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SPE-191947-MS

Novel Eco-Friendly Cationic Surfactant for Improving Oil Recovery from


Carbonate Reservoirs

Manoj Kumar Valluri, Robert Cain, and Ramanathan Lalgudi, Battelle

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Asia Pacific Oil & Gas Conference and Exhibition held in Brisbane, Australia, 23–25 October 2018.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
not be copied. The abstract must contain conspicuous acknowledgment of SPE copyright.

Abstract
Cationic surfactants have been proven to be highly effective in improving oil recovery in carbonate
reservoirs with low surfactant loss due to adsorption. However, toxicity concerns and the cost of formulation
have impeded their widespread usage in the oil and gas industry. Our study focuses on developing an
economic and environmentally friendly solution to this challenge.
Soybean oil was used as the raw material to synthesize a surfactant that had 3 cationic sites. The resulting
formulation, in conjunction with an ethanol co-solvent, was tested for emulsion and rock-fluid behavior
with dolomitic reservoir rocks and oil sampled from a producing well in Morrow County, Ohio. Interfacial
tension (IFT) and contact angle measurements were conducted to characterize rock-fluid behavior of the
surfactant. Estrogenic and anti-estrogenic activity were evaluated to help understand its environmental
impact. Finally, oil recovery was measured using spontaneous imbibition tests and the results were compared
to those obtained using cationic and anionic surfactants supplied by a commercial vendor. All the tests
were conducted at standard atmospheric conditions except the imbibition studies, which were conducted
at reservoir temperature.
Our soy-based surfactant reduced the IFT by 60% and changed wettability from oil-wet to water-wet at
concentrations lower than 3 gpt. No estrogenic or anti-estrogenic activity was detected for the surfactant at
very high testing concentrations. The soy-based surfactant outperformed both the commercial anionic and
cationic surfactants in imbibition tests recovering 35% of the oil originally in place (OOIP) inside the rock
while the commercial cationic and anionic surfactants recovered 27% and 18% of OOIP, respectively.
These encouraging results suggest that our soy-based surfactant has the potential to provide cheap
and eco-friendly solutions for improving oil recovery from tight carbonate reservoirs in addition to other
potential near-wellbore performance enhancements that are currently being investigated. We believe this
novel additive has the potential to solve oil recovery and near-wellbore issues at a lower cost to the operator
and lesser impact on the environment compared to the products in use today.

Introduction
Surfactants can reduce the surface energy at the interface between two immiscible liquids, usually oil
and water, and are thus instrumental in reducing the interfacial tension between crude oil and injection
2 SPE-191947-MS

