Spe 200182 Pa

Catanionic Surfactants for Improving Oil
Production in Carbonate Reservoirs
Limin Xu1*, Ming Han2, Dongqing Cao1, and Alhasan Fuseni2
1
Aramco Asia
2
Saudi Aramco
Summary
This paper presents the development of catanionic surfactants composed of cationic and anionic surfactants to make them high-
performance products for chemical flooding in high-temperature and high-salinity carbonate reservoirs. The objective of this study is to
optimize the surfactant chemistry by mixing oppositely charged anionic surfactants and cationic surfactants (CASs), which results in sig-
nificant synergistic effects in interfacial properties due to electrostatic attraction to improve oil production at the given harsh conditions.
The optimal mixing surfactant ratios were determined according to the brine-surfactant compatibility, microemulsion phase behavior,
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and the interfacial tension (IFT) between oil and surfactant solutions in high-salinity brine at 90°C. Comprehensive performance of the
catanionic surfactants was evaluated, including adsorption of the surfactants onto the carbonate rocks and the long-term stability at 95°C.
The coreflooding displacement experiments were performed using carbonate core plugs at 95°C to evaluate the potential of the optimal
catanionic surfactant in improving oil recovery. Three catanionic surfactants with good compatibility were developed in this study. It
appeared that the synergistic effect between the mixing surfactants was enhanced with increasing temperature. Although the IFT of the
individual surfactants with crude oil was between 10−1 and 100 mN/m, a significant IFT reduction in the magnitude of 10−2 to 10−3 mN/m
was observed by mixing the selected anionic surfactants and CASs. A salinity scan showed that the IFT values maintained a value of
10−2 mN/m in a wide salinity range, which demonstrated the effectiveness of the catanionic surfactant. In microemulsion phase behavior
studies, the developed catanionic surfactant solution in the presence of crude oil exhibited Winsor Type III emulsions. The static adsorp-
tion quantities of the catanionic surfactants were lower than the values of the individual surfactants. All these indicated the feasibility of
catanionic surfactants for their applications in the harsh reservoir conditions. The results of coreflooding displacement tests demonstrated
significant oil recovery improvement beyond waterflooding. This work provides an efficient way to get surfactant formulations by mixing
oppositely charged surfactants to obtain high performance in improving oil production under harsh conditions.
Introduction
Surfactants have been widely used in chemical flooding for several decades to mobilize trapped oil and increase oil production. The main
function of a surfactant is reducing the IFT between crude oil and injected fluid to an ultralow value, which leads to a significant increase
in the capillary number, indicating high oil production potential (Lake 1989).
Traditionally, either anionic or amphoteric surfactants were used for the purpose of reducing IFT between crude oil and water. It is
usually difficult to use a single surfactant to reduce the IFT to an ultralow level (10−3 mN/m), especially for harsh reservoir conditions
with high salinity and high temperature. The success of surfactant application in chemical flooding relies on properly tuning the surfactant
chemistry by use of synergistic surfactant mixtures for particular reservoir conditions. Many different kinds of surfactant mixtures were
investigated, including anionic/nonionic (Falls et al. 1994; Mulqueen and Blankschtein 2002; Mahajan and Nandni 2012; Mandal and Kar
2016), anionic-nonionic/nonionic (Taylor and Nasr-El-Din 1996; Liu et al. 2014), anionic-nonionic/anionic (Flaaten et al. 2009; Sahni
et al. 2010), anionic-nonionic/ amphoteric (Zhang et al. 2015), nonionic/nonionic (Katarzyna and Bronislaw 2007), and cationic/nonionic
(Saien and Asadabadi 2011) surfactants.
Because synergism increases with the degree of charge difference, synergism between anionic/anionic or nonionic/nonionic surfac-
tants is less than that between anionic/nonionic or cationic/nonionic surfactants, which in turn is less than that between cationic/anionic
surfactants (Rosen and Hua 1982; Rosen 2004). Consequently, the higher synergism is obtained by mixing anionic surfactants and CASs.
The mixture of cationic and anionic surfactant is also called catanionic surfactant. It attracted a lot of attention in the past few decades (Yu
and Zhao 1989; Jonsson et al. 1991; Huang and Zhao 1995; Wellington and Richardson 1997; Gogoi 2010) due to the unique interfacial
properties caused by the strong electrostatic interaction between the oppositely charged head groups. Due to the risk of precipitation
(Stellner et al. 1988; Amante et al. 1991; Bergstrom 2001), only a limited number of catanionic surfactants for chemical flooding were
used in the applications (Zhao et al. 2014; Zhang et al. 2015; Li et al. 2016, 2020, 2021; Jia et al. 2017, 2019; He and Xu 2018; Kumari
et al. 2019). These studies show that effective catanionic surfactants have ultralow critical micelle concentration as well as much lower
IFT than the individual surfactants. Field applications of surfactant/polymer and alkali/surfactant/polymer using catanionic surfactant
demonstrated its potential for improving oil production (Li et al. 2020, 2021). To date, these studies were conducted for sandstone reser-
voirs and conditions with low temperature and low salinity (Zhao et al. 2014; Kumari et al. 2019; Li et al. 2016, 2020, 2021) or high
salinity without divalent ions (Zhang et al. 2015; Jia et al. 2017, 2019). The highest temperature in literature is 85°C (Jia et al. 2019). Both
high temperature and high salinity, especially with high hardness, affect the chemical compatibility and effectiveness. Moreover, over
60% of the worldwide hydrocarbon reserves are held in carbonate reservoirs (Jordan Jr. and Wilson 1994; Han et al. 2013), and more and
more reservoirs found recently have harsh conditions; hence, it is essential to develop chemicals for harsh carbonate reservoirs.
The objective of this work is to develop high-performance catanionic surfactants for harsh carbonate reservoir conditions with high
salinity (57,670 ppm) and high temperature (≥90°C). Four different kinds of surfactants were selected, and three catanionic surfactants
were developed. Compatibility, IFT, adsorption, and long-term stability were evaluated, and the effects of salinity and temperature on
*Corresponding author; email: limin.xu@aramcoasia.com

