Novel Application of Cationic Surfactants For Foams With Wettability Alteration in Oil-Wet Low-Permeability Carbonate Rocks

J179598 DOI: 10.
2118/179598-PA Date: 17-November-18 Stage: Page: 2218 Total Pages: 14
Novel Application of Cationic Surfactants

for Foams With Wettability Alteration
in Oil-Wet Low-Permeability
Carbonate Rocks
Pinaki Ghosh and Kishore K. Mohanty, University of Texas at Austin
Summary
Carbonate rocks are typically heterogeneous at many scales, leading to low waterflood recoveries. Polymers and gels cannot be injected
into nonfractured low-permeability carbonates (k < 10 md) because pore throats are smaller than the polymers. Foams have the poten-
tial to improve both oil-displacement efficiency and sweep efficiency in such carbonate rocks. However, foams have to overcome two
adverse conditions in carbonates: oil-wettability and low permeability. This study evaluates several cationic-foam formulations that
combine wettability alteration and foaming in low-permeability oil-wet carbonate cores. Contact-angle experiments were performed on
initially oil-wet media to evaluate the wettability-altering capabilities of the surfactant formulations. Static foam-stability tests were
conducted to evaluate their foaming performance in bulk; foam-flow experiments (without crude oil) were performed in porous media
to estimate the foam strength. Finally, oil-displacement experiments were performed with a crude oil after a secondary gasflood. Two
different injection strategies were studied in this work: surfactant slug followed by gas injection and coinjection of surfactant with gas
at a constant foam quality. Systematic study of oil-displacement experiments in porous media showed the importance of wettability
alteration in increasing tertiary oil recovery for oil-wet media. Several blends of cationic, nonionic, and zwitterionic surfactants were
used in the experiments. In-house-developed Gemini cationic surfactant GC 580 was able to alter the wettability from oil-wet to water-
wet and also formed strong bulk foam. Static foam tests showed an increase in bulk foam stability with the addition of zwitterionic sur-
factants to GC 580. Oil-displacement experiments in oil-wet carbonate cores revealed that tertiary oil recovery with injection of a
wettability-altering surfactant and foam can recover a significant amount of oil [approximately 25 to 52% original oil in place (OOIP)]
over the secondary gasflood. The foam rheology in the presence of oil suggested propagation of only weak foam in oil-wet low-
permeability carbonate cores.
Introduction
Carbonate reservoirs are estimated to have more than 40% of the gas reserves and 60% of the oil reserves worldwide (Schlumberger
2007). Most of these carbonate reservoirs are typically naturally fractured, highly heterogeneous, and are believed to be oil-wet or
mixed-wet (Chilingar and Yen 1983; Roehl and Choquette 1985). During waterflood, the water preferentially flows through the frac-
tures, and because of the oil-wet nature, water does not imbibe into the matrix, leading to a low waterflood recovery. To displace oil,
the injected fluid needs to overcome the negative capillary pressure barrier and invade the rock matrix. Thus, the two major challenges
for enhanced oil recovery (EOR) in carbonate reservoirs are oil-wetness and heterogeneity. Carbonate rocks typically have a complex
pore structure, and the heterogeneity exists in all scales (microporosity, vugs, layers, and natural fractures). Because of this heterogene-
ity, the average recovery factor (the ratio of recoverable oil to OOIP) has been reported to be approximately 35% (Schlumberger 2007).
However, because of heterogeneity, in some reservoirs waterflooding has been reported to have recovery factors as low as 10%
(Montaron 2005). The remaining oil after secondary recovery is either residual oil trapped in the swept portion of the reservoir or oil
bypassed in the unswept portions of the reservoir.
Because carbonate rocks are heterogeneous at many scales from pore to reservoir, foam flooding has the potential to improve both
displacement and sweep efficiency (Kovscek et al. 1994; Rossen et al. 2010). The concept of foam as a mobility-control agent was first
proposed by Boud and Holbrook (1958). Since then, there have been several field tests: carbon dioxide foam flood (Chou et al. 1992),
steam foam flood (Patzek 1996), and foam-assisted water-alternating-gas injection (Blaker et al. 2002). Foam formulations have been
recently improved by including ultralow interfacial tension (IFT) (Wang and Mohanty 2014) and nanoparticles (Singh and Mohanty
2015a). Many studies in the past have addressed foam flow in sandstones, but few studies have been reported on foam flow in carbonate
rocks (Singh and Mohanty 2016). There are two challenges for foams to survive in low-permeability carbonate rocks: The foams have
to deal with low permeability and the oil-wettability of carbonate rocks.
Many studies in the literature are conducted in high-permeability sandpacks or sandstones. As the fractional flow of gas is increased,
the capillary pressure increases (along with gas saturation), but reaches a limiting or “critical” capillary pressure, greater than which
foam lamella starts breaking and gas mobility increases without the change in gas saturation (Ransohoff and Radke 1988; Rossen and
Gauglitz 1990). The critical capillary pressure varies with surfactant type and concentration, gas-flow rate, and porous-medium perme-
ability (Falls et al. 1988; Khatib et al. 1988; Rossen 1990). These studies were conducted in porous media of permeability greater than
1 darcy. Limited studies are available on foam in low-permeability porous media. Raza (1970) reported that the ability of foam to pro-
vide flow resistance is greater in high-permeability porous media than in low-permeability media. Siddiqui et al. (1997) suggested that
the important factors governing the foam flow in low-permeability sandstones are bubble size and pressure drop, which are functions of
flow rate. Very-high pressure gradients (>1,000 psi/ft) were generated in these experiments, which are not feasible in fields.
Wettability indicates the affinity of the rock to different fluids; it affects several parameters such as fluid distribution, relative perme-
abilities, capillary pressure, and residual oil saturation (Anderson 1987; du Pétrole and Malmaison 1990). It is a function of rock miner-
alogy, fluid composition, saturation history, and reservoir temperature. Schramm and Mannhardt (1996) reported lower efficiency of
Copyright V
C 2018 Society of Petroleum Engineers
This paper (SPE 179598) was accepted for presentation at the SPE Improved Oil Recovery Conference, Tulsa, 11–13 April 2016, and revised for publication. Original manuscript received for
review 28 November 2017. Revised manuscript received for review 2 May 2018. Paper peer approved 4 May 2018.
2218 December 2018 SPE Journal
ID: jaganm Time: 13:58 I Path: S:/J###/Vol00000/180065/Comp/APPFile/SA-J###180065

