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org/journal/acsodf Article

Stability Dynamic Characteristic of Oil-in-Water Emulsion from

Alkali−Surfactant−Polymer Flooding
Chunhong Nie,* Guoqiang Han, Jiawen Ni, Shuxia Guan, Huan Du, Yupeng Zhang, and Heting Wang

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ABSTRACT: The relationship model between the droplet lifetime and

interface properties is established to characterize the stability of oil droplets,
and then, the influence of the alkali−surfactant−polymer (ASP) concentration
on the lifetime is analyzed by theoretical calculations. The stability dynamic
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characteristics of oil-in-water (O/W) emulsions from ASP flooding were

evaluated using the emulsion stability model (Civan model) based on two-phase
separation. The effect of ASP on dynamic characteristics of the emulsion was
explored by analyzing film strength qualitatively and measuring interfacial
tension and ζ potential. The results showed that the Civan model was suitable to
evaluate the stability of the O/W emulsion and to obtain the corresponding
dynamic characteristics. The O/W emulsions became more stable with the
increasing alkali concentration first at a low alkali concentration (cNaOH < 200
mg/L) and then became less stable with the increasing alkali concentration at a
high alkali concentration (cNaOH > 200 mg/L). The stabilities of O/W emulsions were improved with the increasing concentrations
of the surfactant and polymer. The mechanism of stabilization of the O/W emulsion by ASP is as follows. The surface-active
substances formed by the reaction of alkali and acidic substances in the oil phase, together with surfactants, adsorb at the oil−water
interface, reducing the interfacial tension and increasing the strength of the oil−water interface film. The polymer only increases the
strength of the interface film by increasing the viscoelasticity of the oil−water interface film.

1. INTRODUCTION large well spacing, multiple good groups, and multiple oil
Petroleum has been an important strategic resource in the layers. It provides a theoretical and practical basis for the large-
world. With the ever-increasing energy competition today, how scale popularization and application of ASP flooding
to improve oil recovery is a concern of the petroleum industry. technology in the Daqing oilfield. In 2000, five industrial
After years of exploitation, most of China’s oilfields have field experiments were carried out in the Daqing oilfield to
entered the late stage of high water content. The crude oil from continue to verify that ASP flooding can increase oil recovery
water flooding is decreasing year by year, and the current by 20% compared with water flooding. In 2014, the technology
recovery rate is generally only 30−40%. The application of and management system of ASP flooding was established,
recovery enhancement technology is a necessary stage of industrial applications were promoted, and large-scale
oilfield development, and it is also an effective method for old commercial applications and complete sets of output
oilfields to suppress the decline in the production and maintain conditions were available.7,8 At present, a relatively supporting
stable production.1−4 technical system has been formed to achieve the goal of
The alkali−surfactant−polymer (ASP) flooding is a increasing oilfield recovery and improving development effects
technology that greatly enhances oil recovery based on binary and has become a new point of output growth.
floodings such as alkaline−polymer flooding and surfactant− The geological reserves suitable for ASP flooding in China
polymer flooding. The ASP flooding has been studied in the are about 83 × 108 t. As far as the Daqing oilfield is concerned,
Daqing oilfield since the 1980s and has gradually achieved the reserves are approximately 14 × 108 t. The ASP flooding
continuous innovation breakthroughs in theoretical research,
system formulations, and industrialization application. In 1997,
five pilot field experiments were carried out in the Daqing Received: May 5, 2021
oilfield. The field test results showed that ASP flooding can Accepted: July 9, 2021
increase oil recovery by 20% compared with water flooding.5,6 Published: July 18, 2021
In 1998, the world’s first industrial test of ASP flooding was
carried out in the Daqing oilfield, which further verified the oil
displacement effect of ASP flooding under the conditions of
© 2021 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsomega.1c02367
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production reached 4.63 million tons in 2020, and the annual for oil droplets to coalesce and grow up, which becomes a
output has been increasing year by year since 2014, as shown bottleneck restricting the implementation of demulsification.
in Figure 1.9−12 Therefore, it is of great significance for oil−water separation to
study the effects of ASP on the stabilization of emulsions. In
this study, we investigate the stability dynamic characteristic of
O/W emulsions using the lifetime model and Civan model. We
investigate the role of ASP in the emulsion stability and the
interface properties to provide quantitative insight into the
microscopic mechanism of emulsion stabilization by ASP.