Copyright © 2023 Society of Petroleum Engineers
This paper (SPE 200182) was accepted for presentation at the SPE Conference at Oman Petroleum & Energy Show, Muscat, Oman, 21–23 March 2022, and revised for publication.
Original manuscript received for review 29 April 2022. Revised manuscript received for review 13 July 2022. Paper peer approved 8 August 2022.
88 February 2023 SPE Reservoir Evaluation & Engineering

synergism were studied. Coreflooding displacement tests were conducted at high-temperature and high-salinity conditions to evaluate the
performance of the catanionic surfactants on improving oil production.
Experimental Material
CAS series CAS-1, CAS-2, and CAS-3 and anionic/nonionic surfactant (ANOS-1) were selected to develop the synergistic catanionic
surfactants. ANOS-1 is alkylphenol ethoxylate carboxylate provided by Sinopec Shanghai Research Institute of Petroleum Technology
with active content of 50%. CAS-1, CAS-2, and CAS-3 are analytical-reagent grade quaternary ammonium salts with different chain
lengths purchased from Sinopharm Chemical Reagent Co., Ltd. The chain length of CASs is CAS-1 < CAS-2 < CAS-3. The crude oil
used is a light oil with density of 0.882 g/cm3 at 25°C and 0.836 g/cm3 at 90°C. High-salinity water (HSW) with total dissolved solids of
57,670 ppm was used in this study. Synthetic connate water was used for core-plug saturation in coreflooding tests. The compositions of
connate water and the HSW are listed in Table 1. Deionized water produced by a Barnstead Genpure water system was used to prepare
the brines.
Composition Connate Water HSW