J179598 DOI: 10.2118/179598-PA Date: 17-November-18 Stage: Page: 2219 Total Pages: 14
foam in oil-wet or intermediate-wet porous media than in water-wet media because of foam/oil interactions. The wettability of
carbonate rocks can be altered from oil-wet to water-wet using anionic surfactants (Seethepalli et al. 2004; Zhang et al. 2006; Sharma
and Mohanty 2013), cationic surfactants (Austad and Milter 1997; Strand et al. 2003), or nonionic surfactants (Gupta and Mohanty
2010; Alvarez et al. 2014). The choice of surfactant depends on reservoir properties such as crude oil, reservoir mineralogy, brine com-
position, and temperature (Adibhatla and Mohanty 2008; Mohan et al. 2011). Wettability can also be altered by low-salinity-water
injection at high reservoir temperature (Tang and Morrow 1997; Yousef et al. 2011; Mahani et al. 2015).
Oil wettability and the presence of crude oil (Schramm and Novosad 1992) have negative effects on the foam strength. The three
predominant mechanisms for foam generation in porous media are leave-behind, snapoff, and lamella division (Mast 1972; Ransohoff
and Radke 1988). Snapoff is the primary and most-common mechanism of foam generation (Holm 1968; Falls et al. 1988). Snapoff
occurs in water-wet pores when a meniscus passes through a narrow throat into an adjacent large pore body, resulting in disconnection
of the nonwetting phase. The necessary condition for snapoff to occur in the porous media is that the body/throat ratio must be larger
than two (Kovscek and Radke 1994), the capillary pressure must be low, and the liquid saturation must be high (Falls et al. 1989). Yu
and Wardlaw (1986) reported that for surfaces with contact angles (with respect to aqueous phase) greater than approximately 70 ,
snapoff does not occur in throats. This signifies that it is crucial to alter the wettability of oil-wet systems to water-wet for foam genera-
tion. Haugen et al. (2012) conducted foam-flow experiments in fractured, oil-wet limestone cores and observed that in-situ foam genera-
tion in the fractures by means of coinjection of gas and surfactant was inefficient and large pore volumes (PVs) (>100 PV) of
pregenerated foam were necessary to recover oil. This is primarily because of the negative effect of crude oil on foam generation and
foam stability. Experimental studies have demonstrated the detrimental effects of oil on foam stability (Arnaudov et al. 2001; Hadjiiski
et al. 2001; Vikingstad et al. 2005; Farajzadeh et al. 2009). The effect of the presence of oil on foam destabilization depends on the
oil-, surfactant-, and aqueous-phase compositions (Farajzadeh et al. 2012). The foam rheology in the presence of oil depends on the
spreading, entering, and bridging coefficients of the gas/surfactant/oil interactions, oil emulsification, and pinchoff.
Formation brines in most carbonate reservoirs have a significant number of divalent ions. The effects of divalent ions on surfactant
adsorption (Yekeen et al. 2017), lamellae drainage (Angarska et al. 1997), and foam rheology have been studied in the past. The
anionic-surfactant adsorption is high on carbonates in the presence of divalent ions (and in the absence of alkali) and may be economi-
cally impractical. Thus, the use of cationic and cationic/zwitterionic surfactants for foam applications in carbonate formations needs to
be explored.
In this work, we have tried to develop formulations that combine wettability alteration and foaming to address the issue of oil-
wetness and heterogeneity in carbonate rocks. Most of the reported studies in the past were conducted in sandpacks or sandstones, the
permeability of which is on the order of darcies or higher (Sanchez and Hazlett 1992; Li et al. 2012). Foam propagation in porous media
is governed by foam quality, injection rate, and pore structure. Thus, it is critical to conduct foam-flow experiments in low-permeability
cores that can be more representative of typical carbonate reservoirs. In this present study, foam-flow and oil-displacement experiments
were performed in outcrop Texas Cream Limestone cores at typical field rates. Several surfactant formulations were studied that have
different degrees of wettability alteration and foaming capability. Contact-angle experiments were performed to evaluate the
wettability-altering ability. Static foam tests and foam-flow experiments (with no crude oil) were then performed to compare their foam
stability and strength. The synergistic effects of cationic/nonionic and cationic/zwitterionic surfactants were explored to develop a
foaming system with wettability alteration in carbonate rocks (with lower adsorption compared with anionic surfactants). Gasfloods and
subsequent foam floods were performed in carbonate cores saturated with a crude oil using different surfactant formulations as the
foaming agent. The methodology is described in the next section, followed by the results.
Methodology
Materials. Table 1 lists the surfactants used in this study and their properties. Cationic surfactants DTAB (from Sigma Aldrich),
R
EthoquadV C/25 (from Akzonobel), and BTC (from Stepan) were chosen because they are good wettability-altering agents. Nonionic
surfactant TergitolTM NP (from Dow Chemical) was chosen because it is considered to be a moderate foaming agent. An in-house-
produced cationic Gemini surfactant GC 580 was chosen because it proved to be a good wettability-altering and foaming agent. In the
literature, betaines, a particular class of zwitterionic surfactants, are generally referred to as foam boosters (Basheva et al. 2000). In the
R
present study, the zwitterionic surfactant Lauryl Betaine (from Rhodia) was used. The anionic surfactant BiotergeV AS-40 (from
Stepan) was used as a good foaming agent for comparison.
Name Structure Active Molecular Weight Type

DTAB Dodecyltrimethylammonium bromide >98% 308.34 g/mol Cationic
BTC Alkyl dimethyl benzyl ammonium chloride 80% – Cationic
GC 580 Gemini cationic 100% 580 g/mol Cationic
Tergitol NP Alkyl ethoxylate 100% 642 g/mol Nonionic
LB Lauryl betaine 29% 271.4 g/mol Zwitterionic
Cocoalkylmethyl[polyoxyethylene (15)]
Ethoquad C/25 95% 911 g/mol Cationic
ammonium chloride
Bioterge AS-40 C14–16 alpha olefin sulfonate 38.86% – Anionic
Table 1—Surfactants used in the present study.
Table 2 lists the properties of the limestone cores (C1 through C6) used in this study. Texas Cream Limestone rocks were used
for all the experiments. Each core was approximately 30 cm long and 3.75 cm in diameter. Oil permeabilities (at Swc) varied from 9.2
to 22 md.
Formation and injection brine used in these experiments are tabulated in Table 3. Crude oil was obtained from a reservoir and had a
viscosity of 11.8 cp at 60 C, density of 0.89 g/cm3, and acid number equal to 0.49 mg of potassium hydroxide/1 g of oil. The viscosity
was measured using an AR G2 rheometer. The pH of the various surfactant formulations was measured using pHTestr 20 (Oakton
Instruments), which has a precision of 60.01. The pH electrode was calibrated with standard pH buffer solutions of pH 4.7 and 10.
Sodium chloride, calcium chloride, sodium sulfate, magnesium chloride, and methane (research grade, Matheson) were used as received.
December 2018 SPE Journal 2219

Texas Cream Texas Cream Texas Cream Texas Cream Texas Cream Texas Cream
Limestone Limestone Limestone Limestone Limestone Limestone
Cores (C1) (C2) (C3) (C4) (C5) (C6)
Length (cm) 29 29 29.8 29.5 29.6 29.5
Diameter (cm) 3.76 3.76 3.74 3.76 3.76 3.76
Porosity (%) 26.25 27.65 25.4 29 30.4 26
3
PV (cm ) 84.5 89 83.3 95.2 100 86
Oil permeability at Swc (md) 12 9.2 13.5 12.9 22 15
Initial oil saturation Soi 0.76 0.75 0.62 0.73 0.64 0.76
Table 2—Properties of different carbonate cores.
Composition Formation Brine Injection Brine

+
Na 2.940 g/L 3.636 g/L
2+
Ca 0.256 g/L 0.740 g/L
2+
Mg 0.049 g/L 0.186 g/L
–
Cl 4.859 g/L 7.294 g/L
2–
SO4 0.365 g/L 0.221 g/L
Total salinity 8,469 ppm 12,077 ppm
Table 3—Formation and injection brine used in the study.
IFT Measurements. The IFTs between the oil and the surfactant solutions were approximately 1 dynes/cm (i.e., not ultralow). The
pendant-drop method was used to measure the IFT between oil and the aqueous phase using a Ramé-Hart goniometer. The surfactant
formulation and oil were mixed and allowed to equilibrate at 60 C. The equilibrated aqueous and oil phases were used for the IFT
measurement. An oil droplet was held in the aqueous phase, and the axisymmetric shape analysis of the droplet was performed using
software that calculates the IFT by fitting the drop profile with the Young-Laplace equation using a contour-fitting algorithm.
Contact-Angle Experiments. Contact-angle experiments were performed using mineral calcite plates as a proxy for limestone cores
because they have the similar mineralogy. First, a 600-mesh diamond grinding plate was used to polish the calcite plates and make the
surface smooth and free from any contamination. Second, the polished plates were immersed in formation brine for 24 hours and then
aged in the crude oil at 80 C for 3 to 4 weeks. Third, the oil-wet calcite plates were immersed in the formation brine at the reservoir
temperature, 60 C, to ensure their oil-wet nature. Finally, the plates were placed in an optical cell and were immersed in different sur-
factant formulations. Magnified images of the oil droplets on the plate were captured and contact angles were observed. The droplet
sizes were too small (<0.5 mm) in some formulations to measure the contact angles accurately.
Static Foam Tests. Static foam tests are the most-common stability technique to measure the foaming ability of surfactant formula-
tions (Vikingstad et al. 2005; Singh and Mohanty 2015b). These experiments were performed to compare the foaming ability of various
surfactant formulations used in oil-displacement experiments. These experiments were performed at 60 C (reservoir temperature in the
present study). The apparatus consisted of a transparent cylinder made of acrylic (diameter of 3 cm, length of 23 cm) with a stainless-
steel sparging frit (pore size of 2 mm) at the bottom, which was used to disperse gas in the surfactant formulation. First, 30 mL of surfac-
tant solution was taken in the cylinder and then a gas was injected at constant pressure of 5 to 10 psi from the bottom, generating static
foam. The height of the foam (above the liquid phase) was monitored as a function of time. The half-life, which is the time for the vol-
ume of foam to be reduced to half of its original volume, was observed for each case. Each experiment was repeated two times and
average half-lives are reported. Experiments were also performed in the presence of crude oil to study the detrimental effect of oil on
foam half-life after mixing 1 to 2 mL of crude oil uniformly across the generated foam.
Foam-Flow Experiments. In the absence of oil, corefloods were performed with the surfactant formulations screened from bulk stabil-
ity tests. The primary objective of these floods was to determine the pressure drop across the core and to estimate the mobility reduction
caused by foam. After the core was saturated with brine and brine permeability was measured, 10 PV of brine and methane gas at 80%
quality were coinjected at 4 ft/D into the core until the pressure drop across the core stabilized. This step was the base case for the foam
study. Then methane and surfactant solution at 80% quality were coinjected into a sandpack to pregenerate foam, and the effluent from
the sandpack was injected into the core. Foam quality is defined as the volume of gas contained in the foam and can be expressed as a
fraction or percentage. In coreflood experiments, foam quality is expressed as a ratio of the injection rates of the gas to the total injec-
tion rate. The pregenerated foam was visible in the view cell attached at the outlet of the sandpack. This pregenerated foam was then
injected at 4 ft/D into the core from the top of the coreholder for approximately 10 PV until the pressure drop stabilized (assuming the
surfactant adsorption had reached equilibrium). The pressure drop across the core was recorded with a pressure transducer. The
mobility-reduction factor (MRF) is defined as the ratio of the pressure drop in the presence of foam to the pressure drop in the base case
(brine and gas at the same quality without any surfactant),
DPsurfþgas Injection-gas rate

