Oil Recovery From Fractured Carbonates
by Surfactant-Aided Gravity Drainage:
Laboratory Experiments and
Mechanistic Simulations
B. Adibhatla, SPE, and K.K. Mohanty, SPE, University of Houston
Summary
Waterflooding recovers little oil from naturally fractured carbonate
reservoirs if the matrix is oil-wet and fracture intensity is high.
Laboratory experiments and mechanistic simulations have been
conducted to understand the injection of dilute anionic surfactant
solutions into oil-wet, fractured reservoirs. In this process, surfac-
tant diffuses into the matrix, lowering the interfacial tension (IFT)
and contact angle, which decreases the capillary pressure and in-
creases oil relative permeability, enabling gravity to drain up the
oil. The rate of oil recovery increases with an increase in matrix
permeability, a decrease in initial gas saturation, a decrease of
fracture height or spacing, and an increase in the wettability-
altering capabilities of the surfactant. Increasing the surfactant
concentration does not necessarily enhance the oil recovery rate,
because IFT and wettability alterations are not linearly related to
surfactant concentration. Adsorption of anionic surfactants on cal-
cite can be suppressed with an increase in pH and a decrease in
salinity.
Introduction
Approximately 60% of the world’s oil is found in carbonate res-
ervoirs (Akbar et al. 2000). Recovery from reservoirs depends on
reservoir heterogeneity, oil quality, drive mechanisms, and reser-
voir management. Many carbonate reservoirs are naturally frac-
tured and oil-wet/mixed-wet (Roehl and Choquette 1985; Chil-
lenger and Yen 1983). Such reservoirs are difficult to produce after
the primary production if the fractures form a connected network
(Allan and Sun 2003). Waterflooding is effective only if the for-
mation is water-wet. Flooding processes do not work in general,
because large, viscous gradients cannot be imposed. Gravity drain-
age (surfactant, gas, and thermal) techniques can be applied, but
the recovery is slow. Surfactant-enhanced gravity drainage and
imbibition processes are being developed (Yang and Wadleigh
2000; Austad and Milter 1997; Standnes and Austad 2000a, 2000b,
2003a, 2003b, 2003c; Xie et al. 2005; Seethepalli et al. 2004;
Hirasaki and Zhang 2004) to improve oil recovery from oil-wet/
mixed-wet, fractured carbonate formations, and are the subject of
this study.
Cationic surfactants of the type alkyl trimethyl ammonium bro-
mide, CnTAB, are effective [recovery approximately 70% original
oil in place (OOIP)] in imbibing water into originally oil-wet
chalks at concentrations greater than their critical micellar concen-
tration (approximately 1 wt%) (Austad and Milter 1997; Standnes
and Austad 2000a, 2000b, 2003b). Cationic surfactants form ion
pairs with adsorbed organic carboxylates of the crude oil, and
solubilize them into the oil thereby changing the rock surface to be
water-wet. This wettability alteration can lead to countercurrent
imbibition of brine and, thus, to oil recovery. The IFT between the
surfactant solution and oil are not low (>0.1 dynes/cm). Several
Copyright 2008 Society of Petroleum Engineers
This paper (SPE 99773) was accepted for presentation at the 2006 SPE/DOE Symposium
on Improved Oil Recovery, Tulsa, 22–26 April, and revised for publication. Original manu-
script received for review 17 February 2006. Revised manuscript received for review 27
May 2007. Paper peer approved 10 June 2007.
February 2008 SPE Reservoir Evaluation & Engineering
cheaper cationic surfactants of the form C10NH2 and bioderiva-
tives from the coconut palm, termed Arquad and Dodigen (priced
at 3 USD/kg), have been identified (Standnes and Austad 2003c,
2003a; Strand et al. 2003). The two key problems with this method
are still the high concentration and the high surfactant cost.