+
Na (mg/L) 59 491 18 300
Ca2+ (mg/L) 19 040 650
Mg2+ (mg/L) 2439 2110
Cl− (mg/L) 132 060 32 200
HCO3− (mg/L) 354 120
−
SO4 (mg/L) 350 4290
Total dissolved solids (mg/L) 213 734 57 670
Table 1—Compositions of connate water and HSW.
Solution Preparation. The 1 wt% stock solutions of single surfactants in HSW were first prepared to conveniently prepare 0.2 wt%
catanionic surfactants with different mixing ratios. When the target volume of 0.2 wt% catanionic surfactants is small, it is difficult
to prepare the mixture using 50% ANOS-1 and CAS in solid form. The 1 wt% stock solutions of CASs were prepared by dissolving
surfactant powder in HSW. The 1 wt% stock solution of ANOS-1 was prepared by diluting 50% ANOS-1 using HSW. The preparation
procedure of 0.2 wt% catanionic surfactants in HSW with different mixing ratios was as follows: (1) Add certain amount of HSW; (2) add
specific amount of 1 wt% stock solution of ANOS-1; (3) add specific amount of 1 wt% stock solution of CASs; and (4) stir the solution for
10 minutes. The solutions were all prepared at room temperature. The pH of the 1 wt% stock solutions and 0.2 wt% catanionic surfactants
was between 6 and 7.
Compatibility Test. Surfactant solutions were prepared and placed at 25 and 95°C for 1 day. The appearance of surfactant solutions in
HSW was observed visually to determine the compatibility. The compatibility results were recorded by the compatibility codes of (A)
clear solution, (B) slightly hazy solution, (C) hazy solution, and (D) precipitation.
IFT Measurement. IFT was measured by spinning drop tensiometer SVT 20 with video camera at 25 and 90°C, respectively. The oil
drop size was about 0.4 μL. The rotation speed used was 5,000 rev/min. Vonnegut formula was used to calculate IFT when the ratio of
the drop length to the drop diameter was larger than 4.0, otherwise the Laplace-Young formula was used.
Phase Behavior Experiment. The phase behavior test results were recorded by visual inspection to determine the microemulsion type
and volume of aqueous phase, middle phase, and oleic phase. One milliliter of surfactant solution and an equal amount of crude oil were
added to a 5-mL pipette. A record of the initial volume of aqueous phase and oleic phase was made, and the pipette was sealed with
epoxy adhesive and then placed in a test tube filled with transparent silicone oil. The tubes were placed in a dry bath heated to 95°C.
Equilibration volumes of aqueous phase and oleic phase were recorded after about 1 hour of heating. The tubes were overturned to mix the
solution and hydrocarbon completely. Thereafter, the tubes were overturned daily after recording the volumes of aqueous phase, middle
phase, and oleic phase.
Long-Term Stability Test. Surfactant solutions and their mixtures were prepared in a glovebox [UNIlab (1250/780)]. Nitrogen was then
injected for 4 hours to get rid of any dissolved oxygen. Ten milliliters of surfactant mixture solutions were placed into test bottles and
sealed tightly. The solutions were then placed in the 95°C oven for aging. Periodic measurements of solution properties were made to
determine long-term stability.
Static Adsorption Test. One gram of carbonate rock grains between 60 and 80 mesh size was added to 5 mL of surfactant solution at
2,000 ppm in a 30-mL test bottle, shaken 10 times, and placed in the oven at 95°C for 1 hour. After an hour in the oven, the samples were
shaken another 10 times and left to age in the 95°C oven for 24 hours. The solutions were then centrifuged at 3,000 rev/min for 30 minutes
to separate the aqueous solution and cores. The surfactant concentration in the aqueous solution was analyzed using a total organic carbon
analyzer. The adsorption amount was quantified by mass balance usingthe following equation:
Ci Cf V
Ca = , (1)
‍ mS ‍
February 2023 SPE Reservoir Evaluation & Engineering 89

