SPE 159979

Surfactant Enhanced Oil Recovery from Naturally Fractured Reservoirs

Jun Lu, SPE, Ali Goudarzi, SPE, Peila Chen, SPE, Do Hoon Kim, SPE, Christopher Britton, SPE, Mojdeh
Delshad, SPE, Kishore K. Mohanty, SPE, Upali P. Weerasooriya, SPE, and Gary A. Pope, SPE
The University of Texas at Austin

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Annual Technical Conference and Exhibition held in San Antonio, Texas, USA, 8-10 October 2012.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
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Abstract
Large volumes of oil remain in naturally fractured carbonate oil reservoirs and water floods are often very inefficient because
many of these reservoirs are mixed-wet or oil-wet as well as extremely heterogeneous. Naturally fractured reservoirs are
challenging targets for chemical flooding because they typically have a high permeability contrast between the fractures and
the matrix with low to extremely low matrix permeability. In addition, some of the world’s largest oil reservoirs are fractured
carbonates with high reservoir temperature and high salinity formation brine and some of them also have low API gravity
oils, which also increases the difficulty of recovering the oil. We have developed a stable surfactant that shows promising
results even when all of these conditions are present at the same time. Both static and dynamic imbibition experiments were
done using a fractured carbonate core. These results were interpreted using a mechanistic chemical reservoir simulator.

Introduction
Carbonate reservoirs hold approximately 60% of the world’s oil reserves (Akbar et al., 2000). A large number of carbonate
reservoirs are naturally fractured and are mixed-wet to oil-wet (Roehl and Choquette, 1985; Chillenger and Yen, 1983). Most
of carbonate reservoirs have a high degree of heterogeneity and complex pore structure. Naturally fractured carbonate
reservoirs typically have high permeability fractures and a low permeability matrix. This high contrast of permeability
between matrix and fractures and mixed-wet or oil-wet reservoir leads to poor water flood efficiency. The oil recovery from
naturally fractured carbonate reservoirs is typically much less than one-third.
Wettability has been long recognized as an important factor strongly affecting oil recovery using EOR methods (Zhou et
al., 2000; Morrow and Mason, 2001; Tong et al., 2002; Hirasaki and Zhang, 2004). Water floods are often inefficient because
many of these reservoirs are mixed-wet or oil-wet as well as extremely heterogeneous. Changing the wettability of the
fractured reservoirs from oil or mixed-wet toward water-wet improves oil recovery efficiency. A lot of research has been
done on wettability alteration by surfactants (Austad et al., 1998; Zhang et al., 2004; Seethepalli et al., 2004; Xie et al., 2004;
Sharma and Mohanty, 2011; Chen and Mohanty, 2012).
Static imbibition experiments have been widely used to evaluate different EOR surfactants. The recovery from fractured
carbonate reservoirs is frequently considered to be dominated by gravity and capillary forces. However, the role of viscous
forces may also be important and should be investigated (Delshad et al., 2009). The Marangoni effect (Austad and Milter,
1997) and spontaneous emulsification (Zhang et al., 2008) might also promote imbibition in some static imbibition
experiments. Goudarzi et al. (2012) suggested that changing the matrix block size affects the oil recovery from static
imbibition experiments.
The imbibition experiments using surfactants that produce low IFT have been done by several investigators (Hirasaki and
Zhang, 2004; Seethepalli et al., 2004; Abidhatla and Mohanty, 2006). Hirasaki and Zhang (2004) suggested the dominant oil
recovery mechanism in low IFT imbibition to be buoyancy and wettability alteration. With some anionic surfactants, the IFT
can be reduced to ultra-low values where the capillary pressure is reduced to nearly zero. When the capillary pressure is
nearly zero, then other forces must be present to account for the rapid imbibition observed in many experiments. The
simulation results by Abbasi-Asl et al. (2010) showed that transverse pressure gradients between the fractures and matrix can
push the surfactant further into the matrix in the dynamic imbibition process.
With the improved understanding of the relationship between the surfactant structure and the performance (Solairaj et al.,
2012; Adkins et al., 2012; Lu et al., 2012), we were able to develop a surfactant formulation that shows promising results
2 SPE 159979

even when all of the difficult reservoir conditions mentioned above are present at the same time. The surfactant formulation
was tested by doing a fractured coreflood.