water or brine which facilitates the movement of treatment fluid into tight pore spaces and mobilization
of the trapped oil. They are used to accomplish a multitude of tasks in the oilfield industry. They form a
major component of well injection and treatments fluids as they aid in cleaning the near wellbore damage,
preventing microbial corrosion, reducing interfacial tension (IFT) between the oil and water phases and
improving oil recovery from oil-wet and tight rocks. Consequently, there are a host of chemicals available
in the market which function specifically to accomplish one or a combination of functions depending on the
rock and fluid conditions in the reservoir. Some of the functions of surfactants include emulsification and
demulsification, biocidal activity, wellbore cleanup and improved oil recovery (IOR). Selection of surfactant
is thus dependent on the effect desired and reservoir rock properties. In this study, we investigate the use
of a cationic surfactant for improving oil recovery from a dolomitic reservoir by altering the rock-fluid
interactions between reservoir crude oil and the rock surface. A typical IOR surfactant affects the rock fluid
behavior by reducing the interfacial tension (IFT) between crude oil and injection water/brine, and altering
the wettability, i.e., the wetting tendency of the reservoir rock from a native oil-wet state to a more water-
wet state, which is more conducive to fluid injection and oil displacement from the rock matrix and into
the bulk fluid phase.
Cationic surfactants are preferred for carbonate formations because they bear the same charge as the
reservoir rock meaning adsorption of surfactant on to the rock surface is not a concern. This implies that
a majority of the surfactant can be retained by the bulk fluid phase that acts on the crude oil adsorbed on
to the reservoir rock and strips it into the aqueous phase. Austad and Milter (1997) conducted imbibition
experiments on oil-wet chalk samples using dodecyltrimethylammonium bromide (C12TAB), a cationic
surfactant. It was deduced that the cationic surfactant altered the wettability of the rock from oil-wet to
water-wet and recovered nearly 65% of OOIP inside the chalk sample. Stadness and Austad (2003) also
conducted tests on oil-wet carbonate rock samples using C12TAB and concluded that concentration of
the surfactant plays a key role in determining the efficiency of a surfactant solution in forming ion pairs
with carboxylates from crude oil that are adsorbed on to the rock surface. Desorption of these carboxylates
switcehs the wettability of the rock to water-wet and consequently improves oil recovery.
However, the use of surfactants in the oil industry is not so straightforward as many of them, particularly
cationic surfactants, may lead to harmful environmental effects as pollution of groundwater thereby
affecting aquatic ecosystems (Ostroumov, 2006). Cationic surfactants are used in the oilfield as biocides,
emulsifiers, demulsifiers and wetting agents. Functional groups in these surfactants can range from amines
that are functional in acidic environments to quaternary ammonium salts that bear a permanent positive
charge. Despite their varied applications, cationic surfactants do not contribute to the chemical treatment
recipes for injection as much as anionic or nonionic surfactants, because cationic surfactants possess acute
aquatic toxicity and very low intermediate biodegradability (Belgacem and Gandini, 2008). For instance,
cationic surfactants such as quaternary ammonium compounds (QAC) may have a negative impact on
bacteria and fungi by altering their estrogenic and anti-estrogenic activity. Holmberg (2003) discussed the
aquatic toxicity of conventional cationic hexadecyl trimethyl ammonium bromide (HTAB) and suggested
that these compounds are highly toxic and their toxicity increases with their hydrophobicity. The impact of
discharging surfactants into the environment can cause water pollution problems if the surfactants do not
degrade biologically and accumulate in groundwater systems. This is typically the case with most cationic
and nonionic surfactants used in the treatment of wells owing, leading to operators spending large sums of
money treating the produced water before reusing it or injecting it into deep saline aquifers for storage.
With increased concern for environmental safety as well as a bearish oil price environment, the oilfield
chemical industry needs to focus on economically and environmentally viable alternatives to those currently
available to reduce costs and the environmental impact of injection chemicals.
SPE-191947-MS 3

Experimental Studies
Materials
Surfactants. A cationic surfactant (v1) was developed using epoxidized soybean oil intermediates that are
generally recognized as safe (GRAS). The molecule contained 9-12 positively charged sites. Initial tests
with this molecule suggested steric hindrance induced by the triglyceride backbone might potentially limit
the effectiveness of the molecule. Accordingly, another version (v2) of the molecule with the capability to
hold 3 cationic sites was formulated using the same substrate by a different methodology. Since the original
surfactant is sparingly soluble in water, a co-solvent was required to improve solubility. Ethanol was used
as an eco-friendlier co-solvent than traditionally used methanol. Co-solvent was added to a fixed weight
of surfactant and solubility was observed visually as the co-solvent concentration was increased at each
step. The final surfactant cocktail used for testing was a 33.33% w/w solution of pure surfactant in ethanol
co-solvent.
Also, for a comparative study of oil recovery using spontaneous imbibition tests, two commercial
surfactants; one anionic (CS1) and another a mixture of anionic and cationic groups (CS2), both having a
carbon chain length similar to Battelle's surfactant were picked. Table 1 shows the chemical composition of
these surfactants. These surfactants were obtained in a thick resin like state and had to be mixed with a co-
solvent for further testing. Both the commercial surfactants were dissolved in ACS grade ethanol to form
33.3% w/w solutions of surfactant in ethanol. All the aqueous surfactant solutions for testing were prepared
using HPLC grade water as the solvent.