2. RESULTS AND DISCUSSION

2.1. Lifetime Model of an O/W Interfacial Film. An
emulsion is a highly dispersed system where work needs to be
done to disperse the dispersed phase and store it at the oil−
water interface in the form of surface energy. The process of
increasing surface free energy is not spontaneous, but the
reverse process (that is, the process of automatically merging
droplets to reduce the surface area) is spontaneous, so
emulsions are thermodynamically unstable.25
Under the same dispersion conditions, to reduce the
instability of the emulsion, it is necessary to reduce the oil−
water interfacial tension, which can be achieved by adding
Figure 1. ASP flooding oil production in the Daqing oilfield. surfactants. The surfactant added to the oil−water system not
only reduces the surface tension but also adsorbs at the
interface and forms an interface film with a certain strength,
The ASP flooding has been identified as the leading which protects the dispersed phase and makes it difficult to
technology for maintaining the output. However, the residual merge after colliding with each other.26 Solid particles
alkali, surfactant, and polymer in the produced water cause suspended in oil−water systems are also good emulsifiers. A
serious emulsification and separation difficulties, which particle emulsifier is the same as the usual surfactants.
severely restrict the large-scale promotion of ASP flooding Adsorption reduces the interfacial area and hence lowers the
technology.13 To break up oil-in-water (O/W) emulsions, a free energy of the system. Furthermore, unlike surfactants, such
variety of demulsification techniques have been applied for particles need not be amphiphilicthe only requirement is
oil−water separation, such as chemical methods,14 physical that they should be partially wetted by both fluids.27
methods,15 biological methods,16 and mechanical methods Due to ionization, adsorption, or friction between the
including gravity demulsification,17 microwave demulsifica- droplets and the medium, most of the stable O/W (or W/O)
tion,18 thermal demulsification,19 electric demulsification,20 air droplets are charged, so the droplets can repel each other when
flotation,21 ultrasonic demulsification,22 and membrane tech- they are close, which prevents them from merging and
nology.23,24 These conventional methods often exhibit low improves the stability of the emulsion.28 The increase in the
efficiency when handling O/W emulsions from ASP flooding. viscosity of the external phase of the emulsion can reduce the
Due to the residue of ASP, the O/W emulsions from ASP diffusion coefficient of the droplets and reduce the collision
flooding have the characteristics of large viscosity, small frequency and coalescence rate, which is conducive to the
particle size, and strong interfacial film. This makes it difficult stability of the emulsion. The size and distribution of emulsion

Figure 2. Interface structure of the O/W emulsion from ASP flooding.