Experimental Materials and Procedure

Surfactants and Materials.
Surfactants. Guerbet alkoxy carboxylates were synthesized from Guerbet alkoxylates in the laboratory at The University
of Texas. Internal olefin sulfonates (IOS) were obtained from Stepan Company.
Electrolytes and brines. Sodium chloride, calcium chloride dihydrate, magnesium chloride hexahydrate, and sodium
sulfate were obtained from Fisher Chemical and used as received. The synthetic sea water (SSW) and the synthetic formation
brine (SFB) were prepared. The mixture of SSW and SFB was used for phase behavior and coreflood experiments.
Crude oil. Crude oil was provided by the company. The surrogate oil (a mixture of dead crude and a low-EACN
hydrocarbon to match the live oil EACN) was used for the experiments at ambient pressure to account for the effect of
solution gas on phase behavior. The surrogate oil contained 30 wt% cyclohexane and 70 wt% dead crude. The API of the oil
was 22, and the viscosity of surrogate was 2.1 cp at 100 °C.

Phase Behavior Experiments. Surfactant phase behavior tests were used to identify good surfactant formulations for this
specific oil at the reservoir temperature. The detailed procedure can be found in Levitt et al. (2006), Flaaten et al. (2008), and
Zhao et al. (2008) among other papers. The surfactant mixtures with oil and brine were carefully observed for a long time
period. The surfactants that form a low viscosity microemulsion in a few days and show ultra-low IFT were selected for
further evaluation. The aqueous surfactant solution was observed for stability and clarity at both room temperature and
reservoir temperature to determine if it was stable up to at least optimum salinity.

Static Imbibition Experiment. The surfactant formulations with good phase behavior were tested for their ability to imbibe
into reservoir core plugs. One reservoir core plug was prepared by cleaning and saturating with the formation brine. The
properties of the core are listed in Table 1. Oil was then injected into the core to reach a saturation of Swi; then it was aged at
the reservoir temperature for about a month. Because of its high heterogeneity, a high initial oil saturation (Soi) could not be
achieved. Imbibition cells were constructed in the Custom Lab Glass Services at The University of Texas, Austin. The oil-
aged core was placed inside the imbibition cell. Then the imbibition cell was filled with the formation brine or the surfactant
solution to its neck. If the surfactant solution imbibed into the core plug then the oil was pushed out of the core and
accumulated in the neck of glass cell. The volume of the produced oil was monitored on a daily basis (or as often as
appropriate).