Table 1—Commercial surfactants used for oil recovery comparison tests

Surfactant name Functionality Major components Composition

A1 Anionic 2-Hexyldecan-1-ol/propoxylate sulfate 90%

C14-15 alcohol/branched and linear/


90%
AC1 Anionic + Cationic propoxylated/sulfated/monoisopropa-nolamine salt

C14-15 alcohol/branched and linear/propoxylated < 8%

Reservoir rocks. This study focused on the Copper Ridge dolomitic reservoir in central Ohio. Cores were
obtained from a vertical well drilled in Morrow county. The zone of interest has a gross thickness of 186 ft.
and a net thickness of 166 ft. providing enough depth to obtain numerous samples and core data. Sidewall
cores in this zone were found to contain hydrocarbons and the oil-water transition zone is estimated to lie
towards the bottom end of this zone. The reservoir initial pressure and temperature are 1120 psi and 91°F.
The zone of interest ranges from 3026 ft. to 3031 ft. as this is a zone with good permeability (>100 mD)
and porosity (~9%). Lithology of this zone is majorly composed of dolomite (94% by mass). A list of cored
plugs is shown in Table 2. All the rock sample including chips, trims and whole core plugs were aged in
reservoir crude oil at a temperature above reservoir temperature (110°F) to accelerate restoration to their
natural state.

Table 2—Core plug samples used for rock-fluid tests

Sample # Depth (ft) Length (in) Diameter (in) Porosity (%) Permeability (mD)

1-49-1 3030.60 2.0350 0.9970 9.3 228

1-49-2 3030.70 2.0555 0.9960 9.3 228

1-49-3 3030.80 2.0775 1.0000 9.3 228

1-49-4 3030.90 2.0705 1.0000 9.3 228


4 SPE-191947-MS

Sample # Depth (ft) Length (in) Diameter (in) Porosity (%) Permeability (mD)

1-50-1 3031.00 2.0790 0.9950 9.3 76.2

Reservoir Oil. The reservoir oil sample used for testing was obtained from a different well which is less
than a mile away from the well that was used to sample core. The oil is a medium to heavy fluid with peak
in between octane and decane. This oil was used to age the rock samples which were assumed to have no
in-situ fluids. The density of the oil sample was found to be 0.82 g/cc at reservoir temperature.

Hormonal Activity Tests


Toxic chemicals typically tend to influence the endocrine system of animals, the result of which is a
disruption in their estrogenic (EA) and anti-estrogenic activity (anti-EA). Hence, testing the soy-based
surfactant for EA and anti-EA would serve as a preliminary indictor to its toxicity. A robotic BG1Luc assay
developed by Stoner, Yang, and Bittner (2014) was used for testing the soy-based surfactant for endocrine
activity. This test had a higher accuracy, greater sensitivity and greater repeatability than many other assays
that are approved by the Interagency Coordinating Committee on the Validation of Alternative Methods
(ICCVAM) and are accepted by the Environmental Protection Agency (EPA). Further information on the
test method can be found in Stoner, Yang, and Bittner (2014). Testing was conducted by CertiChem who
characterized the estrogenic and anti-estrogenic activity of the soy-based surfactant. The reference table for
test results is shown in Table 3.

Table 3—Hormonal activity test protocols

Controls (positive/
Test Activity detectable Activity not detectable
negative)

%RME2 < 3*SD of


Estrogenic Activity 17-beta estradiol/ethanol %RME2 >= 3*SD of VC inhibited by ICI
VC inhibited by ICI

%RMICI < 3*SD of LE2


Anti-estrogenic activity ICI 182,780/ethanol %RMICI >= 3*SD of LE2 and reversed by HE2
or not reversed by HE2

Interfacial Tension Measurements


IFT was measured using the Du Nuoy method which uses a platinum ring that contacts the immiscible
fluids and measures changes in force as it passes through their interface. Tension at the interface is then
calculated using the recorded force and the diameter of the ring. For oil-water IFT measurements, the ring
is originally placed in the aqueous phase and the liquid level is lowered to compute the force as the ring
separates from the aqueous phase and completely into the oil phase. The experimental setup comprises a
Thermo Cahn 300 series surface/interfacial tension measuring device equipped with a platinum-iridium
ring and a glass measurement cell which is about 1.5 inches in diameter. The device was calibrated before
measurements by measuring the air-water IFT which is 72 dynes/cm at standard atmospheric conditions.
All the IFT measurements were conducted at standard atmospheric conditions. Surfactant concentrations
varying from 0.5 gallons per thousand gallons (gpt) to 4 gpt were used to obtain an IFT vs. concentration
profile.