MRF ¼ ; Foam quality ð%Þ ¼ 100: . . . . . . . . . . . . . . . . . . . . . ð1Þ
DPbrineþgas Injection-gas rate þ injection-liquid rate

Adsorption Experiments. Batch adsorption experiments were performed in crushed Texas Cream Limestone, filtered through
200 mesh, at the reservoir temperature. The ratio of the amount of crushed limestone rock to the amount of surfactant solution was kept
constant at 1:2 (weight ratio). The vials were shaken at regular intervals for 3 days and equilibrated at the reservoir temperature. The
anionic surfactants were analyzed in high-performance liquid chromatography, whereas the cationic surfactants were analyzed using a
method proposed by Wang and Langley (1977). The adsorption of the surfactant (q) was expressed in mg/g and calculated using
msolution
q¼ ðCo CÞ 103 ; . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ð2Þ
mcarbonate
where q is the adsorption (in mg/g), Co is the initial surfactant concentration (in ppm), C is the final surfactant concentration (in ppm),
msolution is the mass of the surfactant solution (in g), and mcarbonate is the mass of the crushed limestone (in g).
Oil-Displacement Experiments. The properties of the cores used for these experiments are listed in Table 2. The cores were dried in
an oven at 80 C for 24 hours. They were mounted vertically in a Hassler-type core holder with a confining pressure of 700 psi. Petro-
physical properties such as porosity and permeability of the core were determined after vacuum saturation with the formation brine at
room temperature. Fig. 1 shows the experimental schematic. Two D-Series syringe pumps from Teledyne Isco (Lincoln, Nebraska)
were used in the setup; they are capable of low injection rates (as low as 0.001 mL/min). The apparatus was built to coinject methane gas
and brine/surfactant solution through a sandpack (0.6-in. diameter and 6-in. length) to ensure proper mixing and foam generation. The
pregenerated foam was then injected at the top of the core. The whole setup was placed inside an oven operating at the reservoir tempera-
ture of 60 C. The downstream pressure of the experiment was maintained by a backpressure regulator (Equilibar, North Carolina)
installed downstream of the core holder. The pressure drop across the core was measured using a Rosemount differential-pressure trans-
ducer. An automatic data-acquisition system (DATAQ Instruments and LabView) was used to record the pressure.
Oven
Sandpack
T = 60°C
Surfactant
Brine
Core
Isco pump
ΔP1
Water Waste
gas to vent
Backpressure
regulator
CH4
Oil collector
Accumulator
Isco pump
Fig. 1—Schematic of experimental setup for foam-flow and oil-displacement experiments (Singh and Mohanty 2016).
In an oil-wet system, the mechanisms of foam-mobility control and wettability alteration are quite complex and could be inter-
dependent. In heterogeneous carbonate rocks, foam—if stable—can divert injected fluids to low-permeability regions where
wettability-altering agents can alter the wettability and recover more oil. On the other hand, wettability alteration can also lead to incre-
mental oil recovery in high-permeability regions by mobilizing oil and thus helping with foam stabilization because lower oil saturation
leads to higher foam stability. Hence, the purpose of performing oil-displacement experiments was to study the effects of wettability
alteration and foaming in oil-wet carbonate cores. These experiments are performed using Texas Cream Limestone cores. Table 4 tabu-
lates the list of experiments that were performed, the initial-wettability state of the rock, surfactant formulation, and surfactant proper-
ties. The viscosities of surfactant solutions are reported at 60 C and a shear rate of 10 seconds–1. The total concentration of surfactant in
each formulation was kept at approximately 0.4 to 0.5 wt%.
To achieve initial oil saturation, Texas Cream Limestone cores, fully saturated with brine, were flooded with the filtered crude oil
(at least 2 PV) from the top at a constant pressure of 500 psi at the room temperature until brine production stopped. The oil-saturated
cores were then aged for 1 month at 80 C to make them oil-wet. Fig. 2 shows the core when a water droplet is placed on the core before
and after aging. The droplet imbibes into the core in the former case, indicating initial water-wetness, but does not imbibe after aging,
confirming oil-wetness.
For all the oil-displacement experiments in Table 4, the following injection scheme was followed. First, a methane gasflood was
conducted at 0.5 ft/D until oil recovery stopped. Second, a slug of surfactant formulation of 0.5 PV was injected into the core. Third,
this slug was followed with an injection of methane gas until no additional oil was produced. Finally, surfactant solution and methane
gas were coinjected at 1 ft/D with a foam quality of 70 to 80% from the top until no additional oil was recovered. These floods are
aimed at reservoirs that are gasflooded. Oil recovery and pressure drops were monitored at every step.

Initial Formulation Viscosity at IFT

Coreflood Wettability Surfactant Formulation Label 60°C (cp) pH (dynes/cm)
1 Water-wet 0.5 wt% LB + injection brine S1 0.7 8.0 2.3
2 Oil-wet 0.5 wt% LB + injection brine S1 0.7 8.0 2.3
0.2 wt% DTAB + 0.2 wt% NP-10 +
3 Oil-wet S2 0.6 7.2 3.9
injection brine
0.2 wt% GC 580 + 0.2 wt% Ethoquad C/25 +
4 Oi-wet S3 0.75 7.0 0.7
injection brine
0.3 wt% GC 580 + 0.1 wt% LB +
5 Oil-wet S4 0.7 7.5 1.4
injection brine
0.5% C14–16 AOS + 2% Na2CO3 +
6 Oil-wet S5 1.2 11.7 0.38
1.5% EDTA + injection brine
Table 4—Surfactant formulations used in oil-displacement experiments. AOS 5 alpha olefin sulfonate; EDTA 5 ethylenediaminetetracetic acid.
Fig. 2—Texas Cream Limestone core before (left) and after aging (right).
Results and Discussion

Contact-Angle Experiments. The contact angle, which is the angle between the solid surface and the tangent to the oil/water interface
at the three-phase boundary, is the most fundamental measure of wetting. After aging the calcite plates in oil, the plates were immersed
in the formation brine or surfactant formulations at the reservoir temperature of 60 C. Studies in the literature have reported the use of
cationic surfactants as successful wettability-altering agents (Austad and Milter 1997). Fig. 3a shows the oil droplets on calcite plates
immersed in the injection brine at the reservoir temperature of 60 C. Fig. 3b shows the oil droplets on calcite plates in two cationic sur-
factants; the shape of oil drops indicates wettability alteration. A blend of cationic and nonionic surfactants has also shown a promising
application in the wettability alteration of oil-wet calcite chips (Sharma and Mohanty 2013). Oil droplets were observed on plates
immersed in surfactant formulations S1 through S5 (Table 5) for at least 24 hours. Fig. 4 shows the oil droplets on the calcite plates
after t ¼ 24 hours in the surfactant solutions. It is evident that the surfactant formulations with cationic and nonionic/zwitterionic surfac-
tants changed the wettability of the plate from oil-wet to intermediate-wet. The contact angle was approximately 150 before treatment
and changed to approximately 60 to 90 after treatment with surfactant solutions. On the other hand, the anionic surfactant in Formula-
tion S5 was unable to change the wettability from oil-wet to water-wet.
0.4 wt% DTAB 0.4 wt% BTC 8358

(a) (b)
Fig. 3—Oil droplets on the calcite plate: (a) injection brine at t 5 24 hours; (b) cationic surfactants at t 5 24 hours.
Spontaneous-Imbibition Experiment. The wettability-altering ability of a surfactant solution is further quantified by this static imbi-
bition experiment. This imbibition experiment was conducted on a Texas Cream Limestone plug aged with crude oil for 3 to 4 weeks.
Surfactant Formulations S2 and S3 were used for this experiment. Fig. 5 shows the oil recovered from the hard-brine/surfactant formu-
lation in the imbibition cell after 4 months. Fig. 5a represents the initial oil-wet condition after equilibration with injection brine for
A (Surfactant Formulation S2) and B (Surfactant Formulation S3). Fig. 5b shows the final state of the core plugs after 4 months. The
significant oil production for both Formulations S2 and S3 shows that the surfactants were successful in wettability alteration and
improved oil recovery through spontaneous imbibition. The oil droplets shown on the core plug face for Formulation S2 also show the
clear change in contact angle to an intermediate-wet state. Because of the IFT generated with cationic surfactants, the rate of oil produc-
tion was significantly slower and hence monitored for a longer period of time.