Coreflood.
CT scan. A modified medical CT scanner was used to scan the core before and after being fractured. The core was
scanned at the energy level of 80 kV from the top to the bottom. The thickness of each slice and the distance between
consecutive images was 10 mm. The reservoir core was highly vuggy and heterogeneous by visual observations and CT scan
analysis.
Coreflood experiment. A reservoir core of about 10.8 inches in length and 4.0 inches in diameter was obtained, then dried
and weighed. The core was wrapped with a Teflon heat shrink tube and then inserted into a 4-inch diameter core holder with
a confined pressure of 1000 psi applied. The core was cleaned by injecting many pore volumes of toluene, methanol, and
synthetic formation brine (SFB). Pressure data were recorded and the brine permeability was measured to be about 6 md,
which is close to the matrix permeability.
The core was then taken out of the core holder and cut into 3 pieces for the convenience of further processes. Each piece
of core plug was about 3-4 inches long. Then a slight notch was made along the side of each core plug. The core was
hammered on the notch to create fractures throughout the rock to mimic the natural fractures in the reservoir. The quick-
curing epoxy was used to fill the notches and vugs on the rock surface to prevent the thrust of the robber sleeve when
confined pressure applied. The three core plugs were then stacked together to make a 10.8 inch-length composite core. The
core was dried and put back into core holder again. The core was evacuated by a vacuum pump and then saturated with SFB
to measure the pore volume of about 216 ml by material balance. The core holder was placed in the 100 °C oven with a back
pressure of 100 psi, and flooded with SFB. The brine permeability of the composite fractured core was measured to be about
1970 md. Filtered oil was then flooded from the top of the vertical standup core at a frontal velocity of 6 ft/day until no brine
was produced. After aging for 5 days, another oil flood was conducted to displace out more brine and estimate the oil
permeability and residual water saturation. The water flood was performed with SFB at 12 ft/day and stopped shortly after
the water breakthrough. The residual oil saturation and relative water permeability were determined.
The chemical flood experiment was designed with a favorable salinity gradient to maximize the robustness of the flood
(Pope et al., 1979). The salinities of the surfactant slug and brine drive are determined from phase behavior data. A
differential pressure transducer was used to measure the pressure drop across the entire core. Effluent from the core was
collected by fraction collector and sampled in glass test tubes to analyze the oil content, surfactant concentration, and salinity.
SPE 159979 3

The comparisons of the static imbibition experiment and the fractured coreflood are listed in Table 1. The fractured coreflood
experiment is summarized in Table 2. Table 3 lists the brine compositions in the fractured coreflood.

Description of Numerical Simulation

UTCHEM is a numerical reservoir simulator that models chemical processes such as surfactant flooding. For modeling
wettability alteration, the initial and final wettability conditions are defined by two sets of input parameters. Each set includes
relative permeability, capillary pressure and residual saturation-trapping number parameters. The altered relative permeability
and capillary pressure values used for the multiphase flow calculations are interpolated between the two sets as follows:

k altered r  1  1  k r
 1k final initial (1)
r

Pcaltered  2 Pcfinal  1  2  Pcinitial (2)

where ‘final’ and ‘initial’ are the extreme wetting states and ‘altered’ is the interpolated state due to the surfactant. The
scaling factors 1 and 2 can be constants or dependent on adsorbed surfactant concentration.

Modeling Coreflood Experiment Using UTCHEM. A random heterogeneous permeability distribution was used to model
the extremely heterogeneous fractured and vuggy core. A Cartesian 5×5×10 grid was used as shown in Fig. 1. The average
brine permeability was 1970 md and the Dykstra-Parsons coefficient was 0.9. Both interfacial tension reduction and
wettability alteration were modeled. The surfactant causes more favorable relative permeabilities and capillary pressures by
wettability alteration from mixed-wet to water-wet and also lower residual oil saturation by decreasing interfacial tension.

Results and Discussion

Phase Behavior Results. The Guerbet alkoxy carboxylate surfactants have been tested and shown to be very effective at
high temperature in hard brine (Lu et al., 2012). The surfactant formulation developed was a mixture of 0.5 wt% C28-25PO-
25EO-Carboxylate and 0.5 wt% C15-18 IOS. No co-solvent was needed. This formulation equilibrates fast and shows a high
optimum solubilization ratio of about 16 at the optimum salinity of about 57,000 ppm as shown in Fig. 2. This formulation
has excellent tolerance of divalent cations such as calcium and magnesium. The aqueous solutions were clear and stable up to
58,000 ppm TDS for more than 32 days at the reservoir temperature of 100 °C. This surfactant formulation was used in both
static imbibition and fractured coreflood experiments.

