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 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 (c NaOH < 200 mg/L) and then became less stable with the increasing alkali concentration at a high alkali concentration (c NaOH > 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.
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 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 (c NaOH < 200 mg/L) and then became less stable with the increasing alkali concentration at a high alkali concentration (c NaOH > 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.
Petroleum has been an
important strategic resource in the world.
With the ever-increasing energy competition today, how to improve
oil recovery is a concern of the petroleum industry. After years of
exploitation, most of China’s oilfields have entered the late
stage of high water content. The crude oil from water flooding is
decreasing year by year, and the current recovery rate is generally
only 30–40%. The application of recovery enhancement technology
is a necessary stage of oilfield development, and it is also an effective
method for old oilfields to suppress the decline in the production
and maintain stable production.[1−4]The alkali–surfactant–polymer
(ASP) flooding is a
technology that greatly enhances oil recovery based on binary floodings
such as alkaline–polymer flooding and surfactant–polymer
flooding. The ASP flooding has been studied in the Daqing oilfield
since the 1980s and has gradually achieved continuous innovation breakthroughs
in theoretical research, system formulations, and industrialization
application. In 1997, five pilot field experiments were carried out
in the Daqing oilfield. The field test results showed that ASP flooding
can increase oil recovery by 20% compared with water flooding.[5,6]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 large
well spacing, multiple good groups, and multiple oil layers. It provides
a theoretical and practical basis for the large-scale popularization
and application of ASP flooding technology in the Daqing oilfield.
In 2000, five industrial field experiments were carried out in the
Daqing oilfield to continue to verify that ASP flooding can increase
oil recovery by 20% compared with water flooding. In 2014, the technology
and management system of ASP flooding was established, industrial
applications were promoted, and large-scale commercial applications
and complete sets of output conditions were available.[7,8] At present, a relatively supporting technical system has been formed
to achieve the goal of increasing oilfield recovery and improving
development effects and has become a new point of output growth.The geological reserves suitable for ASP flooding in China are
about 83 × 108 t. As far as the Daqing oilfield is
concerned, the reserves are approximately 14 × 108 t. The ASP flooding production reached 4.63 million tons in 2020,
and the annual output has been increasing year by year since 2014,
as shown in Figure .[9−12]
Figure 1
ASP
flooding oil production in the Daqing oilfield.
ASP
flooding oil production in the Daqing oilfield.The ASP flooding has been identified as the leading technology
for maintaining the output. However, the residual alkali, surfactant,
and polymer in the produced water cause serious emulsification and
separation difficulties, which severely restrict the large-scale promotion
of ASP flooding technology.[13] To break
up oil-in-water (O/W) emulsions, a variety of demulsification techniques
have been applied for oil–water separation, such as chemical
methods,[14] physical methods,[15] biological methods,[16] and mechanical methods including gravity demulsification,[17] microwave demulsification,[18] thermal demulsification,[19] electric
demulsification,[20] air flotation,[21] ultrasonic demulsification,[22] and membrane technology.[23,24] These conventional
methods often exhibit low efficiency when handling O/W emulsions from
ASP flooding. Due to the residue of ASP, the O/W emulsions from ASP
flooding have the characteristics of large viscosity, small particle
size, and strong interfacial film. This makes it difficult for oil
droplets to coalesce and grow up, which becomes a bottleneck restricting
the implementation of demulsification. 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.
Results and Discussion
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 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, which protects
the dispersed phase and makes it difficult to merge after colliding
with each other.[26] Solid particles suspended
in oil–water systems are also good emulsifiers. A particle
emulsifier is the same as the usual surfactants. Adsorption reduces
the interfacial area and hence lowers the free energy of the system.