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droplets have a great influence on the stability of the emulsion. film breakage and droplet coalescence. The difficulty of
Generally, the narrower the droplet size range, the more stable coalescence of oil droplets mainly depends on the strength
the emulsion is.29 of the interfacial film of the oil droplets. Usually, greater
In addition, the phase state and stability of surfactant- interfacial strength can lead to a longer lifetime of the
stabilized emulsions are affected easily by salinity. Generally interfacial film, and it is less likely that the oil droplets coalesce.
speaking, monovalent metal soaps can emulsify oil and water However, the strength of the interfacial film is not easy to be
into O/W emulsions. Adding high-valent metal ions, such as measured, and the film lifetime can be used to characterize the
Ca2+, Mg2+, Al3+, Cr3+, etc., will compress the diffuse electric stability of the oil droplets. The factors affecting the lifetime of
double layer at the oil−water interface, reduce the strength and the interface film are divided into two categories: one is the
thickness of the interface film, and reduce the stability of the chemical substance in the system such as alkali, surfactant,
emulsion. At the same time, after the concentration of high- polymer, and salt and the other is the nature of the oil droplet
valent metal ions dominates, the emulsifier exhibits the itself, that is, the size of the oil droplet.36,37
hydrophobicity of the high-valent metal soap, which makes The interfacial film of oil droplets is elastic and easily
the emulsion phase invert to the W/O type.30−32 deforms by applying an external force. When the oil droplets
The produced water from ASP flooding contains a large are close to each other, external forces such as buoyancy play a
amount of surfactants, polyacrylamide, alkali, and oil. The oil− leading role, and the oil droplets remain spherical, as shown in
water interface of the simulated emulsion prepared in this Figure 4a. When the distance between oil droplets is
experiment mainly adsorbs sodium dodecylbenzene (SDBS)
and HPAM, and the adsorption method is as follows: (1)
SDBS molecules are arranged on the interface to form an
interface film, and the hydrophilic groups interact with the
carboxyl anion or amide anion in the HPAM chain, thus part of
HPAM molecules can be aligned on the oil−water interface
(Figure 2, adsorption form 1). (2) The lipophilic groups of
−CH2− in the HPAM chain can connect with the oil phase,
and the hydrophilic groups of −COOH and −CONH2
dissolve in the water phase. In this adsorption form, HPAM
molecules can adsorb on the oil−water interface (Figure 2,
Figure 4. Morphological changes during the approach of oil droplets:
adsorption form 2). Also, amphiphilic HPAM and SDBS can (a) droplets are spherical and (b) droplets deform to form a flat film.
bond together through hydrophobic forces, electrostatic
interactions, hydrogen bonds, etc., to strengthen the interface
layer. The interface structure of the O/W emulsion is shown in shortened, the intermolecular forces play a dominant role
Figure 2.33−35 and the interface where the oil droplets are close to each other
The O/W emulsion from ASP flooding is a multiphase will sink inward. Thus, an interface film will be formed
dispersion system, and the key to its instability is the between the oil droplets, as shown in Figure 4.
aggregation of suspended oil droplets into larger droplets. As When the emulsion droplets approach each other driven by
shown in Figure 3, when the suspended oil droplets move a certain external force, the life of the interfacial film can be
randomly and approach each other, they will be subject to calculated from eq 137
buoyancy and intermolecular forces (van der Waals attraction, hin dh
electrostatic repulsion, steric hindrance, etc.). Due to the two τ= ∫h c V (1)
forces, the collision of droplets will produce three results: (1)
droplet rebound, (2) droplet flocculation, and (3) interfacial From the literature, eq 2 was obtained
9η ln a 9η ln(10hc) 1 3η 2 15η
τ= − + a − a
2g Δρ a 2g Δρ a 4σhc 2σ
9ηg Δρ 5 25ηg Δρ 3
+ 2 2
a − a
144σ hc 4σ 2 (2)
Based on eq 2, it can be found that the oil droplet size, oil−
water interfacial tension, and viscosity will affect the life of the
interfacial film.
2.1.1. Influence of the Droplet Size on the Lifetime of the
O/W Interfacial Film. To more intuitively study the influence
of the size on the lifetime of the interfacial film, we organize
the formula and reassign A−F
9η 9η ln(10hc) 3η 15η
A= , B= , C= , D= ,E
2g Δρ 2g Δρ 4σhc 2σ
9ηg Δρ 25ηg Δρ
= 2 2
, F=
144σ hc 4σ 2
Figure 3. Possible results of the collision of two emulsion droplets in Then, the mathematical relationship between the lifetime
connection with the droplet−droplet interaction. and the droplet radius is derived as shown in eq 3
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ln a 1 reducing the interfacial tension of oil and water, which is the