Contact Angle Measurements


Wettability was characterized by measuring the contact angle of water on aged reservoir rock in the presence
of an ambient decane phase used to mimic crude oil. The sessile drop technique was used to measure the
contact angle. In this method, a water drop is placed on the rock surface in the presence of a less dense
ambient phase such as air/oil. Devices that use this methodology are often equipped with a goniometer that
captures a snapshot/video of the drop on rock surface, which is later processed using a drop shape analyzer
SPE-191947-MS 5

(DSA) software to yield contact angle. AST Products Inc.'s Video Contact Angle (VCA) Optima was the
instrument used for this study. The device interfaced with VCA OptimaXE image processing software to
capture and analyze rock-fluid snapshots. Contact angles ranging from 0° to 60°, 60° to 120° and 120° to
180° are employed for water, intermediate and oil wet nature, respectively, after Wang and Gupta (1995).
All the measurements were performed at 180°F. Surfactant concentrations of 1, 2, 3, and 4 gpt were tested.

Spontaneous Imbibition
Spontaneous imbibition was conducted using a modified Amott cell which consisted of a base and top
clamped together by a pair of aluminum rings and three aluminum screws. The base holds the core sample
while the base and top parts are filled with testing/imbibing fluid. The top also has a graduated capillary
column which is meant for collecting and measuring the oil recovered from the experiment. The top of the
cell is usually plugged with a stopper or covered in parafilm to prevent loss of vapors. More details on the
construction and working of these cells can be found in Valluri et al (2017). Cylindrical whole core plugs
that were aged for 3 months were used for testing. Prior to being immersed in imbibition fluids, the aged
core samples were removed from oil and excess oil was wiped off to measure the weight of the core after
saturation. This is compared with the weight of the core before saturation and volumetric calculation are
carried out to quantify changes in saturation. This process is described by equation 1 through equation 3. It
is assumed that the cores had no oil present in them prior to aging.
(Eq. 1)

(Eq. 2)

(Eq. 3)

Where,

• Vpore = Pore volume, cc

• r = Radius of the core sample, cm

• h = Height of the core sample, cm

• Φ = Porosity, fraction

• Vo,in = Volume of oil imbibed, cc

• Wb,a = Weight of the sample before aging, g

• Wa,a = Weight of the sample after aging, g

• ρoil = Oil density at aging temperature, g/cc

• So,i = Oil saturation in the core, fraction

Once the post aging weight of samples for saturation calculations are noted, the cores are placed in
the modified Amott cells that are subsequently filled with surfactant solutions. Surfactant solutions were
prepared at 3 gpt concentration. All the experiments were conducted at reservoir temperature. Oil recovered
from the experiments was periodically monitored and converted to a normalized recovery factor based on
the oil originally in place (OOIP) using equation 4.
6 SPE-191947-MS

(Eq. 4)

Where

• Voil recovered = Volume of oil recovered (cc)

• Soi = Initial oil saturation (fraction)

• Vpore = Pore volume (cc)

Results and Discussion


Hormonal Activity Results
Battelle's soy-based surfactant containing a tri-glyceride backbone was tested for estrogenic and anti-
estrogenic activity as previously described. Results for estrogenic and anti-estrogenic activity for the
surfactant are graphically shown in Figure 1 and Figure 2. Based on test protocol criteria shown in Table 2,
it was determined that the surfactant showed no signs of estrogenic or anti-estrogenic activity.

Figure 1—Relative estrogenic activity of the soy-based surfactant compared to ethanol (VC).
Surfactant was dissolved in two media - ICI 182,780 (standard) and ethanol, for testing purposes.

Figure 2—Relative estrogenic activity of the soy-based surfactant compared to ethyl alcohol (VC).
Surfactant was dissolved in two media - 17-beta estradiol (LE2) and 5E-8M E2 (standard, HE2)

Interfacial Tension Results


Figure 3 shows the IFT vs. surfactant concentration profiles for both the versions of soy-based surfactant
obtained at standard atmospheric conditions. Surfactants v1 and v2 both reduced the IFT with increasing
SPE-191947-MS 7

aqueous concentration which is typical of most surfactants used in IOR. However, v2 resulted in lower IFT
than v2 at low concentrations of 1 gpt and 2 gpt. This confirmed our assumption that v1 being a triglyceride-
based molecule, was subjected to steric hindrance which impeded its activity at the oil-water interface and
micelle formation. This problem was eliminated by splicing the triglyceride into three sperate carbon chains
while the monomeric stearic acid-based molecules had lesser steric hindrance issues and hence, improved
activity and lower IFT at lower concentrations. Going forward, the second-generation surfactant v2, which
shall be referred to as the soy-based surfactant, was down selected for testing.