Nonionic and anionic surfactants have also been considered for
fractured reservoirs (Xie et al. 2005; Seethepalli et al. 2004;
Hirasaki and Zhang 2004). Dilute anionic surfactants have been
considered in the presence of a low concentration potential deter-
mining ion (approximately 0.3 M Na2CO3). IFT can be lowered to
low levels (approximately 10−2 dynes/cm), which reduces capil-
lary forces. Anionic surfactants can remove the adsorbed organic
carboxylates from the solid surface by solubilizing them in mi-
celles because of the hydrophobic effect that can lead to prefer-
entially water-wet or intermediate wettability and an increase in oil
relative permeability. Gravitational forces can pull the oil out of
the matrix because of lower capillarity and increased oil relative
permeability leading to >50% OOIP recovery (Seethepalli et al.
2004, Hirasaki and Zhang 2004).
The surfactant treatment of fractured reservoirs is very different
from the traditional surfactant or alkaline-surfactant-polymer
flooding of nonfractured reservoirs (Bragg et al. 1982; Kalpakci et
al. 1990; Krumrine et al. 1982a, 1982b; Falls et al. 1994). For
surfactant flooding, the initial oil saturation is the waterflood re-
sidual (approximately 35%), and the expected recovery is approxi-
mately 20% of OOIP. For a surfactant-aided-gravity-drainage pro-
cess in fractured reservoirs, the initial oil saturation is approxi-
mately 75% and the target oil recovery is approximately 50% of
OOIP. The oil saturation at the end of this process is the waterflood
residual, approximately 35%. Therefore, this process does not need
ultralow tension or high surfactant concentration. IFT should be
low enough such that the gravitational force exceeds the capillary
forces to minimize capillary end effect [i.e., the inverse Bond
number, N−1 B <0.1 (Du Prey and Lefebvre 1978, Schechter et al.
1994)]. The inverse Bond number is defined as
冑
␾
␴
k
N−1 = . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (1)
B
⌬␳gL
Surfactant-aided gravity drainage of oil from matrix blocks of
fractured reservoirs is driven by a combination of capillary, grav-
ity, diffusive, and viscous forces. Capillarity-controlled imbibition
of brine (surfactant-free) into matrix blocks has been studied by
many (Zhou et al. 1996; Morrow and Mason 2001; Mattax and
Kyle 1962; Ma et al. 1999; Cuiec et al. 1994). Ma et al. (1999)
proposed a scaling group that is given as:
tPc =
冑 k
␾
␴
t, Lc =
Ld
, . . . . . . . . . . . . . . . . . (2)
公 ␮o␮wL2c 2公d2 + 2L2
where tPc is dimensionless time; k is the rock permeability; ␾ is the
porosity; ␴ is the IFT; ␮w and ␮o are the viscosities of water and
oil phases, respectively; Lc is the characteristic length for imbibi-
tion; and t is the actual time of imbibition. The imbibition experi-
119
ments conducted by Morrow and Mason (2001) and Ma et al.
(1999) for water-wet cases all fit a unique curve using this dimen-
sionless time, which is referred to as the very strongly water-wet
curve.
Hagoort (1980) has analyzed the 1D gravity-driven oil drainage
by a gas, and the expression for dimensionless time is
kk0ro⌬␳g
tDg = t. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (3)
共Soi − Sor兲␸␮oL
The combined effects of both gravitational and capillary forces has
been considered by Morrow and Songkran (1982) and Li and
Horne (2006). The above scaling groups do not apply strictly to
imbibition processes with changing wettability and IFT.
Diffusion plays an important role in this process, because the
surfactant has to penetrate the matrix first by diffusion. It should be
recognized that this process is not a purely diffusive process in
which the injected-surfactant-concentration boundary condition is
applied at the boundary of the matrix at all times. In this process,
injected surfactant concentration boundary moves into the matrix
because of flow caused by wettability alteration and IFT reduction.
On the laboratory scale, the diffusive time scale is small and does
not limit the overall rate of the process. On the field scale, the
diffusive time scale is larger and may be the limiting step. Thus,
capillary- or gravity-scaling groups may not be used directly to
scale up this process from the laboratory scale to the field scale.
Numerical simulation can be used to scale up laboratory results
to the field scale. Numerical simulators (John et al. 2005, Shutang
et al. 1996) have been developed in the past for chemical flooding
in which the IFT changes along the reservoir with time. John et al.