Viscosity at Half-Life, No Crude Half-Life, With Crude

Formulation Surfactant Formulation 60°C (cp) Oil (minutes) Oil (minutes)
S1 0.5 wt% LB + injection brine 0.53 3±0.5 2.5±0.25
S2 0.2 wt% DTAB + 0.2 wt% NP-10 + injection brine 0.6 2±0.25 1.5±0.1
0.2 wt% GC 580 + 0.2 wt% Ethoquad C/25 +
S3 0.7 29±2 10±0.5
injection brine
S4 0.3 wt% GC 580 + 0.1 wt% LB + injection brine 0.7 180±20 7.0±0.5
0.5 wt% C14–16 AOS + 1.5 wt% EDTA +
S5 1.2 79±7 5.7±1
2 wt% Na2CO3 + injection brine
Table 5—Static foam-test results.
(S1) (S2) (S3)
(S4) (S5)
Fig. 4—Oil droplets on the calcite plate at t 5 24 hours for Surfactant Formulations S1, S2, S3, S4, and S5 from Table 5.
(a) (b)
Fig. 5—Spontaneous-imbibition experiment performed with Surfactant Formulations S2 and S3.
The two experiments for Formulation S2 (shown in Figs. 4 and 5) show that the oil recovery can be improved significantly by
changing the rock wettability from oil-wet to intermediate-wet. Gravity helps in the upward movement of oil in the core, whereas the
oil-wetness opposes this flow through capillary pressure, which is proportional to ccosh, where c is IFT and h is the contact angle. The
addition of surfactant decreases the IFT and reduces the contact angle, both reducing the opposing force. It is not necessary to reduce
the contact angle to lower than 90 to cause imbibition.
Static Foam Tests. Static foam tests were performed to compare the bulk foam stability of surfactant formulations. Single cationic sur-
factants such as DTAB and BTC 8358 showed weak foaming (not shown here). The anionic surfactant C14–16 alpha olefin sulfonate
(AOS) was used as a good foaming agent for reference. The foaming of mixed Surfactant Formulations S1 through S5 are shown in Table 5.
Average half-lives for Formulations S1 and S2 were found to be 3 and 2 minutes, respectively, whereas for Formulations S3, S4, and S5,
the half-lives were found to be 29, 180, and 79 minutes, respectively, in the absence of crude oil. GC 580 showed strong foaming with
the addition of a zwitterionic foam booster. Note that different proportions of surfactant blends were investigated for optimal perform-
ance depending on foaming properties and tolerance to crude oil, and the best combinations have been reported. Table 5 also shows the
effect of crude oil on foam stability, when crude oil is vigorously mixed with the foam. It significantly reduces the foam half-life.
Foam-Flow Experiments. Foam-flow experiments without oil were conducted in Texas Cream Limestone cores (varying between 15
and 20 md) to investigate the strength of foams in low-permeability cores. The total surfactant concentration was kept at 0.4 wt%. These
experiments were conducted in the absence of oil, and therefore in water-wet cores. The total flow rate in these experiments was

maintained at 4 ft/D. These experiments were performed at 60 C with a backpressure of 500 psi. Before each run, sufficient time
(>12 hours) was allowed to achieve isothermal conditions in the system. First, a base case was performed in which brine and gas were
coinjected at 80% quality. The average pressure drop after 10 PV of injection was recorded. Then, coinjection of surfactant formulation
and gas were performed at foam quality of 80% and the average steady-state pressure drop after 10 PV of injection was recorded. The
MRF (calculated as a ratio of steady-state pressure drop during surfactant/gas coinjection to the base case) was estimated for each
experiment. Table 6 summarizes the effective mobility reduction obtained with different surfactant formulations in low-permeability
cores. The MRF varied from 1.5 to 5. Formulation S4 had the highest half-life in the bulk stability test, and Formulation S5 had the
highest MRF in the absence of crude oil. In high-permeability cores, typical MRFs are approximately 10 to 30 (Fuseni et al. 2017).
Note the study performed in this reference was performed at a higher temperature. Hence, the MRF values reported would be slightly
higher at our reservoir conditions. Table 6 shows that weak foam was generated in low-permeability carbonate cores with low MRFs,
as suggested by Chabert et. al. (2012).
Pressure Drop
Pressure Drop (Surfactant + Brine +
Surfactant Formulation Type (Brine + CH4) (psi) CH4) (psi) MRF
S2: 0.2 wt% DTAB + 0.2 wt% NP-10 Cationic + nonionic 8.35 12.44 1.5
S4: 0.3 wt% GC 580 + 0.1 wt% LB Cationic + zwitterionic 3.7 14.14 3.8
S5: 0.5 wt% C14–16 AOS + 1.5 wt% EDTA
Anionic 8.84 43.93 5.0
+ 2 wt% Na2CO3
Table 6—Pressure drop in flow experiments with foam at 80% quality and without oil.
Foam Injection in Oil-Displacement Experiments. Coreflood experiments were performed to evaluate surfactant formulations with
wettability alteration and foaming ability. The total surfactant concentration was kept constant at 0.4 to 0.5 wt%. These experiments
were conducted with Texas Cream Limestone cores. The wettability state of the cores and the surfactant formulations used for each
experiment are reported in Table 4. A dead reservoir crude oil of with viscosity of 11.8 cp (at 60 C) was used in these experiments.
To understand the importance of wettability alteration along with foaming for incremental oil recovery in oil-wet carbonate rocks,
we first performed an experiment in a water-wet core (no aging with the oil). Coreflood 1 was performed on the water-wet Core C1
(Table 2) as the base case with a moderate-strength foaming Surfactant Formulation S1. The initial oil saturation was 76%. Fig. 6 shows
the injection sequence, cumulative oil recovery, residual oil saturation (primary y-axis), and overall pressure drop (secondary y-axis)
across the core. Methane gas was injected at 0.5 ft/D for approximately 2.5 PV until no additional oil was produced. The gasflood
recovery was 11% OOIP, and oil saturation was reduced to 67.7%. The pressure drop during the gasflood was between 1.5 and 2 psi.
The oil recovery is low in this flood because of viscous instability associated with gasflood and capillary end effect. Then, the core was
flooded with a slug of 0.5 PV of Surfactant Formulation S1 at the same rate, resulting in an additional oil recovery of 37% OOIP. The
pressure drops during this step varied between 3 and 8 psi. This recovery is high because the core is water-wet; water goes into the
smaller pores and displaces oil, whereas the previous gasflood displaced oil from mostly larger pores. Then, this surfactant-slug injec-
tion was followed with methane gas for approximately 2 PV until no oil was produced. This step produced 4.5% OOIP of additional oil,
with pressure drop between 2 and 3 psi. The injection of gas into some of the surfactant-saturated pores can form foam, which contrib-
uted to the incremental oil recovery. Finally, methane gas and Surfactant Formulation S1 were coinjected for approximately 3 PV at
1 ft/D with 70% foam quality, which produced an incremental oil recovery of approximately 8% OOIP. The pressure drops during this
stage varied between 10 and 18 psi. The higher pressure drops in the last stage suggest that initially in the presence of crude oil a weak
foam propagated through the core, and eventually foam stability increased with decreasing oil saturation in the experiment. The
ultimate cumulative oil recovery was 60.7% OOIP, oil recovery caused by surfactant and foam (over gasflood) was approximately
41.5% OOIP, and final oil saturation was reduced to 29.8%.
Gasflood S1 slug Gasflood S1 and

(0.5 ft/D) (0.5 ft/D) (0.5 ft/D) gas: 70% (1 ft/D)
80 30
70
Oil Recovery (%) and Sor (%)
25
Pressure Drop (psi)
60
Oil recovery (%)
20
50 Sor (%)
Pressure drop (psi)
40 15
30
10
20
5
10
0 0
0 1 2 3 4 5 6 7 8
PV Injection (60°C, 500 psi)
Fig. 6—Pressure-drop profile (right axis) and cumulative oil recovery and oil saturation (left axis) for Coreflood 1.
Coreflood 2 was performed in the oil-wet Core C2 (Table 2) with the same Surfactant Formulation S1 as in Coreflood 1. This surfac-
tant does not change wettability. The initial oil saturation was 75.3%. Fig. 7 shows the injection sequence, cumulative oil recovery,
residual oil saturation (primary y-axis), and overall pressure drop (secondary y-axis) across the core. Methane gas was injected at 0.5 ft/D

for approximately 3 PV until no oil was produced. The gasflood recovery was 8.2% OOIP and oil saturation was reduced to 69.1%. The
pressure drop during the gasflood was between 1 and 1.5 psi. Again, the oil recovery caused by gasflood is low because of unstable gas-
flood and capillary end effect. Then, the core was flooded with a 0.5-PV slug of Surfactant Formulation S1 at the same rate, resulting in
an additional oil recovery of 22.4% OOIP. The pressure drops during this step varied from 6 to 10 psi. The oil recovery in this step is
lower than that in Coreflood 1 because this core is oil-wet. The surfactant solution recovers oil because of a stable front contributed by
the surfactant itself and in-situ foam generation through mixing of methane and the surfactant solution in a porous medium. However, it
does not recover oil from smaller pores because of the oil-wetness of the rock with respect to water. Then, the surfactant-slug injection
was followed with methane gas for approximately 1.5 PV until no oil was produced. This step produced an additional oil of 3% OOIP,
with pressure drop between 1.5 and 2 psi. Foaming was the only mechanism but contributed a small incremental recovery. Finally,
methane gas and Surfactant Formulation S1 were coinjected for approximately 3 PV at 1 ft/D with 70% foam quality, which produced
an incremental recovery of approximately 21% OOIP. The pressure drops during this stage varied between 8 and 14 psi. The higher
pressure drops in the last stage suggest that in the presence of crude oil only a weak foam propagated through the core, and foam stabil-
ity increased with decreasing oil saturation in the experiment. The ultimate cumulative oil recovery was 54.5% OOIP, oil recovery
caused by in-situ foam generation (over gasflood) was approximately 25.4% OOIP, and final oil saturation was reduced to 34.4%. This
coreflood showed lower recovery because of injection of Surfactant S1 and gas (compared with Coreflood 1), primarily caused by the
oil-wetness of the rock. Hence, the wettability of the rock plays an important role in foam stability in porous media, and wettability
alteration is crucial to stabilize foam and enhance oil recovery.