Furthermore, unlike surfactants, such particles need not be amphiphilic—the
only requirement is that they should be partially wetted by both fluids.[27]Due to ionization, adsorption, or friction
between the droplets
and the medium, most of the stable O/W (or W/O) droplets are charged,
so the droplets can repel each other when they are close, which prevents
them from merging and improves the stability of the emulsion.[28] The increase in the viscosity of the external
phase of the emulsion can reduce the diffusion coefficient of the
droplets and reduce the collision frequency and coalescence rate,
which is conducive to the stability of the emulsion. The size and
distribution of emulsion droplets have a great influence on the stability
of the emulsion. Generally, the narrower the droplet size range, the
more stable the emulsion is.[29]In
addition, the phase state and stability of surfactant-stabilized
emulsions are affected easily by salinity. Generally speaking, monovalent
metal soaps can emulsify oil and water into O/W emulsions. Adding
high-valent metal ions, such as Ca2+, Mg2+,
Al3+, Cr3+, etc., will compress the diffuse
electric double layer at the oil–water interface, reduce the
strength and thickness of the interface film, and reduce the stability
of the emulsion. At the same time, after the concentration of high-valent
metal ions dominates, the emulsifier exhibits the hydrophobicity of
the high-valent metal soap, which makes the emulsion phase invert
to the W/O type.[30−32]The produced water from ASP flooding contains
a large amount of
surfactants, polyacrylamide, alkali, and oil. The oil–water
interface of the simulated emulsion prepared in this 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 , 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 , adsorption form 2). Also, amphiphilic HPAM and SDBS
can 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 Figure .[33−35]
Figure 2
Interface structure of the O/W emulsion
from ASP flooding.
Interface structure of the O/W emulsion
from ASP flooding.The O/W emulsion from
ASP flooding is a multiphase dispersion system,
and the key to its instability is the aggregation of suspended oil
droplets into larger droplets. As shown in Figure , when the suspended oil droplets move randomly
and approach each other, they will be subject to buoyancy and intermolecular
forces (van der Waals attraction, electrostatic repulsion, steric
hindrance, etc.). Due to the two forces, the collision of droplets
will produce three results: (1) droplet rebound, (2) droplet flocculation,
and (3) interfacial film breakage and droplet coalescence. The difficulty
of coalescence of oil droplets mainly depends on the strength of the
interfacial film of the oil droplets. Usually, greater interfacial
strength can lead to a longer lifetime of the interfacial film, and
it is less likely that the oil droplets coalesce. However, the strength
of the interfacial film is not easy to be measured, and the film lifetime
can be used to characterize the stability of the oil droplets. The
factors affecting the lifetime of the interface film are divided into
two categories: one is the chemical substance in the system such as
alkali, surfactant, polymer, and salt and the other is the nature
of the oil droplet itself, that is, the size of the oil droplet.[36,37]
Figure 3
Possible
results of the collision of two emulsion droplets in connection
with the droplet–droplet interaction.
Possible
results of the collision of two emulsion droplets in connection
with the droplet–droplet interaction.The interfacial film of oil droplets is elastic and easily deforms
by applying an external force. When the oil droplets are close to
each other, external forces such as buoyancy play a leading role,
and the oil droplets remain spherical, as shown in Figure a. When the distance between
oil droplets is shortened, the intermolecular forces play a dominant
role and the interface where the oil droplets are close to each other
will sink inward. Thus, an interface film will be formed between the
oil droplets, as shown in Figure .
Figure 4
Morphological changes during the approach of oil droplets:
(a)
droplets are spherical and (b) droplets deform to form a flat film.
Morphological changes during the approach of oil droplets:
(a)
droplets are spherical and (b) droplets deform to form a flat film.When the emulsion droplets approach each other
driven by a certain
external force, the life of the interfacial film can be calculated
from eq (37)From the literature, eq was obtainedBased on eq , it
can be found that the oil droplet size, oil–water interfacial
tension, and viscosity will affect the life of the interfacial film.
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–FThen, the mathematical
relationship
between the lifetime and the droplet radius is derived as shown in eq where
τ is the lifetime of a single
droplet, σ is the interfacial tension, g is
the gravitational acceleration, Δρ is the density difference, a is the droplet radius, hc is
the distance between the droplets, and η is the viscosity of
the film phase. According 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 be performed.
Moreover, the mathematical relationship between the lifetime of the
liquid film and the radius of the droplet is shown in Figure .
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.
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 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 ref (38).
Influence
of Alkali on the Lifetime of the
O/W Interfacial Film
It can be found from eq that the influence of alkali on
the lifetime of the interfacial film cannot be directly analyzed by
this model. However, it can be found[39] that
the effect of alkali on the interfacial film of oil droplets has two
main aspects: first, the alkali can react with the acidic substances
in the crude oil to form surfactant; thus, high strength of the interfacial
film can be obtained. Second, as the alkali concentration continues
to increase, the ions electrolyzed will compress the electric double
layer at the interface of the oil droplet, weaken the strength of
the interface film of the oil droplet, and reduce the lifetime of
the interfacial film.
