, et al. Study
of the stability and homogeneity of water in oil emulsions of heavy oil. Fuel
2018;226:278–85.
[33] McGurn MK, Baydak EN, Sztukowski DM, Yarranton HW. The effect of inorganic
solids on emulsion layer growth in asphaltene-stabilized water-in-oil emulsions.
Can J Chem Eng 2017.
[34] Zhong D-L, Ding K, Lu Y-Y, Yan J, Zhao W-L. Methane recovery from coal mine gas
using hydrate formation in water-in-oil emulsions. Appl Energy 2016;162:1619–26.
[35] Lukanov B, Firoozabadi A. Specific ion effects on the self-assembly of ionic sur-
factants: a molecular thermodynamic theory of micellization with dispersion forces.
Langmuir 2014;30(22):6373–83.
[36] Shojaati F, Mousavi SH, Riazi M, Torabi F, Osat M. Investigating the effect of
salinity on the behavior of asphaltene precipitation in the presence of emulsified
water. Ind Eng Chem Res 2017;56(48):14362–8.
[37] Lashkarbolooki M, Ayatollahi S, Riazi M. The impacts of aqueous ions on interfacial
tension and wettability of an asphaltenic–acidic crude oil reservoir during smart
water injection. J Chem Eng Data 2014;59(11):3624–34.
[38] Czarnecki J. Stabilization of water in crude oil emulsions. Part 2. Energy Fuels
2008;23(3):1253–7.
[39] Zolfaghari R, Fakhru’l-Razi A, Abdullah LC, Elnashaie SS, Pendashteh A.
Demulsification techniques of water-in-oil and oil-in-water emulsions in petroleum
industry. Sep Purif Technol 2016;170:377–407.
[40] Subramanian D, May N, Firoozabadi A. Functional molecules and the stability of
water-in-crude oil emulsions. Energy Fuels 2017;31(9):8967–77.
27
Fuel 243 (2019) 15–27
[41] Fu T, Ma Y, Funfschilling D, Zhu C, Li HZ. Squeezing-to-dripping transition for
bubble formation in a microfluidic T-junction. Chem Eng Sci 2010;65(12):3739–48.
[42] Umar AA, Saaid IB, Sulaimon AA. Rheological and stability study of water-in-crude
oil emulsions. AIP Conf Proc 1774. AIP Publishing; 2016.
[43] Czarnecki J, Moran K. On the stabilization mechanism of water-in-oil emulsions in
petroleum systems. Energy Fuels 2005;19(5):2074–9.
[44] Lashkarbolooki M, Riazi M, Ayatollahi S, Hezave AZ. Synergy effects of ions, resin,
and asphaltene on interfacial tension of acidic crude oil and low–high salinity
brines. Fuel 2016;165:75–85.
[45] Jian C, Poopari MR, Liu Q, Zerpa N, Zeng H, Tang T. Reduction of water/oil in-
terfacial tension by model asphaltenes: the governing role of surface concentration.
J Phys Chem B 2016;120(25):5646–54.
[46] Guzmán R, Ancheyta J, Trejo F, Rodríguez S. Methods for determining asphaltene
stability in crude oils. Fuel 2017;188:530–43.
[47] Jafari SM, Assadpoor E, He Y, Bhandari B. Re-coalescence of emulsion droplets
during high-energy emulsification. Food Hydrocolloids 2008;22(7):1191–202.
[48] Jaffrin MY. Dynamic shear-enhanced membrane filtration: a review of rotating
disks, rotating membranes and vibrating systems. J Membr Sci
2008;324(1–2):7–25.
[49] Floury J, Desrumaux A, Lardieres J. Effect of high-pressure homogenization on
droplet size distributions and rheological properties of model oil-in-water emul-
sions. Innovative Food Sci Emerg Technol 2000;1(2):127–34.
[50] Lashkarbolooki M, Ayatollahi S. Effect of asphaltene and resin on interfacial tension
of acidic crude oil/sulfate aqueous solution: experimental study. Fluid Phase
Equilib 2016;414:149–55.
[51] Doryani H, Malayeri M, Riazi M. Visualization of asphaltene precipitation and de-
position in a uniformly patterned glass micromodel. Fuel 2016;182:613–22.
[52] Doryani H, Malayeri M, Riazi M. Precipitation and deposition of asphaltene in
porous media: impact of various connate water types. J Mol Liq 2018;258:124–32.
[53] Goual L, Sedghi M. Role of ion-pair interactions on asphaltene stabilization by al-
kylbenzenesulfonic acids. J Colloid Interface Sci 2015;440:23–31.