80 30
70
25
60
Pressure Drop (psi)

Sor (%) 20
50
Oil recovery (%)
40 Pressure drop (psi) 15
30
10
20
5
10
0 0
0 1 2 3 4 5 6 7 8
Coreflood 3 was conducted in the oil-wet Core C3 with a wettability-altering and moderate-strength foaming Surfactant Formulation
S2; its properties are listed in Table 2. The oil permeability of this core was higher (13.5 md) and the initial oil saturation was lower
(62%) than the preceding two cores. Fig. 8 shows cumulative oil recovery, residual oil saturation (primary y-axis), and overall pressure
drop (secondary y-axis) across the core. Methane gas was injected at 0.5 ft/D for approximately 5 PV until no additional oil was pro-
duced. The gasflood recovery was 24.2% OOIP, and oil saturation was reduced to 47.3%. The pressure drop during the gasflood was
between 2.5 and 3 psi. Then, the core was flooded with a slug of 0.5 PV of Surfactant Formulation S2 at the same rate, resulting in an
additional oil recovery of 28.3% OOIP. The oil recovery caused by surfactant increased (compared with Coreflood 2) because of the
wettability-alteration ability of Surfactant Formulation S2. The pressure drops during this step varied from 6.3 to 15.5 psi. This slug
injection was followed with methane gas for approximately 2 PV until no oil was produced. This step produced an additional oil recov-
ery of 4% OOIP with pressure drop between 2.5 to 3 psi. Finally, methane gas and Surfactant Formulation S2 were coinjected for
approximately 1 PV at 0.5 ft/D with 80% foam quality, which produced approximately 6.5% OOIP. The pressure drops during this stage
varied between 2.5 and 4.2 psi. The low pressure drops suggest that in the presence of crude oil only weak foam propagated through the
core. The ultimate cumulative oil recovery was 62% OOIP, oil recovery caused by in-situ foam generation (over gasflood) was approxi-
mately 32.3% OOIP, and final oil saturation was reduced to 23.6% (which was lower than 34.4% for Coreflood 2). This coreflood shows
that a combination of wettability and weak foaming can enhance oil recovery if the reservoir is first developed with a secondary gas
injection. It is important to note that the pressure-drop fluctuations are not observed in this experiment because of lower sampling-data
frequency compared with the results in other corefloods.
On the basis of the results from Corefloods 2 and 3, we performed Coreflood 4 on an oil-wet core (Core C4) (Table 2) to demonstrate
the combined effect of wettability alteration and good foaming properties (Surfactant Formulation S3). The initial oil saturation was
63%. Fig. 9 shows the injection procedure, cumulative oil recovery, residual oil saturation (primary y-axis), and overall pressure drop
(secondary y-axis) across the core. Methane gas was injected at 0.5 ft/D and continued for approximately 2.3 PV until no additional oil
was produced. The gasflood recovery was 25% OOIP (similar to that in Coreflood 3), and oil saturation was reduced to 47.3%. The
pressure drop during the gasflood was between 1.5 and 2 psi. Then, the core was flooded with a 0.5-PV slug of Surfactant Formulation
S3 at the same rate, resulting in additional oil recovery of 9% OOIP. The pressure drops during this step varied from 3.5 to 5 psi. Then,
this slug injection was followed with methane gas for approximately 1.5 PV until no oil was produced. This step produced an additional
oil of 2% OOIP, with pressure drop between 1.5 and 2 psi. Wettability alteration and foaming were the suggested mechanisms that
would contribute to the incremental oil recovery, but because of the lack of aqueous stability of the surfactant solution at 25 C, lower
recovery and pressure drop were reported in the experiment. The phase separation of the aqueous-surfactant solution at this temperature
resulted in injection of fluid at an inconsistent mixing ratio, thus negatively affecting the recovery and pressure drop. In the last step,
the surfactant solution was preheated to 60 C and methane gas and Surfactant Formulation S3 were coinjected for approximately 4 PV

at 1 ft/D with 70% foam quality, which produced an incremental oil recovery of approximately 43% OOIP. The pressure drops during
this stage varied between 12 and 30 psi. The significant increase in recovery in the last stage of the experiment was primarily because
of the resolved issue of aqueous stability (no phase separation by preheating the surfactant solution at the reservoir temperature) and
generation of stronger foam along with wettability alteration. The ultimate cumulative oil recovery was 78.5% OOIP, oil recovery
caused by in-situ pregenerated foam was approximately 52% OOIP, and the final residual oil saturation was reduced to 13.6%. This
experiment proves the significance of the combined strategy of wettability alteration with foaming as a novel method to increase oil
production in oil-wet carbonate rocks after gasfloods.

70 30
60
25
Pressure Drop (psi)

50
20
40 Oil recovery (%)
Sor (%) 15
30 Pressure drop (psi)
10
20
5
10
0 0
0 1 2 3 4 5 6 7 8 9

90 30
80 Oil recovery (%)

25
Sor (%)
70
Pressure Drop (psi)

Pressure drop (psi)
60 20
50
15
40
30 10
20
5
10
0 0
0 1 2 3 4 5 6 7 8 9
Coreflood 5 was conducted in the oil-wet Core C5 with another wettability-altering and good foaming Surfactant Formulation S4; its
properties are listed in Table 2. The oil permeability of this core was higher (22 md), and the initial oil saturation was 64%. Fig. 10 shows
cumulative oil recovery, residual oil saturation (primary y-axis), and overall pressure drop (secondary y-axis) across the core. Methane
gas was injected at 0.5 ft/D for approximately 2 PV until no additional oil was produced. The gasflood recovery was 22% OOIP, and oil
saturation was reduced to 50%. The pressure drop during the gasflood was between 0.9 and 1.5 psi. Then, the core was flooded with a
0.5-PV slug of Surfactant Formulation S4 at the same rate, resulting in an additional oil recovery of 15.5% OOIP. The oil recovery caused
by surfactant increased because of the wettability-alteration ability of Surfactant Formulation S4. The pressure drops during this step
varied from 5 to 15 psi. Then, this slug injection was followed with methane gas for approximately 1.5 PV until no oil was produced.
This step produced 6% OOIP of additional oil with pressure drop between 2 and 3 psi. Finally, methane gas and Surfactant Formulation
S4 were coinjected for approximately 3 PV at 1 ft/D with 70% foam quality, which produced approximately 27% OOIP. The pressure
drops during this stage varied between 7 and 16 psi. The significant pressure drops suggest that in the presence of crude oil moderate
foam propagated through the core. The ultimate cumulative oil recovery was 70.3% OOIP, oil recovery caused by in-situ foam genera-
tion (over gasflood) was approximately 48% OOIP, and final oil saturation was reduced to 19%. This coreflood shows that a combination
of wettability and good foaming can enhance oil recovery if the reservoir is developed with secondary gas injection.
Coreflood 6 was conducted in the oil-wet Core C6 with a good foaming and nonwettability-altering Surfactant Formulation S5; its
properties are listed in Table 2. The oil permeability of this core was 15 md, and the initial oil saturation was 76%. Fig. 11 shows the
cumulative oil recovery, residual oil saturation (primary y-axis), and overall pressure drop (secondary y-axis) across the core. Methane

gas was injected at 0.5 ft/D for approximately 2.5 PV until no additional oil was produced. The gasflood recovery was 12.2% OOIP, and
oil saturation was reduced to 66.7%. The pressure drop during the gasflood was between 1 and 3 psi. Then, the core was flooded with a
0.5-PV slug of Surfactant Formulation S5 at the same rate, resulting in an additional oil recovery of 22.2% OOIP. The surfactant
increased oil recovery because of the lower IFT and the foaming ability of Surfactant Formulation S5. The pressure drops during this
step varied from 4 to 11 psi. Then, this slug injection was followed with methane gas for approximately 1.5 PV until no oil was produced.
This step produced an additional oil recovery of 8.4% OOIP, with pressure drop between 1 and 2.5 psi. Finally, methane gas and Surfac-
tant Formulation S5 were coinjected for approximately 3 PV at 1 ft/D with 70% foam quality, which produced approximately
26% OOIP. The pressure drops during this stage varied between 2 and 13 psi. The larger fluctuations in pressure drops during the last
phase suggest that in the presence of crude oil and no wettability alteration, foam stability is poor inside the porous medium. The ultimate
cumulative oil recovery was 68.8% OOIP, oil recovery caused by in-situ foam generation (over gasflood) was approximately
56.6% OOIP, and final oil saturation was 24%. This coreflood shows that good foaming alone with no wettability alteration is not suffi-
cient to have maximum oil recovery if the reservoir is developed with secondary gas injection. Note that the reported oil recovery caused
by surfactant injection in this experiment is higher because of the additional effect of IFT reduction by use of the anionic surfactant.