where Ca is the surfactant adsorption quantity (mg/g), Ci is the initial concentration of surfactant solution (mg/L), Cf is the surfactant
concentration remaining in the solution after adsorption (mg/L), V is the volume of solution (L) used, and mS is the mass of carbonate
cores (g).
Total Organic Carbon Measurement. Total organic carbon (TOC) analysis of surfactant amounts in solutions was performed using
TOC Analyzer (TOC-L CPH, Shimadzu, Japan). In order to optimize the TOC analysis, the solutions were diluted using deionized water.
Coreflooding Test Procedure. Three Indiana limestone core plugs with diameter of 3.8 cm and length of 7 cm were used for displacement
tests. The detailed parameters were listed in Table 2. The brine permeability is about 20 md.
Pore
Diameter Length Volume Gas Perm. Brine Perm.
Core No. (cm) (cm) (mL) Original Oil in Core (mL) Initial Oil Saturation (%) (md) (md)
1 3.81 7.15 12.028 7.777 64.66 50.41 21.2
2 3.81 7.08 10.769 7.020 65.19 55.09 22.8
3 3.81 7.00 11.609 7.331 63.15 50.45 21.6
Table 2—Core plug information.
The coreflooding test was conducted on an AFS-300 Coreflooding System, Core Lab, USA. The procedure is:
1. Saturate core plugs with connate water: The core plugs were dried at 105°C in an oven to obtain the dry weight. The gas permea-
bility of core plugs was measured using He, and then the core plugs were saturated with connate water by vacuum. The wet weight
after saturation was recorded to calculate the pore volume (PV).
2. Test the brine permeability of core plugs: (1) Precharge the accumulator with connate water; (2) load the core into the core holder;
(3) set the confining pressure to 600 psi and the backpressure to 100 psi; (4) inject the connate water into the core plug at different
flow rates; and (5) unload the core from the core holder. The differential pressure for different flow rates was recorded and used for
calculating brine permeability by Darcy’s law.
3. Saturate and age the core plugs with crude oil: The core plugs were saturated with crude oil by high-speed centrifuge at 6,000 rev/
min for 1 hour. Then, the core plugs were reversed and centrifuged again with the same rotary rate and time. The weight before
and after centrifuge was recorded to calculate the original oil in core. The saturated cores were aged at 95°C for 3 weeks for the
wettability restoration.
4. Reload the core plug and set up the coreflooding system: (1) Precharge the accumulators with crude oil, HSW, and surfactant
solution; (2) reload the aged core into the core holder; (3) set the confining pressure to 600 psi and the backpressure to 100 psi;
and (4) inject fresh oil into the core to displace the aged oil at flow rate of 0.5 cm3/min. After the replacement of aged oil
with fresh oil, set the oven to 95°C to heat the system. The confining pressure and pore pressure were increased to 4,500 and
3,100 psi, respectively.
5. Conduct water and chemical flood: The injection strategy with velocity of 0.5 cm3/min is as follows: (1) Waterflooding: When tem-
perature and differential pressure were stable, HSW was injected into the core plug until the water cut reached 100%. (2) Surfactant
flooding: 1 PV of surfactant slug was injected after waterflooding. (3) Post-waterflooding: HSW was reinjected until no oil was
produced. The produced fluid was collected at the outlet based on the calculation of the arriving time with the dead volume. The
produced oil volume was recorded with time to calculate the oil production.
Results and Discussion
Compatibility of Mixed Surfactants with HSW. To study the effect of chain length of CASs on the interaction between oppositely
charged surfactants, CAS-1, CAS-2, and CAS-3 were mixed with anionic surfactant ANOS-1. The chain length of CASs is CAS-1 <
CAS-2 < CAS-3. The developed catanionic surfactants were SD-1, SD-2, and SD-3 as listed in Table 3.
Catanionic Surfactant Anionic Surfactant CAS

SD-1 ANOS-1 CAS-1
SD-2 ANOS-1 CAS-2
SD-3 ANOS-1 CAS-3
Table 3—Compositions of synergistic catanionic surfactants.
Compatibility of chemicals with brines is critical to predict whether the chemicals can be applied successfully, since the efficiency of
chemical solutions will be greatly reduced if precipitation or insoluble particles form. Fig. 1 shows the compatibility of surfactants CAS-
1, ANOS-1, and mixture of these two components with different ratios in HSW at 95°C. The compatibility results were recorded in
Table 4 by the compatibility codes of (A) clear solution, (B) slightly hazy solution, (C) hazy solution, and (D) precipitation. CAS-1
solution was transparent with Code A. ANOS-1 solution was not homogeneous and had a hazy appearance after shaking. The solutions of
mixtures presented better compatibility. The compatibility of surfactant mixture changed from transparent to slightly hazy with the
increase of ANOS-1/CAS-1 ratio. The boundary is around 3/2. The solution became hazy when the ratio reached 7/1. Similar compatibil-
ity was observed in SD-2 and SD-3 surfactants as summarized in Table 4. Most of these surfactant mixtures with different mixing ratios
exhibited good compatibility with Code A or Code B. For SD-2 and SD-3 with CAS of longer chain length, slightly hazy solutions
appeared at larger mixing ratio of ANOS-1/CASs.