Influence of Surfactant
on the Lifetime
of the O/W Interfacial Film
It can be found from eq that the influence of
interfacial tension on the film lifetime of oil droplets can be directly
analyzed by this model. Surfactants have the effect of reducing the
interfacial tension of oil and water, which is the main reason for
the stable existence of oil droplets in water. The interfacial tension
of oil and water in the produced water from ASP flooding mainly depends
on the concentration of surfactants.[40] Therefore,
interfacial tension can be used to reflect the effect of the surfactant
concentration on the film lifetime. We organize eq and reassign A–E:Then, the mathematical
relationship
between the film lifetime and the interfacial tension is derived and
is shown in eq 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 relationship between
the film lifetime and the interfacial tension is shown in Figure .
Figure 6
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 interfacial tension.
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 interfacial tension.It can be seen from Figure that the lifetime of the O/W droplet increases with
the decrease
in the interfacial tension, which shows that the stability of the
O/W droplet increases with the increasing concentration of the surfactant.
As the interfacial tension decreases, the lifetime of the O/W droplet
changes greatly. In the case of smaller σ (interfacial tension,
the left-hand side branches of curves in Figure ), the film lifetime increases sharply with
the decrease in the interfacial tension, which shows that the concentration
of surfactants greatly affects the film lifetime of the O/W droplet.
At the same time, it was also found that with the increase in the
oil droplet size, the influence of surfactants on the film lifetime
gradually weakened, and the reduction range gradually became smaller.
Influence of Polymers on the Lifetime of
the O/W Interfacial Film
As eq deforms and reassigns A–E, the mathematical model of the film lifetime and viscosity
can be described as eqTaking the size of the oil
droplet
as 2, 3, 4, and 5μm, the values of A–F can be calculated, and the mathematical relationship between
the film lifetime and viscosity is shown in Figure .
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.
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 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 concentration, and the stability of the
oil droplet increases with the polymer concentration. At the same
time, it can also be found from Figure 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]
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. Only a few studies
described quantitative theoretical analyses.[43] These works provide valuable insight into the mechanism of emulsion
formation and a method to determine and interpret the key parameters
of emulsion formation, including the reaction order, rate constant,
and half-life.Based on the stability model established by Civan,
the influence of alkali, surfactant, and polymer on oil droplet dynamics
has been analyzed. According to the stability model, the instantaneous
demulsification rate can be calculated by eq where X is the demulsification
rate of the emulsion at time t, Xf is the maximum demulsification rate of the emulsion,
and n is the reaction order during the demulsification
process of the emulsion, n = 0.4.[44] The initial state is defined as X = 0
and dt = t, and eq is organized as eq where td is the
delay time of emulsion instability, a plot of Xf1– – (Xf – X)1– vs t – td should yield a linear correlation, and the slope of m is equal to (1 – n)kd. Therefore, the rate constant of emulsion instability (kd) can be defined as eqThe half-life of
the O/W emulsion from ASP flooding can be determined
using eq by combining eqs and 8
Effect
of Alkali on the Stability Dynamic
Characteristic 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– – (Xf – X)1– with t – td. Therefore, the slope m can be obtained by linear fitting of scattered points,
as shown in Figure .
Figure 8
Straight-line plot of the present data of the fraction of separated
water from various emulsions vs time with different alkali additions.
Straight-line plot of the present data of the fraction of separated
water from various emulsions vs time with different alkali additions.According to eq ,
the instability rate of the O/W emulsion from ASP flooding can be
calculated. Finally, according to eq , the half-life of oil droplets can be calculated.
The results are shown in Table .
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
Effect of Surfactant
on the Stability Dynamic
Characteristic of Emulsions
The emulsions used in the tests
were prepared by mixing water samples containing 0.025%, 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 and Table .
Figure 9
Straight-line
plot of the present data of the fraction of separated
water from various emulsions vs time with different surfactant additions.
Table 2
Effect of Surfactant on the Instability
Rate and Half-Life of the Oil–Water Emulsion
mass percentage (%)
(1 – n)kd
kd (h–1)
(t – td)1/2 (h)
0.025
0.1132
0.1887
2.1226
0.05
0.1102
0.1837
2.1333
0.1
0.0642
0.1070
2.4333
0.2
0.0507
0.0845
2.4510
Straight-line
plot of the present data of the fraction of separated
water from various emulsions vs time with different surfactant additions.