80 30
70 Oil recovery (%)

25
Sor (%)
60 Pressure drop (psi)
Pressure Drop (psi)

20
50
40 15
30
10
20
5
10
0 0
0 1 2 3 4 5 6 7

80 30
70
25
60
Pressure Drop (psi)
Oil recovery (%)

20
50 Sor (%)
Pressure drop (psi)
40 15
30
10
20
5
10
0 0
0 1 2 3 4 5 6 7
These previously discussed corefloods were designed for an alternating injection of gas and surfactant solution followed by a
coinjection of surfactant and gas at a fixed quality. Results in each of the corefloods showed that the initial slug of surfactant solution
with wettability-altering capability helps in changing the rock from oil-wet to water-wet and helps in stabilizing the foam in a porous
medium at reduced oil saturations. Coinjection of surfactant solution and gas immediately after the first gas-injection process would
have possibly provided similar recovery results but with increased amounts of fluid injection. With a reduced amount of aqueous surfac-
tant solution in the coinjection, the wettability alteration is a slower process and hence longer time is required for foam stabilization in
the porous medium. Additional experiments need to be performed to investigate this injection scheme for a comparative study.

Post-Coreflood Analysis. After the completion of Coreflood 5, we visually inspected the outside of the core. Some of the key findings
are as follows. First, the oil saturation increased from the top to the bottom, as shown in Fig. 12a. This is primarily because of better
sweep efficiency at the top of the core (point of injection of the foam) and also because of gravity drainage. Second, we observed visual
evidence of fluid channeling. Fig. 12b shows evidence of fluid channeling through the edges of the core, and the water-drop test proved
that areas swept by the wettability-altering surfactant solution were water-wet, whereas the unswept areas were still intermediate-to
oil-wet. Fig. 12c also confirms that the injection side of the core was altered from oil-wet to water-wet at the end of the experiment.
Injection Oil-wet Injection face
Production
Water-wet
(a) (b) (c)
Fig. 12—Post-experiment analysis for Coreflood 5: (a) fluid redistribution, (b) fluid channeling, (c) injection face.
Adsorption Experiments. Static adsorption experiments performed at the reservoir temperature showed promising results for cationic
surfactants compared with anionic surfactants for carbonate rocks. The cationic surfactants showed significantly lower adsorption
because of the positively charged carbonate-rock surface (compared with the anionic surfactants in the absence of alkali). Table 7 pro-
vides a summary of the adsorption obtained with the anionic foaming agent C14–16 AOS and cationic surfactant GC 580.
Surfactant GC 580 C14–16 AOS

Concentration (wt%) (mg/g rock) (mg/g rock)
0.1 0.007 0.14
0.5 0.009 0.19
1.0 0.01 0.26
Table 7—Comparative study of static adsorption in Texas

Cream Limestone.
Summary and Recovery Factors. To summarize the results from the oil-displacement experiments discussed previously and to under-
stand the efficiency of the processes, we have defined tertiary recovery factors (TRFs) to quantify the normalized reduction in residual
oil saturation caused by only surfactant injection (TRF1) and the surfactant/gas-coinjection processes (TRF2). TRF1 is calculated using
the normalized change in the residual oil saturation at the end of surfactant-solution-slug injection with wettability alteration, and TRF2
is calculated as the total normalized change in residual oil saturation at the end of surfactant/gas coinjection, which followed the slug-
injection process. That is,
ðSorg Sors Þ ðSorg Sorc Þ
TRF1 ¼ ; TRF2 ¼ : . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ð3Þ
Sorg Sorg
Table 8 summarizes the results of all the oil-displacement experiments with residual oil saturations at different stages of the process
and the corresponding TRF values. The results showed that Coreflood 3 has the highest TRF1 with good wettability alteration and mod-
erate foaming; it proved to be the most successful in reduction of residual oil saturation in oil-wet cores with only the surfactant-slug
injection. Note that Coreflood 1 has higher TRF1 than Coreflood 3, but that experiment was performed in a water-wet core (base case),
and hence was not included in the comparison. On the other hand, Corefloods 4 and 5, with good foaming and good wettability altera-
tion, were the most successful in total reduction of residual oil saturation (highest TRF2) at the end of the coinjection process. In addi-
tion, the results of Coreflood 6 were in agreement, where the TRF1 value was low because of no wettability-altering capability of the
surfactant formulation and the TRF2 value was high because of low IFT and good foaming ability. These results also emphasize
the fact that TRF1 is governed mostly on the wettability-altering ability of the surfactant solution, whereas TRF2 is governed mostly by
the foaming ability of the surfactant solution. The TRF values calculated agreed with our proposed strategy of a synergistic effect of
wettability alteration with foaming for increasing oil production.
Coreflood Soi Sorg Sors Sorc TRF1 TRF2

1 0.76 0.68 0.36 0.3 0.46 0.56
2 0.75 0.69 0.5 0.34 0.28 0.51
3 0.62 0.47 0.27 0.24 0.43 0.49
4 0.73 0.47 0.39 0.14 0.17 0.70
5 0.64 0.5 0.36 0.19 0.28 0.62
6 0.76 0.67 0.5 0.24 0.25 0.64
Table 8—Summary of oil-displacement experiments.