Fig. 1—Compatibility results of surfactant mixture ANOS-1/CAS-1 with different mixing ratios at 95°C.
manionic/mcationic 0/1 1/5 1/4 1/3 1/2 1/1 3/2 2/1 3/1 4/1 5/1 6/1 7/1 1/0
ANOS-1/CAS-1 A A A A A A C B B B B B C C
ANOS-1/CAS-2 A A A A A A A A C B B – – C
ANOS-1/CAS-3 A A A A A A A A B B B – – C
Table 4—Compatibility results of catanionic surfactants with different mixing ratios at 95°C.
Synergism of Cationic and Anionic Surfactants. IFT Reduction of Catanionic Surfactant—Phase Behavior. For surfactant
formulations, IFT is one of the most important parameters to evaluate their potential for chemical flooding application. Lower IFT
indicates higher oil production potential.
Phase behavior is an efficient way to evaluate surfactant performance for chemical flooding including IFT and compatibility of surfac-
tant with crude oil. By varying the salinity of ionic surfactant solutions from low to high values, the microemulsion type could pass from
Winsor Type I (oil in water), Winsor Type III (bicontinuous oil and water in a third phase known as middle-phase microemulsion) to
Winsor Type II (water in oil). The screening effect of inorganic counter ions on the charge of surfactant head group increases with the salt
concentration which reduces the hydrophilicity. As a result, the ionic surfactant changes from hydrophilic to hydrophobic leading to the
microemulsion transition. Type III at optimal salinity exhibits lowest IFT and is preferred for chemical flooding. The IFT value can be
estimated using the correlation between solubilization parameters and IFT (Huh 1979; Levitt et al. 2009; Hirasaki et al. 2011; Fuseni et al.
2013).
In this study, phase behavior experiments of surfactant mixtures with different mixing ratios were conducted with fixed salinity at
95°C. By increasing the percentage of ANOS-1, there is a change from Winsor Type I to Winsor Type III (Fig. 2). Slightly yellow bottom
phase was observed indicating oil/water emulsion when the ratio of ANOS-1/CAS-1 was below 2/1 (Fig. 2b). The bottom phase became
colorless and middle phase appeared when the ratio reached 2/1 (Fig. 2c and 2d). The volume of middle phase is too small to obtain an
accurate value for IFT calculation. However, the appearance of middle phase indicates low IFT of the surfactant mixture. In addition, the
phase behavior result suggested that this surfactant mixture turned from hydrophilic to hydrophobic with increase of ANOS- 1
percentage.
IFT Reduction of Surfactant Mixtures—Spinning Drop Tensiometer. Spinning drop tensiometer was used to measure IFT to obtain
lowest IFT within the test range. The IFTs of CAS-1 and ANOS-1 at 90°C were 2.94 and 0.20 mN/m, respectively, which is too high for
application in chemical flooding. Significant IFT reduction was observed when these two components were mixed as shown in Fig. 3.
With the increase of ANOS-1 percentage, IFT of the surfactant mixture first decreased and then increased. The optimal ratio is 5/2 with
ultralow equilibrium IFT of 1.5×10−3 mN/m indicating strong synergistic interaction between the two components. This result is consis-
tent with the phase behavior result.
IFTs of SD-2 and SD-3 at different mixing ratios were also measured and the lowest IFTs were summarized in Table 5. Though IFTs
of CAS-2 and CAS-3 are lower than that of CAS-1, they are still too high for application. By mixing the oppositely charged surfactants,
the IFT of all three mixtures was reduced to 10−3 mN/m indicating strong synergism between these individual surfactants. Compared with
the IFT of the individual surfactants, IFT reduced from 10−1 to 10−3 mN/m for the SD series. The optimal mixing ratio for SD-2 and SD-3
using CAS with longer chain length was larger than that of SD-1 using CAS-1 with shortest chain length.
Salinity Effect on Surfactant Mixtures. As discussed previously, high-salinity condition has an adverse impact on the solubility of
ionic surfactants in aqueous phase due to reduction of hydrophilicity of head group. The surfactant tends to stay in the oleic phase which
hinders achieving low IFT. Based on the previous IFT and phase behavior results, the optimum ratio of ANOS-1/CAS-1 mixture is 5/2
for HSW (57,670 ppm). This indicates that the optimal salinity of ANOS-1/CAS-1 = 5/2 is 57,670 ppm. For the systems with ratio larger
than 5/2, the surfactants are too hydrophobic under this salinity, which means their optimal salinity is smaller than 57,670 ppm. Here,
surfactant mixture with ratio 4/1 was chosen, and solutions with different salinities were prepared. Fig. 4 shows the IFT results of this
formulation in brines with total dissolved solids from 0 to 57,670 ppm at 90°C. The salinity where lowest IFT appears is the optimal
salinity. The optimal salinity is 14,400 ppm with ultralow IFT of 8×10−4 mN/m. This suggests the formulation can be applied to field with
different salinities by tuning the mixing ratio. Moreover, IFT remained in 10−2 mN/m in this wide salinity range indicating the robustness
of the surfactant mixture.
Temperature Effect on Synergism. Table 6 shows the compatibility results of 0.2% ANOS-1/CAS-1 with different mixing ratios at
25°C. Different from the results of solutions at 95°C, transparent solutions were overserved in both individual surfactants and surfac-
tant mixtures. The IFTs of CAS-1 and ANOS-1 at 25°C were 1.25 and 0.19 mN/m, respectively. The IFT of the surfactant mixture was
between IFTs of individual surfactants and decreased slowly with the increase of ANOS-1 percentage (Fig. 5). Both compatibility and IFT
results indicate that there is no synergistic interaction between ANOS-1 and CAS-1 at 25°C. Fig. 6 shows the IFTs of ANOS-1/CAS-1 =
5/2 at different temperatures. The equilibrium IFT decreased from 0.35 to 0.0015 mN/m as the temperature increased from 25 to 90°C and
was in 10−2 mN/m range when temperature was higher than 70°C. The synergism becomes obvious with increasing temperature, leading
to significant IFT reduction. Generally, the increase of temperature leads to a decrease in the solubility of the hydrophobic tail in the