Static Imbibition Experimental Results. The objective of static imbibition test is to investigate the oil recovery mechanism
by an ultra-low IFT surfactant formulation, and also compare this result with that of the dynamic imbibition process. In this
study, one reservoir core plug 1.5 inches × 3.09 inches was saturated with formation brine and then flooded with surrogate oil
to reach residual water saturation. The core was then immersed into the surrogate oil to age. After rendering oil-wet, the
reservoir core was placed inside the imbibition cell along with the surfactant solution. The surfactant formulation was
evaluated by static spontaneous imbibition test. The imbibition oil recovery reached 33.3 % OOIP in 17 days, reducing the oil
saturation to 0.39 as shown in Figure 3. In this experiment, most of oil was observed to be produced from the top edge of the
core, which indicates that buoyancy is important in this experiment.

CT Scan Analysis. A CT scan of the core was conducted before and after the core was fractured. The images in Fig. 4 show
that the reservoir core is extremely heterogeneous and vuggy before fractures were made. Some vugs are connected and some
are isolated. Some parts of the core have higher vug density than other parts. The size of the vugs also varies a lot. The
images in Fig. 5 show the core after it was fractured. Some vugs are connected with fractures and some are not.

Coreflood Results. The brine permeability was 6 md before the core was fractured. After it was fractured, the permeability
of the core was 1970 md. The permeability contrast between fractures and matrix was then about the same as the actual
fractured reservoir. It is very difficult to use polymer for mobility control under the reservoir conditions of 100 °C and 6 md
matrix permeability, so the surfactant solution was injected at a low velocity (0.2 ft/D) both to take advantage of buoyancy
and to allow more time for imbibition and wettability alteration.
After water breakthrough during a short water flood, surfactant solution was injected to displace the surrogate oil at 100
°C. The formulation consisted of 0.5 wt% C28-25PO-25EO-Carboxylate and 0.5 wt% C15-18 IOS. A 0.25 PV surfactant slug
was injected into the core, the core was soaked for 20 hours, and then brine was injected to displace the surfactant. The initial
(formation) brine had a salinity of about 117,000 ppm TDS with a divalent cation concentration of about 4,000 ppm. The
salinity of the surfactant slug was 57,000 ppm TDS with a divalent cation concentration of about 1,800 ppm. The novel
Guerbet alkoxy carboxylate and IOS surfactant mixture can tolerate such high temperature, salinity and hardness, and still
produce ultra-low IFT and aqueous stability.
The oil recovery data are shown in Fig. 6. The oil cut was high in the beginning because of the short water flood. The
second oil cut bump occurred due to the 20 hours soaking after surfactant slug injection. After soaking, about 1.46 PV brine
4 SPE 159979

was injected with a salinity of 10,000 ppm TDS. The chemical flood was stopped after about 1.71 PV of injection at an oil
cut of about 5 %. The cumulative oil recovery was 65.9% of the remaining oil after the water flood, and the final oil
saturation decreased from 0.412 to 0.140. More oil would have been recovered if the chemical flood had continued.
Compared with the static imbibition experimental results, the coreflood showed higher oil recovery and the oil was produced
at a faster rate. Because of the high permeability fractures, low injection rate and low viscosity of the injected surfactant
solution, the pressure drop was close to zero during the entire flood as shown in Fig. 7.
The surfactant formulation developed in this coreflood reduces the IFT to ultra-low values on the order of 0.001 dyne/cm,
and consequently the capillary pressure in the presence of surfactant was reduced to essentially zero. Then the question is
how does the surfactant flow into the low permeability matrix if the pressure drop is extremely low and the capillary pressure
is nearly zero? A plausible explanation is that the transverse pressure between the fractures and the matrix is sufficient to
induce surfactant transport into the matrix. This gradient may be enhanced by the in-situ formation of microemulsion since it
has a higher viscosity than the water. Once the surfactant is in the matrix, it changes the wettability and reduces the IFT and
both mechanisms increase the oil relative permeability. The oil can then flow upward due to buoyancy until it reaches a
fracture and then it can flow in the fracture until it is produced. Figure 8 shows the produced surfactant concentration for this
coreflood. No chromatographic separation or preferential retention was observed. The total surfactant retention was 0.086
mg/g of rock with the individual contribution of 0.044 mg/g of C15-18 IOS and 0.042 mg/g of C28-25PO-25EO-Carboxylate.
The coreflood was successful especially taking into account that (1) the core was extremely vuggy, fractured, and
heterogeneous, (2) no mobility control (i.e. polymer) was used, and (3) only a small amount of surfactant was injected.