τ=A − B + Ca2 − Da + Ea5 − Fa3
a a (3) main reason for the stable existence of oil droplets in water.
The interfacial tension of oil and water in the produced water
where τ is the lifetime of a single droplet, σ is the interfacial from ASP flooding mainly depends on the concentration of
tension, g is the gravitational acceleration, Δρ is the density surfactants.40 Therefore, interfacial tension can be used to
difference, a is the droplet radius, hc is the distance between reflect the effect of the surfactant concentration on the film
the droplets, and η is the viscosity of the film phase. According lifetime. We organize eq 1 and reassign A−E:
to ref 16, hc = 5 nm, g = 9.8 m/s2, Δρ = 200 kg/m3, and the
experimental η = 1.33 mPa s and the calculations for A−F can 9η ln a 9η ln(10hc) 1 3ηa 2
A= − , B= ,C
be performed. Moreover, the mathematical relationship 2g Δρ a 2g Δρ a 4hc
between the lifetime of the liquid film and the radius of the
droplet is shown in Figure 5. 15aη 9ηg Δρa5 25ηg Δρa3
= , D= , E =
2 144hc 2 4
Then, the mathematical relationship between the film
lifetime and the interfacial tension is derived and is shown in
eq 4
B−C D−E
τ=A+ +
σ σ2 (4)
where τ is the lifetime of a single droplet and σ is the interfacial
tension. According to the literature, hc = 5 nm, g = 9.8 m/s2,
Δρ = 200 kg/m3, and the experimental η = 1.33 mPa s. Taking
the sizes of oil droplets as 1, 2, 3, 4, and 5 μm, the values of A−
F can be calculated. Furthermore, the mathematical relation-
ship between the film lifetime and the interfacial tension is
shown in Figure 6.

Figure 5. Calculated lifetime, τ, of O/W drops approaching from

below a water−oil interface in the Taylor regime and Reynolds regime
(other lines) as a function of the droplet radius, a.

The various curves in Figure 5 correspond to different values

of the interfacial tension (σ). The left-side branches of the
curves correspond to the Taylor regime (nondeformed
droplets), and the right-side branches correspond to the
Reynolds regime (formation of the film between the droplets).
In the Taylor regime, the lifetime of the O/W droplet
decreases with the increase in the radius of droplets. In the case
of a larger radius (the Reynolds regime), the lifetime increases
with the increasing radius of droplets. This is exactly the
opposite trend to that of the Taylor regime. There is a
minimum value in the curve of τ vs a, which was proposed in Figure 6. Calculated lifetime, τ, of O/W drops approaching from
ref 38. below a water−oil interface in the Taylor regime and Reynolds regime
2.1.2. Influence of Alkali on the Lifetime of the O/W (other lines) as a function of the interfacial tension.
Interfacial Film. It can be found from eq 1 that the influence of
alkali on the lifetime of the interfacial film cannot be directly
analyzed by this model. However, it can be found39 that the It can be seen from Figure 6 that the lifetime of the O/W
effect of alkali on the interfacial film of oil droplets has two droplet increases with the decrease in the interfacial tension,
main aspects: first, the alkali can react with the acidic which shows that the stability of the O/W droplet increases
substances in the crude oil to form surfactant; thus, high with the increasing concentration of the surfactant. As the
strength of the interfacial film can be obtained. Second, as the interfacial tension decreases, the lifetime of the O/W droplet
alkali concentration continues to increase, the ions electrolyzed changes greatly. In the case of smaller σ (interfacial tension, the
will compress the electric double layer at the interface of the oil left-hand side branches of curves in Figure 6), the film lifetime
droplet, weaken the strength of the interface film of the oil increases sharply with the decrease in the interfacial tension,
droplet, and reduce the lifetime of the interfacial film. which shows that the concentration of surfactants greatly
2.1.3. Influence of Surfactant on the Lifetime of the O/W affects the film lifetime of the O/W droplet. At the same time,
Interfacial Film. It can be found from eq 1 that the influence of it was also found that with the increase in the oil droplet size,
interfacial tension on the film lifetime of oil droplets can be the influence of surfactants on the film lifetime gradually
directly analyzed by this model. Surfactants have the effect of weakened, and the reduction range gradually became smaller.
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2.1.4. Influence of Polymers on the Lifetime of the O/W dX