Fig. 2—Phase behavior results of 0.2% surfactant mixture ANOS-1/CAS-1 in HSW at 95°C with (a) different mixing ratios, (b) Winsor Downloaded from http://onepetro.org/REE/article-pdf/26/01/88/3066395/spe-200182-pa.pdf by Eni SPA E&P Division user on 12 April 2023
Type I and Type III behavior, (c) mixing ratio of 2/1 and (d) mixing ratio of 5/2.
water and thus decreases the IFT (Gao and Sharma 2013). However, it was also found that IFT increased with the increase of temperature
(Jia et al. 2019). In this work, ANOS-1 is an anionic/nonionic surfactant containing ethoxyl group, which is temperature-sensitive. The
solubility of nonionic group in water reduces with the increase of temperature due to the break of hydrogen bond between nonionic group
and water molecule. This is the reason that the ANOS-1 solution was transparent at 25°C and became hazy at 95°C. This also changes
the morphology of ANOS-1 in solution and further affects the interaction between ANOS-1 and CAS-1 leading to IFT reduction at high
temperature.
Adsorption of Catanionic Surfactants on Carbonate Rock. Surfactant adsorption on the rock surface reduces the surfactant
concentration in bulk solution and leads to higher IFT. Therefore, low adsorption surfactant formulations are preferred. The adsorption
results of catanionic surfactants and individual surfactants on carbonate rock are shown in Table 7. Adsorption depends primarily on the
electrostatic charges of the rock surface and the surfactant component. On positively charged carbonate rock, the adsorption of CASs
was almost zero. Anionic surfactant ANOS-1 presented much higher adsorption of 1.43 mg/g rock. The adsorption quantity of catanionic
surfactants was 0.90, 1.06, and 1.25 mg/g rock for SD-1, SD-2, and SD-3, respectively. The adsorption levels of the SD series are lower
than the value of ANOS-1. The mixture SD-1 presented lowest and desirable adsorption.