Conclusions
Secondary gasflooding in carbonate rocks is often poor because of oil-wetness and heterogeneity. Surfactant solutions and foams have
the potential to improve oil recovery but must overcome two adverse conditions in carbonates: oil-wettability and low permeability.
This study evaluates several surfactant solutions and foam formulations that combine wettability alteration and foaming in low-
permeability oil-wet carbonate cores. The following conclusions can be drawn from this study.
1. Cationic surfactants DTAB and BTC altered the wettability of the oil-wet calcite plate to water-wet but were ineffective in forming
foam. The addition of a nonionic surfactant TergitolTM NP helped in the foaming ability of these formulations.
2. Mixtures of in-house-developed Gemini cationic surfactant GC 580 and zwitterionic surfactants were able to alter the wettability
from oil-wet to intermediate-wet/water-wet and formed strong bulk foam.
3. The results obtained from the bulk foam tests without and with crude oil were a good indicator of the performance of the surfactant
formulations in porous media in the absence of crude oil and presence of crude oil, respectively. Higher half-life led to higher MRF
and higher oil recovery.
4. The foam generated in low-permeability water-wet carbonate cores (without oil) is weak with low MRFs, on the order of 3 (com-
pared with 20 for high-permeability cores).
5. Oil-displacement experiments in oil-wet carbonate cores revealed that injection of a wettability-altering surfactant can recover a sig-
nificant amount of oil (approximately 20 to 30% OOIP) over the secondary gasflood.
6. Foams with wettability-altering surfactants can also recover additional oil. The foam rheology in the presence of oil suggests propa-
gation of only weak/moderate foam in oil-wet carbonate cores.
7. Post-coreflood analysis showed visual evidence of successful wettability-alteration and fluid-channeling effects caused by weak
foam generated in the porous media.
8. Wettability alteration in synergy with foaming improves oil recovery significantly and is crucial to make foam stable in oil-wet
porous media.
Nomenclature
C ¼ final surfactant concentration, ppm
Co ¼ initial surfactant concentration, ppm
mcarbonate ¼ mass of crushed limestone, g
msolution ¼ mass of surfactant solution, g
MRF ¼ mobility reduction factor
PV ¼ pore volume, cm3
q ¼ adsorption of surfactant, mg/g
Soi ¼ initial oil saturation
Sorc ¼ residual oil saturation to surfactant/gas coinjection
Sorg ¼ residual oil saturation to gasflood
Sors ¼ residual oil saturation to surfactant injection
Swc ¼ connate water saturation
TRF1 ¼ tertiary recovery factor to surfactant injection
TRF2 ¼ tertiary recovery factor to surfactant/gas coinjection
DP ¼ pressure drop, psi
Acknowledgments
We are thankful to the sponsors of the Gas EOR Industrial Affiliates Project at the University of Texas at Austin for partial funding of
this work.
References
Adibhatla, B. and Mohanty, K. K. 2008. Oil Recovery From Fractured Carbonates by Surfactant-Aided Gravity Drainage: Laboratory Experiments and
Mechanistic Simulations. SPE Res Eval & Eng 11 (1): 119–130. SPE-99773-PA. https://doi.org/10.2118/99773-PA.
Alvarez, J. O., Neog, A., Jais, A. et al. 2014. Impact of Surfactants for Wettability Alteration in Stimulation Fluids and the Potential for Surfactant
EOR in Unconventional Liquid Reservoirs. Presented at the SPE Unconventional Resources Conference, The Woodlands, Texas, 1–3 April. SPE-
169001-MS. https://doi.org/10.2118/169001-MS.
Anderson, W. G. 1987. Wettability Literature Survey—Part 4: Effects of Wettability on Capillary Pressure. J Pet Technol 39 (10): 1283–1300. SPE-
15271-PA. https://doi.org/10.2118/15271-PA.
Angarska, J. K., Tachev, K. D., Ivanov, I. B. et al. 1997. Effect of Magnesium Ions on the Properties of Foam Films Stabilized With Sodium Dodecyl
Sulfate. J. Colloid Interf. Sci. 195 (2): 316–328. https://doi.org/10.1006/jcis.1997.5133.
Arnaudov, L., Denkov, N. D., Surcheva, I. et al. 2001. Effect of Oily Additives on Foamability and Foam Stability. 1. Role of Interfacial Properties.
Langmuir 17 (22): 6999–7010. https://doi.org/10.1021/la010600r.
Austad, T. and Milter, J. 1997. Spontaneous Imbibition of Water Into Low Permeable Chalk at Different Wettabilities Using Surfactants. Presented at
the International Symposium on Oilfield Chemistry, Houston, 18–21 February. SPE-37236-MS. https://doi.org/10.2118/37236-MS.
Basheva, E. S., Ganchev, D., Denkov, N. D. et al. 2000. Role of Betaine as Foam Booster in the Presence of Silicone Oil Drops. Langmuir 16 (3):
1000–1013. https://doi.org/10.1021/la990777+.
Blaker, T., Aarra, M. G., Skauge, A. et al. 2002. Foam for Gas Mobility Control in the Snorre Field: The FAWAG Project. SPE Res Eval & Eng 5 (4):
317–323. SPE-78824-PA. https://doi.org/10.2118/78824-PA.
Boud, D. C. and Holbrook, O. C. 1958. Gas Drive Oil Recovery Process. US Patent No. 28,665,07A.
Chabert, M., Morvan, M., and Nabzar, L. 2012. Advanced Screening Technologies for the Selection of Dense CO2 Foaming. Presented at the SPE
Improved Oil Recovery Symposium, Tulsa, 14–18 April. SPE-154147-MS. https://doi.org/10.2118/154147-MS.
Chilingar, G. V. and Yen, T. F. 1983. Some Notes on Wettability and Relative Permeabilities of Carbonate Reservoir Rocks, II. Energ. Source. 7 (1):
67–75. https://doi.org/10.1080/00908318308908076.
Chou, S. I., Vasicek, S. L., Pisio, D. L. et al. 1992. CO2 Foam Field Trial at North Ward-Estes. Presented at the SPE Annual Technical Conference and
Exhibition, Washington, DC, 4–7 October. SPE-24643-MS. https://doi.org/10.2118/24643-MS.

du Pétrole, F. and Malmaison, F. R. 1990. Evaluation of Reservoir Wettability and Its Effect on Oil Recovery. In Interfacial Phenomena in Petroleum
Recovery, ed. N. R. Morrow, Chap. 9, 319–376. Boca Raton, Florida: CRC Press.
Falls, A. H., Hirasaki, G. J., Patzek, T. W. et al. 1988. Development of a Mechanistic Foam Simulator: The Population Balance and Generation by Snap-
Off. SPE Res Eng 3 (3): 884–892. SPE-14961-PA. https://doi.org/10.2118/14961-PA.
Falls, A. H., Musters, J. J., and Ratulowski, J. 1989. The Apparent Viscosity of Foams in Homogeneous Bead Packs. SPE Res Eval & Eng 4 (2):
Farajzadeh, R., Andrianov, A., and Zitha, P. L. J. 2009. Investigation of Immiscible and Miscible Foam for Enhancing Oil Recovery. Ind. Eng. Chem.
Res. 49 (4): 1910–1919. https://doi.org/10.1021/ie901109d.
Farajzadeh, R., Andrianov, A., Krastev, R. et al. 2012. Foam–Oil Interaction in Porous Media: Implications for Foam Assisted Enhanced Oil Recovery.
Adv. Colloid Interf. Sci. 183–184 (15 November): 1–13. https://doi.org/10.1016/j.cis.2012.07.002.
Fuseni, A. B., Julaih, A. H., Al-Aseeri, A. A. et al. 2017. Development and Evaluation of Foam-Based Conformance Control for a High Salinity and
High Temperature Carbonate. Presented at the SPE Middle East Oil & Gas Show and Conference, Manama, Bahrain, 6–9 March. https://doi.org/
10.2118/183772-MS.
Gupta, R. and Mohanty, K. 2010. Temperature Effects on Surfactant-Aided Imbibition Into Fractured Carbonates. SPE J. 15 (3): 588–597. SPE-110204-
PA. https://doi.org/10.2118/110204-PA.
Hadjiiski, A., Tcholakova, S., Denkov, N. D. et al. 2001. Effect of Oily Additives on Foamability and Foam Stability. 2. Entry Barriers. Langmuir 17
(22): 7011–7021. https://doi.org/10.1021/la010601j.
Haugen, Å., Fernø, M. A., Graue, A. et al. 2012. Experimental Study of Foam Flow in Fractured Oil-Wet Limestone for Enhanced Oil Recovery. SPE
Res Eval & Eng 15 (2): 218–228. SPE-129763-PA. https://doi.org/10.2118/129763-PA.
Holm, L. W. 1968. The Mechanism of Gas and Liquid Flow Through Porous Media in the Presence of Foam. SPE J. 8 (4): 359–369. https://doi.org/
10.2118/1848-PA.
Khatib, Z. I., Hirasaki, G. J., and Falls, A. H. 1988. Effects of Capillary Pressure on Coalescence and Phase Mobilities in Foams Flowing Through Porous
Media. SPE Res Eng 3 (3): 919–926. SPE-15442-PA. https://doi.org/10.2118/15442-PA.
Kovscek, A. R., Patzek, T. W., and Radke, C. J. 1994. Mechanistic Prediction of Foam Displacement in Multidimensions: A Population Balance
Approach. Presented at the SPE/DOE Improved Oil Recovery Symposium, Tulsa, 17–20 April. SPE-27789-MS. https://doi.org/10.2118/27789-MS.
Li, R. F., Hirasaki, G., Miller, C. A. et al. 2012. Wettability Alteration and Foam Mobility Control in a Layered, 2D Heterogeneous Sandpack. SPE J. 17
(4): 1207–1220. SPE-141462-PA. https://doi.org/10.2118/141462-PA.
Mahani, H., Keya, A. L., Berg, S. et al. 2015. Insights Into the Mechanism of Wettability Alteration by Low-Salinity Flooding (LSF) in Carbonates.
Energy Fuels 29 (3): 1352–1367. https://doi.org/10.1021/ef5023847.
Mast, R. F. 1972. Microscopic Behavior of Foam in Porous Media. Presented at the Fall Meeting of the Society of Petroleum Engineers of AIME, San
Antonio, Texas, 8–11 October. SPE-3997-MS. https://doi.org/10.2118/3997-MS.
Mohan, K., Gupta, R., and Mohanty, K. K. 2011. Wettability Altering Secondary Oil Recovery in Carbonate Rocks. Energy Fuels 25 (9): 3966–3973.
https://doi.org/10.1021/ef200449y.
Montaron, B. 2005. Increasing Oil Recovery Factors: A Technical Challenge Key to Future World Energy Supply. Oral presentation given at the AFTP
Conference, Paris, October.
Patzek, T. W. 1996. Field Applications of Steam Foam for Mobility Improvement and Profile Control. SPE Res Eng 11 (2): 79–86. SPE-29612-PA.
https://doi.org/10.2118/29612-PA.
Ransohoff, T. C. and Radke, C. J. 1988. Mechanisms of Foam Generation in Glass-Bead Packs. SPE Res Eng 3 (2): 573–585. SPE-15441-PA. https://
doi.org/10.2118/15441-PA.
Raza, S. H. 1970. Foam in Porous Media: Characteristics and Potential Applications. SPE J. 10 (4): 328–336. SPE-2421-PA. https://doi.org/10.2118/
2421-PA.
Roehl, P. O. and Choquette, P. W. eds. 1985. Carbonate Petroleum Reservoirs. Berlin: Springer Science and Business Media.
Rossen, W. R. 1990. Minimum Pressure Gradient for Foam Flow in Porous Media: Effect of Interactions With Stationary Lamellae. J. Colloid Interf.
Sci. 139 (2): 457–468. https://doi.org/10.1016/0021-9797(90)90118-8.
Rossen, W. R. and Gauglitz, P. A. 1990. Percolation Theory of Creation and Mobilization of Foams in Porous Media. AIChE J. 36 (8): 1176–1188.
https://doi.org/10.1002/aic.690360807.
Rossen, W. R., van Duijn, C. J., Nguyen, Q. P. et al. 2010. Injection Strategies To Overcome Gravity Segregation in Simultaneous Gas and Water Injec-
tion Into Homogeneous Reservoirs. SPE J. 15 (1): 76–90. SPE-99794-PA. https://doi.org/10.2118/99794-PA.
Sanchez, J. M. and Hazlett, R. D. 1992. Foam Flow Through an Oil-Wet Porous Medium: A Laboratory Study. SPE Res Eng 7 (1): 91–97. SPE-19687-
PA. https://doi.org/10.2118/19687-PA.
Schlumberger Market Analysis. 2007. https://www.slb.com/~/media/Files/industry_challenges/carbonates/brochures/cb_carbonate_reservoirs_07os003.pdf.
Schramm, L. L. and Novosad, J. J. 1992. The Destabilization of Foams for Improved Oil Recovery by Crude Oils: Effect of the Nature of the Oil. J. Pet.
Sci. Eng. 7 (1–2): 77–90. https://doi.org/10.1016/0920-4105(92)90010-X.
Schramm, L. L. and Mannhardt, K. 1996. The Effect of Wettability on Foam Sensitivity to Crude Oil in Porous Media. J. Pet. Sci. Eng. 15 (1): 101–113.
https://doi.org/10.1016/0920-4105(95)00068-2.
Seethepalli, A., Adibhatla, B., and Mohanty, K. K. 2004. Physicochemical Interactions During Surfactant Flooding of Fractured Carbonate Reservoirs.
SPE J. 9 (4): 411–418. SPE-89423-PA. https://doi.org/10.2118/89423-PA.
Sharma, G. and Mohanty, K. 2013. Wettability Alteration in High-Temperature and High-Salinity Carbonate Reservoirs. SPE J. 18 (4): 646–655. SPE-
Siddiqui, S., Talabani, S., Saleh, S. T. et al. 1997. A Laboratory Investigation of Foam Flow in Low-Permeability Berea Sandstone Cores. Presented at
the SPE Production Operations Symposium, Oklahoma City, Oklahoma, 9–11 March. SPE-37416-MS. https://doi.org/10.2118/37416-MS.
Singh, R. and Mohanty, K. K. 2015a. Foams Stabilized by In-Situ Surface-Activated Nanoparticles in Bulk and Porous Media. SPE J. 21 (1): 121–130.
SPE-170942-PA. https://doi.org/10.2118/170942-PA.
Singh, R. and Mohanty, K. K. 2015b. Synergy Between Nanoparticles and Surfactants in Stabilizing Foams for Oil Recovery. Energy Fuels 29 (2):
467–479. https://doi.org/10.1021/ef5015007.
Singh, R. and Mohanty, K. K. 2016. Foams With Wettability-Altering Capabilities for Oil-Wet Carbonates: A Synergistic Approach. SPE J. 21 (4):
Strand, S., Standnes, D. C., and Austad, T. 2003. Spontaneous Imbibition of Aqueous Surfactant Solutions Into Neutral to Oil-Wet Carbonate Cores:
Effects of Brine Salinity and Composition. Energy Fuels 17 (5): 1133–1144. https://doi.org/10.1021/ef030051s.
Tang, G. Q. and Morrow, N. R. 1997. Salinity, Temperature, Oil Composition, and Oil Recovery by Waterflooding. SPE Res Eng 12 (4): 269–276. SPE-