= kd(X f − X )n
Interfacial Film. As eq 1 deforms and reassigns A−E, the dt (6)
mathematical model of the film lifetime and viscosity can be
described as eq 5 where X is the demulsification rate of the emulsion at time t, Xf
is the maximum demulsification rate of the emulsion, and n is
9ln a 9ln(10hc) 3a 2 15a the reaction order during the demulsification process of the
A= , B= , C= , D= ,E emulsion, n = 0.4.44 The initial state is defined as X = 0 and dt
2g Δρa 2g Δρa 4σhc 2σ
= t, and eq 6 is organized as eq 7
9g Δρa5 25g Δρa3
= 2 2
, F= (X f − X )1 − n = X f 1 − n − (1 − n)kd(t − td) (7)
144σ hc 4σ 2
where td is the delay time of emulsion instability, a plot of Xf1−n
τ = (A − B + C − D + E − F )η (5) − (Xf − X)1−n vs t − td should yield a linear correlation, and
Taking the size of the oil droplet as 2, 3, 4, and 5μm, the the slope of m is equal to (1 − n)kd. Therefore, the rate
values of A−F can be calculated, and the mathematical constant of emulsion instability (kd) can be defined as eq 8
relationship between the film lifetime and viscosity is shown in kd =
m
Figure 7. (1 − n) (8)
The half-life of the O/W emulsion from ASP flooding can be
determined using eq 9 by combining eqs 7 and 8
X f 0.6 − (0.5X f )0.6
(t − td) =
0.6kd (9)
2.2.1. Effect of Alkali on the Stability Dynamic Character-
istic of Emulsions. The emulsions used in the tests were
prepared by mixing water samples containing 200, 400, 800,
and 1200 mg/L NaOH; 0.1% SDBS; and 450 mg/L HPAM
and emulsifying them for 10 min with a speed of 1500 rpm.
The bottle tests with 100 mL of emulsions were used to
measure the water separation rate at different settling times.
Based on the water separation rate, we can acquire the scatter
plot of Xf1−n − (Xf − X)1−n with t − td. Therefore, the slope m
can be obtained by linear fitting of scattered points, as shown
in Figure 8.

Figure 7. Calculated lifetime, τ, of O/W drops approaching from

below a water−oil interface in the Taylor regime and Reynolds regime
(other lines) as a function of the viscosity.

It can be seen from Figure 7 that the film lifetime increases

with the increase in the viscosity in the water phase, that is, the
lifetime increases with the increase in the polymer concen-
tration, and the stability of the oil droplet increases with the
polymer concentration. At the same time, it can also be found
from Figure 7 that the smaller size of the oil droplet can result
in a longer lifetime, which shows that the larger size of the oil
droplet makes it break easily.41,42
2.2. Quantitative Theoretical Model of Emulsion
Stability. The stability of emulsions is a key parameter in
the petroleum industry for the separation of oil and water. The
stability of emulsions was studied generally by experiments. Figure 8. Straight-line plot of the present data of the fraction of
Only a few studies described quantitative theoretical separated water from various emulsions vs time with different alkali
analyses.43 These works provide valuable insight into the additions.
mechanism of emulsion formation and a method to determine
and interpret the key parameters of emulsion formation, According to eq 8, the instability rate of the O/W emulsion
including the reaction order, rate constant, and half-life. from ASP flooding can be calculated. Finally, according to eq
Based on the stability model established by Civan, the 9, the half-life of oil droplets can be calculated. The results are
influence of alkali, surfactant, and polymer on oil droplet shown in Table 1.
dynamics has been analyzed. According to the stability model, 2.2.2. Effect of Surfactant on the Stability Dynamic
the instantaneous demulsification rate can be calculated by eq Characteristic of Emulsions. The emulsions used in the tests
6 were prepared by mixing water samples containing 0.025%,
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Table 1. Effect of the NaOH Concentration on the

Instability Rate and Half-Life of O/W Emulsion
concentration (mg/L) (1 − n)kd kd (h−1) (t − td)1/2 (h)
200 0.0804 0.1340 2.8144
400 0.0794 0.1324 2.8920
800 0.0778 0.1296 2.9438
1200 0.0762 0.1270 3.1269

0.5%, 0.1%, and 0.2% SDBS, 200 mg/L NaOH, and 450 mg/L
HPAM at 1500 rpm for 10 min. The calculation steps are the
same as above, and the results are shown in Figure 9 and Table
2.

Figure 10. Straight-line plot of the present data of the fraction of

separated water from various emulsions vs time with different PAM
additions.