Simulation Results. The surfactant phase behavior data were matched using the microemulsion phase behavior model in
UTCHEM. The results are shown in Fig. 9. Good agreement between simulation results and experimental data was obtained
for the oil recovery as shown in Fig. 10. The simulated oil saturation and surfactant concentration at the end of the flood is
shown in Figs. 11 and 12. These maps show lower oil saturation correlates with higher surfactant concentrations. A
comparison of simulated oil and water relative permeability values at the end of the water flood and at the end of the
surfactant flood are shown in Figs. 13 through 16. The capillary pressure and relative permeability curves were altered by the
surfactant and moved toward more favorable water-wet conditions.

Conclusions
Experiments using an extremely heterogeneous reservoir core were performed using a mixture of a novel large-hydrophobe
Guerbet alkoxy carboxylate surfactant and an IOS co-surfactant under harsh reservoir conditions. These surfactants are stable
at high temperature. The surfactant both reduces the IFT to ultra-low values and alters the wettability of the rock toward more
favorable water-wet conditions. Both static and dynamic experiments were performed. In the dynamic coreflood experiment,
the oil saturation was reduced to 0.14 using only a small amount of surfactant and no polymer and the surfactant retention
was only 0.086 mg/g rock. The results are excellent taking into account that (1) the core was extremely vuggy and fractured,
(2) no mobility control was used, and (3) only a small surfactant slug was injected. The oil recovery from the dynamic
coreflood was higher than for a similar static imbibition experiment (see comparison in Table 1). The UTCHEM simulator
was used to match the coreflood data by using an extremely heterogeneous random permeability distribution to model the
fractured core as opposed to attempting to model the fractures directly. Matching the experimental data is an important first
step before using the simulator to predict field performance on a much larger scale than the coreflood experiment.

Acknowledgements
The authors would like to thank the industrial affiliates of the Chemical Enhanced Oil Recovery research project at The
University of Texas at Austin for the financial support of this research. We would also like to acknowledge the resources,
staff, and undergraduate research assistants of the Center for Petroleum and Geosystems Engineering at The University of
Texas at Austin, and in particular we would like to thank Stephanie Adkins, Gayani P. Arachchilage, Sriram Solairaj,
Mengyuan Chen, and Scott Hyde II for helping with the laboratory measurements.

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Table 1—Comparison of Static Imbibition and Fractured Coreflood Results

Experiment Static imbibition Fractured coreflood
Core Name Reservoir core Reservoir core
Type Carbonate Carbonate
Length (cm) 7.86 27.4
Diameter (cm) 3.78 10.2
Pore Volume (ml) 7.25 216.0
Porosity 0.082 0.097
Brine Permeability (md) 42.9 6 (before fractured)
1970 (after fractured)
Soi 0.586 0.495
Sorw - 0.412
Oil Recovery (%) 33.3 64.9
Sorc 0.390 0.140
6 SPE 159979

Table 2—Summary of Fractured Coreflood

Experiment
Temperature (°C) 100
Initial salinity (ppm) 116,969
Surfactant Slug
Surfactant concentration (wt%) 1
PV injected 0.25
PV×C (%) 25
Viscosity (cp) 0.33
Salinity (ppm) 57,000
Velocity (ft/day) 0.2
Brine Drive
PV injected 1.46
Viscosity (cp) 0.33
Salinity (ppm) 1,000
Velocity (ft/day) 0.2
Results
Recovery (%) 64.9
Final residual oil saturation, Sorc 0.140
Surfactant retention (mg/g) 0.086