Effect
of the Polymer on the Stability Dynamic
Characteristic of Emulsions
The emulsions used in the tests
were prepared by mixing water samples containing 150, 300, and 450
mg/L HPAM; 0.1% SDBS; and 200 mg/L NaOH and emulsifying them for 10
min with a speed of 1500 rpm. The calculation steps are the same as
above, and the results are shown in Figure and Table .
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
Straight-line plot of the present data of the fraction
of separated
water from various emulsions vs time with different PAM additions.
Microscopic Mechanism of the Influence of
ASP on the Stability of O/W Emulsions
The stability of O/W
emulsion from ASP flooding is related to many factors, such as the
composition and ratio of the two phases, particle size and distribution,
temperature, viscosity, and properties of the interfacial film. Among
them, the interfacial properties including interfacial film strength,
ζ potential, and interfacial tension play a vital role in the
stability of the emulsion.[45−47]
Influence
of ASP on O/W Interfacial Strength
It can be seen from Table that with the increase
in the NaOH concentration, the instability
rate of the O/W emulsion gradually decreases and the half-life of
instability gradually increases. The reason is that NaOH reacts with
acidic substances in the oil phase to form certain surfactants, which
improves the strength of the interfacial film.[39] The influence of surfactants on the oil–water interface
film is shown in Figure and Table . With
the increase in the surfactant concentration, the lifetime of the
O/W droplet and the half-life of instability increase and the instability
rate constant decreases, indicating that the increase in the surfactant
enhances the strength of the oil–water interface film of the
emulsion. This is because the increased surfactants are arranged more
closely at the oil–water interface, increasing the strength
of the interface film.[26] The influence
of the polymer on the oil–water interface film is shown in Figure and Table . With the increase in the HPAM
concentration, the lifetime of the interfacial film and the instability
rate of the oil–water emulsion gradually decrease and the half-life
of droplet demulsification increases, which shows that the increase
in the polymer concentration improves the strength of the oil–water
interface film. This is due to the adsorption and orientation of a
high concentration of polymers at the interface between the solution
and the oil phase, forming a tightly arranged oil–water interface
film, which increases the viscoelasticity of the oil–water
interface film, thereby improving the strength of the film.[48,49]
Influence of ASP on the Interfacial Tension
The interface between two immiscible fluids has high interfacial
tension, which produces droplets of one liquid dispersed in a second
immiscible liquid, forming an inherently unstable system. The interfacial
tension reflects the adsorption of active substances at the interface.
Therefore, the study of interfacial tension can explain the influence
of ASP on the oil–water interfacial film, and then, dynamic
characteristics of the emulsion are further discussed.[49]As shown in Figure a, the interfacial tension first decreases
and then slightly increases with the increase in the NaOH concentration.
This is because NaOH can react with acidic substances in the oil phase,
which can adsorb at the oil–water interface and decrease the
interfacial tension. When the concentration of NaOH is higher than
200 mg/L, all acidic substances react, and NaOH has no obvious effect
on the interfacial tension. As shown in Figure b, the interfacial tension decreases as
the surfactant concentration increases. When the surfactant content
is less than 0.1%, the interfacial tension decreases sharply. While
continuing to increase the surfactant content, the interfacial tension
slowly decreases. This is because 0.1% surfactant can make the oil–water
interface adsorption saturated. As shown in Figure c, as the polymer concentration increases,
the oil–water interfacial tension remains unchanged, which
shows that the polymer has a small effect on the interfacial tension.
Furthermore, the lower interfacial tension also benefits from the
salinity of the oil–water system, which increases the activity
of the surfactant molecules and helps reduce the interfacial tension.[28]
Figure 11
Influence of alkali (a)–surfactant (b)–polymer
(c)
on the interfacial tension.
Influence of alkali (a)–surfactant (b)–polymer
(c)
on the interfacial tension.
Influence of ASP on ζ Potential
The ζ potential is the main parameter describing the interface
charge of the dispersed droplets. Its absolute value characterizes
the magnitude of the charge on the surface of the droplets. It is
related to the structure of the charge layer and reflects the strength
of the charge repulsion between the dispersed droplets. It is generally
believed that a larger ζ potential led to a more stable emulsion.[17] The influence of ASP on the ζ potential
is shown in Figure .