Table 3. Effect of HPAM on the Instability Rate and Half-

Life of the Oil−Water Emulsion
concentration (mg/L) (1 − n)kd kd (h−1) (t − td)1/2 (h)
150 0.1033 0.1722 2.2244
300 0.0862 0.1436 2.3354
450 0.0587 0.09777 2.4223

increases. The reason is that NaOH reacts with acidic

substances in the oil phase to form certain surfactants, which
Figure 9. Straight-line plot of the present data of the fraction of improves the strength of the interfacial film.39 The influence of
separated water from various emulsions vs time with different surfactants on the oil−water interface film is shown in Figure 6
surfactant additions. and Table 2. With the increase in the surfactant concentration,
the lifetime of the O/W droplet and the half-life of instability
Table 2. Effect of Surfactant on the Instability Rate and increase and the instability rate constant decreases, indicating
Half-Life of the Oil−Water Emulsion that the increase in the surfactant enhances the strength of the
oil−water interface film of the emulsion. This is because the
mass percentage (%) (1 − n)kd kd (h−1) (t − td)1/2 (h)
increased surfactants are arranged more closely at the oil−
0.025 0.1132 0.1887 2.1226 water interface, increasing the strength of the interface film.26
0.05 0.1102 0.1837 2.1333 The influence of the polymer on the oil−water interface film is
0.1 0.0642 0.1070 2.4333 shown in Figure 7 and Table 3. With the increase in the
0.2 0.0507 0.0845 2.4510 HPAM concentration, the lifetime of the interfacial film and
the instability rate of the oil−water emulsion gradually
2.2.3. Effect of the Polymer on the Stability Dynamic decrease and the half-life of droplet demulsification increases,
Characteristic of Emulsions. The emulsions used in the tests which shows that the increase in the polymer concentration
were prepared by mixing water samples containing 150, 300, improves the strength of the oil−water interface film. This is
and 450 mg/L HPAM; 0.1% SDBS; and 200 mg/L NaOH and due to the adsorption and orientation of a high concentration
emulsifying them for 10 min with a speed of 1500 rpm. The of polymers at the interface between the solution and the oil
calculation steps are the same as above, and the results are phase, forming a tightly arranged oil−water interface film,
shown in Figure 10 and Table 3. which increases the viscoelasticity of the oil−water interface
2.3. Microscopic Mechanism of the Influence of ASP film, thereby improving the strength of the film.48,49
on the Stability of O/W Emulsions. The stability of O/W 2.3.2. Influence of ASP on the Interfacial Tension. The
emulsion from ASP flooding is related to many factors, such as interface between two immiscible fluids has high interfacial
the composition and ratio of the two phases, particle size and tension, which produces droplets of one liquid dispersed in a
distribution, temperature, viscosity, and properties of the second immiscible liquid, forming an inherently unstable
interfacial film. Among them, the interfacial properties system. The interfacial tension reflects the adsorption of active
including interfacial film strength, ζ potential, and interfacial substances at the interface. Therefore, the study of interfacial
tension play a vital role in the stability of the emulsion.45−47 tension can explain the influence of ASP on the oil−water
2.3.1. Influence of ASP on O/W Interfacial Strength. It can interfacial film, and then, dynamic characteristics of the
be seen from Table 1 that with the increase in the NaOH emulsion are further discussed.49
concentration, the instability rate of the O/W emulsion As shown in Figure 11a, the interfacial tension first decreases
gradually decreases and the half-life of instability gradually and then slightly increases with the increase in the NaOH
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Figure 11. Influence of alkali (a)−surfactant (b)−polymer (c) on the interfacial tension.