Fig. 3—IFT results of ANOS-1/CAS-1 with different mixing ratios at 90°C.
Anionic Surfactant CAS Mixture

Catanionic Surfactant (mN/m) (mN/m) (mN/m)
SD-1 (ANOS-1/CAS-1 = 5/2) 0.20 2.94 1.5×10−3
SD-2 (ANOS-1/CAS-2 = 11/2) 0.20 2.19 2.1×10−3
SD-3 (ANOS-1/CAS-3 = 9/2) 0.20 1.56 1.1×10−3
Table 5—IFTs of individual surfactants and catanionic surfactants at 90°C.
Fig. 4—Salinity effect on IFT of ANOS-1/CAS-1 = 4/1 at 90°C.

ANOS-1/CAS-1 0/1 1/5 1/4 1/3 1/2 1/1 3/2 2/1 3/1 4/1 5/1 6/1 7/1 1/0
25°C A A A A A A A A A A A A A A
Table 6—Compatibility results of surfactant mixture ANOS-1/CAS-1 with different mixing ratios at
25°C.
Fig. 5—IFT results of 0.2% ANOS-1/CAS-1 with different mixing ratios at 25°C.
Fig. 6—Temperature effect on IFT of 0.2% ANOS-1/CAS-1 = 5/2.

Mixture
Catanionic Surfactant Anionic Surfactant (mg/g rock) CAS (mg/g rock) (mg/g rock)
SD-1 (ANOS-1/CAS-1 = 5/2) 1.43 0.03 0.90
SD-2 (ANOS-1/CAS-2 = 1.43 0.01 1.06
11/2)
SD-3 (ANOS-1/CAS-3 = 9/2) 1.43 0.00 1.25
Table 7—Static adsorption data of 0.2% surfactant solutions at 95°C.
Long-Term Stability of Catanionic Surfactants. To be effective, chemical solutions must remain stable for a long time at field
application conditions. The IFTs of catanionic surfactant solutions aged at 95°C for different times were measured, and the results are
shown in Fig. 7. The equilibrium IFT of SD-1 was stable and kept ultralow during the 2 months aging time. IFT of SD-2 and SD-3
increased to 0.018 mN/m after aging for 70 days. This again points to SD-1 as the best performing mixture.
Fig. 7—IFT results of SD-1, SD-2, and SD-3 aged at 95°C for different days.
Oil Production by Coreflooding Displacement. The coreflooding displacement experiment was performed at 95℃ to examine the oil
production potential of the three developed catanionic surfactants. The main parameters of the core plugs were listed in Table 2. The
initial oil saturation of three core plugs was less than 70% due to low permeability of about 20 md. Fig. 8 shows the oil production and
differential pressure with the fluid injection, and the results are summarized in Table 8. As shown by the blue lines on the figures, the
injection pressure of the waterflooding using HSW increased at the beginning and then decreased indicating the water breakthrough along
the core. HSW was injected for 5 PV until oil production was negligible with stable differential pressure. The oil production for the three
tests is 43.7, 47.7, and 48.4% by waterflooding, respectively. After waterflooding, the injection was switched to surfactant solutions. A 1
PV slug of 2,000 ppm surfactant solution with optimal ratio listed in Table 5 was injected. The differential pressure increased and then
decreased with the surfactant injection. Meanwhile, additional oil production was observed at the outlet. A possible explanation is that the
surfactants with ultralow IFT mobilize the residual oil, forming a continuous oil bank in the displacement front. The flow of the oil bank
with higher viscosity than water produces a higher differential pressure. After the oil bank is produced out, the pressure decreases with
only discontinuous oil blobs flow in the core. The oil production continued in the post water injection using HSW. Final oil production
reached 64.5, 69.1, and 68.5% for SD-1, SD-2, and SD-3, respectively. The additional oil production by SD-1, SD-2, and SD-3 beyond
that produced by waterflooding was 20.8, 21.4, and 20.1%. All three catanionic surfactants significantly improved the oil production.
Chemical Formula Core No. Waterflood Production (%) Final Production (%) Tertiary Production (%)
0.2% SD-1 (ANOS-1/CAS-1 = 5/2) 1 43.7 64.5 20.8
0.2% SD-2 (ANOS-1/CAS-2 = 11/2) 2 47.7 69.1 21.4
0.2% SD-3 (ANOS-1/CAS-3 = 9/2) 3 48.4 68.5 20.1
Table 8—Coreflooding results of 0.2% catanionic surfactants.