Figure 12
Influence of alkali (a)–surfactant (b)–polymer (c)
on the ζ potential.
Influence of alkali (a)–surfactant (b)–polymer (c)
on the ζ potential.As shown in Figure a, as the NaOH concentration increases, the ζ potential first
decreases and then rises slightly. The reason may be that the anionic
surfactant generated by sodium hydroxide and acidic substances in
the oil sample increases the negative charge density at the oil–water
interface and the ζ potential decreases at low concentrations.[31] As the concentration of sodium hydroxide increases,
sodium ions play a dominant role in the compression of the interfacial
diffusion double layer, thereby increasing the ζ potential.
As shown in Figure b,c, surfactants and polymers have similar effects on the ζ
potential. As their concentrations increase, the ζ potential
decreases. This is mainly because both the surfactant molecules and
polymer molecules adsorbed at the oil–water interface are negatively
charged. As their concentrations increase, the repulsive force between
the charges increases, making the polymers tightly arranged at the
oil–water interface. The ability of oil droplets to coalesce
decreases, which leads to an increase in the absolute value of the
ζ potential, and the influence of surfactants is greater.[50]
Conclusions
The influence of the alkali, surfactant, and polymer concentration
on the stability of droplets was analyzed using a lifetime model of
the O/W interfacial film. The dynamic characteristics of the O/W emulsion
from ASP flooding conform to the emulsion stability model based on
two-phase separation, which is closely related to the properties of
the oil–water interface. While the strength of the oil–water
interfacial film increases with the increasing alkali concentration
at a low alkali concentration (cNaOH <
200 mg/L), the rate constant kd decreases
and the emulsion stability increases. While the strength of the oil–water
interfacial film decreases with the increasing alkali concentration
at a high alkali concentration (cNaOH >
200 mg/L), the rate constant kd increases
and the emulsion stability decreases. Furthermore, the strength of
the oil–water interface film increases with the increasing
surfactant and polymer concentration, the rate constant kd decreases, and the stability of the emulsion increases.
The mechanism of stabilization of the O/W emulsion by ASP can be described
as follows: alkali and surfactants reduce the interfacial tension
and increase the interfacial strength, and the polymer only increases
the strength of the interface film by increasing the viscoelasticity
of the oil–water interface film.
Experimental
Section
Chemicals and Materials
Diesel was
supplied by a gas station in Daqing (Heilongjiang Province, China).
Sodium hydroxide (NaOH) was purchased from Liaoning Quanrui Reagent
Co., Ltd., China. SDBS was purchased from Aladdin Chemistry, Shanghai,
China. Polyacrylamide (HPAM, Mw ∼
5 × 106, 99%) was obtained from the Tianjin BA Chemical
Reagent Factory. Sodium carbonate (Na2CO3),
calcium chloride (CaCl2), sodium chloride (NaCl), sodium
sulfate (Na2SO4), sodium bicarbonate (NaHCO3), and magnesium chloride hexahydrate (MgCl2·6H2O) were purchased from Macklin Chemical Reagent, Shanghai,
China. All chemicals are of analytical grade and directly used without
further treatment.
Emulsion Preparation
The water samples
used in the experiment are prepared according to the analysis data
of the produced water from ASP flooding. The total salinity is 4600
mg/L, and the salt content is shown in Table .
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
A model O/W emulsion was obtained
by mixing diesel containing 200
mg/L NaOH, 0.1% SDBS, and PAM with deionized water (Vdiesel/Vwater = 3:4) and emulsifying
it for 10 min with a speed of 1500 rpm.
Emulsion
Test and Performance Evaluation
To evaluate the stability
of the oil–water emulsion from
ASP flooding, the tubes with stoppers were filled with 50 mL of the
model emulsion. To record the volume of the water layer every 0.5
h and calculate the water separation ratio Wd, the formula in eq is used
Authors: Ian M Tucker; Jordan T Petkov; Craig Jones; Jeffrey Penfold; Robert K Thomas; Sarah E Rogers; Ann E Terry; Richard K Heenan; Isabelle Grillo Journal: Langmuir Date: 2012-10-09 Impact factor: 3.882