Vikingstad, A. K., Skauge, A., Høiland, H. et al. 2005. Foam–Oil Interactions Analyzed by Static Foam Tests. Colloids Surfaces A 260 (1): 189–198.
https://doi.org/10.1016/j.colsurfa.2005.02.034.
Wang, L. and Mohanty, K. 2014. Enhanced Oil Recovery in Gasflooded Carbonate Reservoirs by Wettability-Altering Surfactants. SPE J. 20 (1): 60–69.
SPE-166283-PA. https://doi.org/10.2118/166283-PA.
Wang, L. K. and Langley, D. F. 1977. Identification and Determination of Ionic Surface Active Agents. Arch. Environ. Con. Tox. 5 (1): 447–456. https://
doi.org/10.1007/BF02220924.
Yekeen, N., Manan, M. A., Idris, A. K. et al. 2017. Influence of Surfactant and Electrolyte Concentrations on Surfactant Adsorption and Foaming Char-
acteristics. J. Pet. Sci. Eng. 149 (20 January): 612–622. https://doi.org/10.1016/j.petrol.2016.11.018.
Yousef, A. A., Al-Saleh, S., and Al-Jawfi, M. S. 2011. Smart WaterFlooding for Carbonate Reservoirs: Salinity and Role of Ions. Presented at the SPE
Middle East Oil and Gas Show and Conference, Manama, Bahrain, 25–28 September. SPE-141082-MS. https://doi.org/10.2118/141082-MS.
Yu, L. and Wardlaw, N. C. 1986. The Influence of Wettability and Pore-Throat Size Ratio on Snap-Off. J. Colloid Interf. Sci. 109 (2): 461–472. https://
doi.org/10.1016/0021-9797(86)90324-3.
Zhang, D. L., Liu, S., Puerto, M. et al. 2006. Wettability Alteration and Spontaneous Imbibition in Oil-Wet Carbonate Formations. J. Pet. Sci. Eng. 52
(13–4): 213–226. https://doi.org/10.1016/j.petrol.2006.03.009.
Pinaki Ghosh is a PhD degree student in petroleum and geosystems engineering at the University of Texas at Austin. His research
interests include gas EOR, chemical EOR, and reservoir simulation targeted for challenging carbonate reservoirs. Ghosh holds a
bachelor’s degree in chemical engineering from the Indian Institute of Technology, Kharagpur, and a master’s degree in petro-
leum and geosystems engineering from the University of Texas at Austin.
Kishore K. Mohanty is a professor of petroleum engineering at the University of Texas at Austin and the director of the Center for
Petroleum and Geosystems Engineering. He worked at Arco Oil and Gas Company from 1981 to 1991 and taught at the Univer-
sity of Houston from 1991 to 2008. Mohanty’s research is directed at EOR, formation evaluation, improved fracturing, and nano-
technology. He holds a bachelor’s degree from the Indian Institute of Technology, Kanpur, and a PhD degree from the
University of Minnesota, both in chemical engineering. Mohanty received a Pioneer Award at the SPE Improved Oil Recovery
Symposium in 2008, the 2013 SPE/AIME Anthony F. Lucas Gold Medal, and the 2016 SPE Distinguished Achievement Award for
Petroleum Engineering Faculty. He was the executive editor of SPE Journal from 2002 to 2003.

Novel Application of Cationic Surfactants For Foams With Wettability Alteration in Oil-Wet Low-Permeability Carbonate Rocks

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Novel Application of Cationic Surfactants For Foams With Wettability Alteration in Oil-Wet Low-Permeability Carbonate Rocks

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J179598 DOI: 10.

2118/179598-PA Date: 17-November-18 Stage: Page: 2218 Total Pages: 14

Novel Application of Cationic Surfactants

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Name Structure Active Molecular Weight Type

Table 1—Surfactants used in the present study.

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Table 2—Properties of different carbonate cores.

Composition Formation Brine Injection Brine

Table 3—Formation and injection brine used in the study.

DPsurfþgas Injection-gas rate

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Initial Formulation Viscosity at IFT

Results and Discussion

0.4 wt% DTAB 0.4 wt% BTC 8358

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Viscosity at Half-Life, No Crude Half-Life, With Crude

Table 5—Static foam-test results.

(S1) (S2) (S3)

Fig. 5—Spontaneous-imbibition experiment performed with Surfactant Formulations S2 and S3.

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Gasflood S1 slug Gasflood S1 and

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Gasflood S1 slug Gasflood S1 and

Pressure Drop (psi)

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Gasflood S2 slug Gasflood S2 and

Pressure Drop (psi)

Gasflood S3 slug Gasflood S3 and

80 Oil recovery (%)

Pressure Drop (psi)

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Gasflood S4 slug Gasflood S4 and

70 Oil recovery (%)

Pressure Drop (psi)

Gasflood S5 slug Gasflood S5 and

Oil recovery (%)

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Injection Oil-wet Injection face

(a) (b) (c)

Surfactant GC 580 C14–16 AOS

Table 7—Comparative study of static adsorption in Texas

Coreflood Soi Sorg Sors Sorc TRF1 TRF2

Table 8—Summary of oil-displacement experiments.

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