Figure 3—Changes in interfacial tension with concentration for the two versions of soy-based surfactant

Contact Angle Results


Prior to contact angle measurements, the reservoir rock chips were aged as described above to restore their
native state. Figure 4 represents a plot of contact angle with respect to water (water-on-rock) vs. surfactant
concentration. The initial contact angle without any surfactant was found to be 132.6° which implies the
original state of the reservoir was oil-wet. An increase in concentration of soy-based surfactant in the
aqueous phase resulted in the reduction of contact angle implying the adhesive forces between water and
rock improved i.e., water-wetness increased. At a typical oilfield concentration of 2 gpt of the surfactant, the
contact angle was 77.4° implying mixed wetness tending towards water-wet. Figure 5 captures the profile
of water droplets on the reservoir rock at ambient conditions in the presence of an ambient decane phase.
The left and right images of the figure correspond to before and after addition of 2 gpt of the surfactant. The
water droplet tends to flatten with increasing surfactant concentration as the adhesive forces between the
aqueous phase and reservoir rock increase due to altered wettability. The primary reason for this reduction
is believed to be ion-pair formation between the cationic moieties and carboxylate groups from crude oil
that originally adsorb on to the positively charged carbonate rock surface. It is essential to note that all the
contact angle measurements were at ambient temperature and increasing temperature would only lower the
contact angle values as noted by Anderson (1986)1. Hence, it is safe to say the surfactant will likely reduce
the contact angle to a lower value at reservoir temperature. Therefore, it is understood that the soy-based
surfactant has the potential to alter the wettability of an oil-wet carbonate reservoir rock to a more water-
wet state.
8 SPE-191947-MS

Figure 4—Change in contact angle for a water in decane on rock system


with increasing aqueous phase concentration of the soy-based surfactant

Figure 5—Water drop profile on reservoir rock in the presence of an ambient decane
phase before (left) and after the addition of 2 gpt (right) of soy-based surfactant

Spontaneous Imbibition Results


Spontaneous imbibition experiments were conducted to evaluate the impact of rock-fluid behavior
alterations of the soy-based surfactant on oil recovery from the carbonate reservoir. Prior to imbibition
testing, whole core plugs used in the tests were aged in reservoir crude oil and the resulting saturation
changes within the core are calculated volumetrically as previously described in equation 1 through equation
3. Table 4 shows the weight, volume, and percent change in saturation of oil in the core plugs. It was
assumed that the cores contained no oil in them prior to aging. Thus, the change in oil saturation within
the core is assumed to be initial oil saturation before the experiment and this ranged from 50% to 90%.
Recovery factor was calculated as shown in equation 4 to facilitate a fair comparison the performance of
all the imbibing fluids.

Table 4—Saturation changes due to aging process of core samples

Change in
Sample # Weight pre-aging (g) Weight post-aging (g) Weight of oil in (g) Volume of oil in (cc)
saturation (%)

1-49-1 64.82 66.57 1.74 2.12 87.67

1-49-2 66.41 68.19 1.78 2.17 88.82

1-49-3 68.36 69.74 1.38 1.68 67.46

1-49-4 68.89 70.21 1.32 1.61 64.80

1-50-1 69.99 71.07 1.08 1.32 52.41


SPE-191947-MS 9

Baseline test. Initial imbibition testing focusing on establishing a baseline recovery where water without
any additives was used as the imbibing fluid. Next, imbibing fluid containing 3 gpt of soy-based surfactant
was used to quantify the change in oil recovery due to the addition of soy-based surfactant. Figure 6 shows
the plot of recovery factor vs. time for the baseline case for pure HPLC grade water and an aqueous solution
of 3 gpt soy-based surfactant as imbibing fluids. Water recovered 14% OOIP while the soy-based surfactant
recovered 35% OOIP, which is about 1.5 times more than the base water case. Hence, it is evident that the
soy-based surfactant can potentially improve oil recovery by favorably altering rock-fluid behavior in the
tested carbonate reservoir.