Table 3—Composition of Brines Used in Fractured Coreflood Experiment

+ 2+ 2+ 2- -
Experiment Brine Na (ppm) Ca (ppm) Mg (ppm) SO4 (ppm) Cl (ppm) TDS (ppm)
Static imbibition Initial brine 41,473 3,880 145 500 70,971 116,969
Surfactant solution 19,216 1,296 1,055 2,590 33,094 57,251
Fractured coreflood Initial brine 41,473 3,880 145 500 70,971 116,969
Surfactant slug 19,216 1,296 1,055 2,590 33,094 57,251
Brine drive 3,291 130 362 878 5,706 10,366

Fig. 1—Permeability distribution in Darcy used for modeling fractured coreflood.

SPE 159979 7

50

Aqueous Stability = 58,000 ppm

40
Solubilization Ratio (cc/cc)

30

20

Oil
10
Water

0
45,000 55,000 65,000 75,000
TDS Concentration (ppm)

Fig. 2—Phase behavior of 0.5 wt% C28-25PO-25EO-Carboxylate and 0.5 wt% C15-18 IOS surfactant mixture at 100 °C with 50 vol% oil
after 32 days.

100% 70%

60%
80%
Cumulative Oil Recovery (%)

Oil Saturation 50%

Oil Saturation (%)

60%
40%

30%
40%

20%
20% Cumulative Oil
10%

0% 0%
0 100 200 300 400 500
Time (hour)

Fig. 3—Oil recovery and oil saturation from static imbibition experiment at 100 °C.
8 SPE 159979

Fig. 4—CT images of the core before it was fractured.

Fig. 5—CT images of the core after it was fractured.

SPE 159979 9

100% 50%

Surf
Brine Drive
.
80% 40%
Cumulative Oil Recovered (%)

Cumulative Oil

Oil Saturation (%)

60% 30%
Oil Cut (%)

Oil Saturation
40% 20%

Oil Cut
20% 10%

0% 0%
0.0 0.5 1.0 1.5 2.0
Pore Volumes

Fig. 6—Measured oil recovery, oil cut, and oil saturation for coreflood.

0.20

Whole Core
0.15
Pressure Drop (psi)

0.10

0.05

0.00
0.0 0.5 1.0 1.5 2.0
Pore Volumes

Fig. 7—Measured pressure drop during coreflood.

10 SPE 159979

700 100%

Oil Cut
600
C28-25PO-25EO
Carboxylate
80%
Surfactant concentration (ppm)

500

Oil Cut (%)

60%
400
C15-18 IOS

300
40%

200

20%
100

0 0%
0.0 0.5 1.0 1.5 2.0
Pore Volumes

Fig. 8—Measured oil cut and surfactant concentration in the effluent samples from coreflood.

50

40
Solubilization Ratio (cc/cc)

30

20
Experiment Model

10
Oil Water

0
45,000 55,000 65,000 75,000
TDS Concentration (ppm)

Fig. 9—Comparison of model and phase behavior data.

SPE 159979 11

100% 50%
Surf. Cumulative Oil Experiment Cumulative Oil Model
Brine Drive
Slug Oil Cut Experiment Oil Cut Model
Oil Saturation Experiment Oil Saturation Model
80% 40%
Cumulative Oil Recovered (%)

Oil Saturation (%)

60% 30%
Oil Cut (%)

40% 20%

20% 10%

0% 0%
0.0 0.5 1.0 1.5 2.0
Pore Volumes

Fig. 10—Comparison of simulated and measured fractured coreflood results.

Fig. 11—Simulated oil saturation profile at 1.7 PV. Fig. 12—Simulated surfactant concentration (in vol. fraction)
profile at 1.7 PV.
12 SPE 159979

Fig. 13—Simulated oil relative permeability at end of surfactant Fig. 14—Simulated water relative permeability at end of
flood. surfactant flood.

Fig. 15—Simulated oil relative permeability at end of water flood. Fig. 16—Simulated water relative permeability at end of water
flood.