Figure 12. Influence of alkali (a)−surfactant (b)−polymer (c) on the ζ potential.

concentration. This is because NaOH can react with acidic a dominant role in the compression of the interfacial diffusion
substances in the oil phase, which can adsorb at the oil−water double layer, thereby increasing the ζ potential. As shown in
interface and decrease the interfacial tension. When the Figure 12b,c, surfactants and polymers have similar effects on
concentration of NaOH is higher than 200 mg/L, all acidic the ζ potential. As their concentrations increase, the ζ potential
substances react, and NaOH has no obvious effect on the decreases. This is mainly because both the surfactant molecules
interfacial tension. As shown in Figure 11b, the interfacial and polymer molecules adsorbed at the oil−water interface are
tension decreases as the surfactant concentration increases. negatively charged. As their concentrations increase, the
When the surfactant content is less than 0.1%, the interfacial repulsive force between the charges increases, making the
tension decreases sharply. While continuing to increase the polymers tightly arranged at the oil−water interface. The
surfactant content, the interfacial tension slowly decreases. ability of oil droplets to coalesce decreases, which leads to an
This is because 0.1% surfactant can make the oil−water increase in the absolute value of the ζ potential, and the
interface adsorption saturated. As shown in Figure 11c, as the influence of surfactants is greater.50
polymer concentration increases, the oil−water interfacial
tension remains unchanged, which shows that the polymer has 3. CONCLUSIONS
a small effect on the interfacial tension. Furthermore, the lower The influence of the alkali, surfactant, and polymer
interfacial tension also benefits from the salinity of the oil− concentration on the stability of droplets was analyzed using
water system, which increases the activity of the surfactant a lifetime model of the O/W interfacial film. The dynamic
molecules and helps reduce the interfacial tension.28 characteristics of the O/W emulsion from ASP flooding
2.3.3. Influence of ASP on ζ Potential. The ζ potential is conform to the emulsion stability model based on two-phase
the main parameter describing the interface charge of the separation, which is closely related to the properties of the oil−
dispersed droplets. Its absolute value characterizes the water interface. While the strength of the oil−water interfacial
magnitude of the charge on the surface of the droplets. It is film increases with the increasing alkali concentration at a low
related to the structure of the charge layer and reflects the alkali concentration (cNaOH < 200 mg/L), the rate constant kd
strength of the charge repulsion between the dispersed decreases and the emulsion stability increases. While the
droplets. It is generally believed that a larger ζ potential led strength of the oil−water interfacial film decreases with the
to a more stable emulsion.17 The influence of ASP on the ζ increasing alkali concentration at a high alkali concentration
potential is shown in Figure 12. (cNaOH > 200 mg/L), the rate constant kd increases and the
As shown in Figure 12a, as the NaOH concentration emulsion stability decreases. Furthermore, the strength of the
increases, the ζ potential first decreases and then rises slightly. oil−water interface film increases with the increasing surfactant
The reason may be that the anionic surfactant generated by and polymer concentration, the rate constant kd decreases, and
sodium hydroxide and acidic substances in the oil sample the stability of the emulsion increases. The mechanism of
increases the negative charge density at the oil−water interface stabilization of the O/W emulsion by ASP can be described as
and the ζ potential decreases at low concentrations.31 As the follows: alkali and surfactants reduce the interfacial tension and
concentration of sodium hydroxide increases, sodium ions play increase the interfacial strength, and the polymer only increases
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Table 4. Mineral Content of Produced Water

minerals NaCl Na2CO3 NaHCO3 Na2SO4 CaCl2 MgCl2·6H2O
concentration (mg/L) 1523 168.7 2820 10.5 56.9 35.5

the strength of the interface film by increasing the Complete contact information is available at:
viscoelasticity of the oil−water interface film. https://pubs.acs.org/10.1021/acsomega.1c02367

4. EXPERIMENTAL SECTION Notes

The authors declare no competing financial interest.

■
4.1. Chemicals and Materials. Diesel was supplied by a
gas station in Daqing (Heilongjiang Province, China). Sodium
hydroxide (NaOH) was purchased from Liaoning Quanrui ACKNOWLEDGMENTS
Reagent Co., Ltd., China. SDBS was purchased from Aladdin This work was financially supported by the National Nature
Chemistry, Shanghai, China. Polyacrylamide (HPAM, Mw ∼ 5 Science Foundation of China (NSFC Project no. 51704076).
× 106, 99%) was obtained from the Tianjin BA Chemical
Reagent Factory. Sodium carbonate (Na2CO3), calcium
chloride (CaCl2), sodium chloride (NaCl), sodium sulfate
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19066 https://doi.org/10.1021/acsomega.1c02367
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