Figure 6—Change in oil recovery factor with time for pure water and water with 3 gpt of soy-based surfactant

Comparison test. Once the baseline comparison was established, the next step was to compare the soy-
based surfactant‘s performance with that of some commercially available surfactants. The two commercial
surfactants CS1 and CS2 used for this purpose were chosen from a group of commercial surfactants that
were available in house because their alkyl chain length was close to that of Battelle's soy-based surfactant.
The composition of these surfactants is listed in Table 1. All the imbibing fluids contained 3 gpt of surfactant
in them. Before preparing aqueous solutions, the commercial surfactants had to be mixed with an ethanol co-
solvent as previously described. The results from comparative oil recovery tests for the surfactants employed
in this study are shown in Figure 7. An initial observation is that the soy-based surfactant outperformed the
commercial surfactants used in this study. Surfactants CS-1 and CS-2 recovered 18% and 27% of OOIP
while the soy-based surfactant recovered 35% OOIP as previously established. This can be attributed to the
difference in functionality of the surfactants as anionic moieties tend to be adsorbed onto a carbonate rock
surface. This reduces the penetration of surfactant deeper into the rock and thereby its ability to alter rock
behavior. Electrostatic repulsion between cationic moieties of the soy-based surfactant and the positively
charged carbonate rock ensure surfactant adsorption is very limited and hence, most of the surfactant remains
in solution and penetrates deeper into the reservoir rock. Accordingly, more surface area is contacted by the
surfactant which leads to stripping of more oil from the surface and higher oil recovery.
10 SPE-191947-MS

Figure 7—Oil recovery performance of soy-based surfactant compared to two commercial surfactants

Conclusions
A cationic surfactant with three positively charged sites was developed using epoxidized soybean oil as
a starting material. The resulting soy-surfactant was tested using an EPA approved technique to for signs
of estrogenic or anti-estrogenic activity in test samples. The surfactant also blended well with water in the
presence of an ethanol co-solvent and this mixture was used to characterize its effectiveness in altering rock
fluid behavior in a carbonate reservoir at ambient conditions. The following conclusions were drawn based
on the testing methodology outlined:
1. The soy-based surfactant showed no evidence of estrogenic or anti-estrogenic activity, which is a good
starting point towards an environmentally friendly formulation.
2. The soy-based surfactant was effective in reducing interfacial tension between oil and water as well
as altering wettability of the reservoir rock from a native oil-wet state to an intermediate-wet state
tending towards water-wet. It can be safely assumed the end state would be predominantly water-wet
at reservoir conditions as elevation in temperature enhances water wetness.
3. Spontaneous imbibition tests conducted to quantify oil recovery suggested that the soy-based
surfactant can improve oil recovery by favorably altering the rock-fluid behavior as well as out-
perform some commercially available products.
SPE-191947-MS 11

Table 5—Results for water and brine imbibition tests

Final penetration
Final contact
Fluid Sample IFT (mN/m) magnitude Oil Recovery (%OOIP)
angle (degrees)
(Hounsfield Units)

Water 1 34.03 85.3 8 1.9

2.5 wt% NaCl 2 31.57 41.1 14 8.1

5 wt% CaCl2 3 29.33 44.8 12 7.3

Acknowledgments
That authors would like to thank the Ohio Soybean Council for sponsoring our soy-based surfactant work.
The authors would also like to thank Barry McGraw at eh Ohio Soybean Council for his continued support
as well as Rick Peterson for his valuable inputs in preparing this manuscript.

References
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Using Surfactants. Paper SPE 37236 presented at the International Symposium of Oilfield Chemistry, Houston, TX,
USA, 18-21 February.
Stadness, D.C. and Austad, T., 2003. Wettability alteration in carbonates Interaction between cationic surfactant and
carboxylates as a key factor in wettability alteration from oil-wet to water-wet conditions. Colloids and Surfaces A:
Physiochemical Eng. Aspects, Vol. 216 (2003), pp 243–259.
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Oil Recovery from Liquid Rich Shale by Spontaneous Imbibition. Journal of Petroleum Science Research, Vol. 6
(2017), pp 1–15.

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