Fig. 8—Oil production and differential pressure with injection volume of (a) 0.2% SD-1, (b) 0.2% SD-2, and (c) 0.2% SD-3.
Discussion
Three catanionic surfactants SD-1, SD-2, and SD-3 with ultralow IFT were developed for harsh carbonate reservoirs based on the syner-
gistic effect between oppositely charged surfactants. The chain length of CASs affects the optimal mixing ratio. All three catanionic sur-
factants with optimal ratio significantly improved oil production by 20% beyond waterflooding using low-permeability limestone core
plugs. This could be explained by the reduction of capillary number due to the low IFT of these three surfactants. The capillary number
(Nc) is defined as follows:
u
NC = , (2)
‍ cos ‍
where µ is the viscosity of displacing fluid, u is the displacing Darcy’s velocity, θ is the contact angle, and σ is the IFT between the
displacing fluid and the oil. Many experimental data show that the residual oil saturation decreases as the capillary number increases
(Lake 1989; Sheng 2011). IFT between HSW and oil was about 15 mN/m. All three catanionic surfactants reduced the IFT to 10−3mN/m,
which significantly increased the capillary number leading to high oil production. Oil droplets can flow more easily through pore throats
due to reduced capillary trapping by low IFT. Surfactants can also improve oil production for low-permeability reservoirs as surfactants
could reduce the IFT to ultralow value in very small pore spaces (Gupta et al. 2020).
Among the three catanionic surfactants, SD-1 presented the lowest adsorption and best long-term stability. These two properties did
not affect the coreflooding results. This is because the coreflooding test lasted only several hours, and the core plug volume was small. For
surfactant flooding of field application, low adsorption and good long-term stability are preferred. High adsorption will reduce surfactant
concentration, which further decreases the efficiency of surfactant to reduce IFT. The increase of IFT with time also reduces the efficiency
in oil production. Based on the results of IFT, adsorption, long-term stability, and coreflooding test, SD-1 with optimal ratio is recom-
mended for the carbonate reservoir with high temperature and high salinity.
Conclusions
In this work, one anionic surfactant and three CASs were used to develop high-performance catanionic surfactants based on synergistic
interaction for improving oil recovery in harsh field conditions. The following conclusions were drawn:
• Three developed catanionic surfactants exhibited good compatibility and ultralow IFT for high-temperature and high-salinity reservoir
conditions based on synergistic effect. The synergism between the surfactants became more obvious at high temperature indicating the
good potential for high-temperature conditions.

• All three catanionic surfactants SD-1, SD-2, and SD-3 presented high efficiency in improving oil recovery. SD-1 presented lowest
adsorption and best long-term stability. As a result, SD-1 is recommended for the use in the harsh carbonate reservoir condition.
• The surfactant mixtures with different mixing ratios show different optimal salinities.−2The formulations can be applied in the field with
different salinities by tuning the mixing ratio. In addition, IFT values maintained 10 mN/m in a wide salinity range, which indicates
the robustness of the mixing surfactants.
• It is an efficient way to develop surfactant formulations for harsh conditions by mixing oppositely charged low-performance surfactants
to obtain good synergism for oil recovery applications.
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Catanionic Surfactants for Improving Oil

*Corresponding author; email: limin.xu@aramcoasia.com

88 February 2023 SPE Reservoir Evaluation & Engineering

Composition Connate Water HSW

Table 1—Compositions of connate water and HSW.

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Table 2—Core plug information.

Catanionic Surfactant Anionic Surfactant CAS

Table 3—Compositions of synergistic catanionic surfactants.

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Anionic Surfactant CAS Mixture

Table 5—IFTs of individual surfactants and catanionic surfactants at 90°C.

Fig. 4—Salinity effect on IFT of ANOS-­1/CAS-­1 = 4/1 at 90°C.

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Fig. 6—Temperature effect on IFT of 0.2% ANOS-­1/CAS-­1 = 5/2.

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Table 7—Static adsorption data of 0.2% surfactant solutions at 95°C.

Table 8—Coreflooding results of 0.2% catanionic surfactants.

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Fig. 4—Salinity effect on IFT of ANOS-1/CAS-1 = 4/1 at 90°C.

Fig. 6—Temperature effect on IFT of 0.2% ANOS-1/CAS-1 = 5/2.