(2005) incorporate oil/surfactant/brine-phase behavior using
Hand’s rule and trapping number model for relative permeability
in their simulator. Most simulation studies are focused on the study
of chemical EOR in nonfractured reservoirs without wettability
alteration. In order to better understand the process of oil recovery
from an initially oil-wet matrix block using surfactant-aided drain-
age, a numerical model of the system was developed that accounts
for surfactant convection/diffusion, consequent IFT and contact
angle changes, and resulting capillary pressure/relative permeabil-
ity changes. A description of the numerical simulator is given
elsewhere (Adibhatla et al. 2005).
This paper focuses on a parametric study of the surfactant-
aided gravity drainage of an initially oil-wet core. Surfactant con-
centration, water/oil ratio (WOR), salinity, matrix dimensions, per-
meability, and initial gas saturation have been varied, and their
impact on the process has been studied experimentally. A numeri-
cal simulator has been used to match these experiments and esti-
mate the performance of this process for field-scale matrix blocks.
Methodology
Material. The properties of the surfactants evaluated are listed in
Table 1. Surfactants were used as supplied. A synthetic brine
composed of Na2CO3 was used with the anionic surfactants to
lower adsorption. The properties of the cores used for this imbi-
bition study are listed in Table 2. All cores had a 1.5-in. diameter.
Cores 1 through 11 are limestone outcrop with a permeability of
approximately 150 md and porosity of approximately 22.5%.
120
Cores 12–15 are Cordova cream limestone with a permeability of
approximately 7 md and porosity of approximately 29.1%. The oil
was from a west Texas fractured carbonate field; it is 28.2°API
with 19.1 cp viscosity, 0.2 acid number, and 1.17 base number.
Reformulated reservoir brine (Table 3) was used for our imbibi-
tion studies.
Experimental Procedure. On the basis of our previous work
(Seethepalli et al. 2004), the surfactant solution of 0.05 wt% Alf-38
and 0.3 M Na2CO3 (its optimal salinity) was used as the base case
for the parametric study. Other surfactants chosen for this study
were of B-330, CS-230, AOS, and 5166. The surfactant solutions
were prepared at their optimal-salinity Na2CO3 concentration. Ni-
trogen gas was used as the gas phase for studying the effect of
initial gas saturation on oil recovery rates. The following experi-
ments were conducted for screening of the surfactants: phase be-
havior study, IFT measurement, wettability test, and adsorption.
Phase Behavior Study. 0.05 active wt% dilute anionic surfac-
tants were prepared with varying concentrations of Na2CO3. These
solutions were equilibrated with equal volumes of oil on a tube
shaker for 2 days and then left to settle for 1 day. The phase
behavior was studied to observe the change from Winsor Type II−
to Type II+ phase behavior with the increase in salinity of the
solution.
IFT Measurement. The IFT between the equilibrated brine and
oil phases was measured with the help of a spinning-drop tensi-
ometer. In cases where third-phase microemulsion was found to
exist, the oil phase was taken near the middle phase for an accurate
measurement of the IFT. Optimal salinity was taken as the salinity
of the system, which gave the least IFT between the oil and the
aqueous phase. In the phase behavior studies, a middle-phase mi-
croemulsion was always present near the optimal salinity. The
subsequent wettability experiments were performed at the optimal
salinity obtained from these measurements.
Wettability Test. The wettability tests were conducted on cal-
cite plates. The plates were polished on a 600-mesh diamond lap
and equilibrated with synthetic brine for 1 day. The contact angle
measurements were made with the help of a goniometer. The
brine-equilibrated plate was aged with oil at an elevated tempera-
ture (approximately 80°C) for approximately 2 days to make it
oil-wet. The aged plate was contacted with synthetic (Na2CO3)
brine for 1 hour, and the advancing contact angle was measured.
Thereafter, the synthetic brine was replaced by the surfactant/brine
solution, and the evolution of contact angle was monitored for 2
days by a goniometer. In the cases where the drops were too small
(<<0.1 mm), it was difficult to measure an accurate contact angle,
and a post-wettability test was performed (Krumrine et al. 1982a).
In such cases, the plate was further washed with brine, and a drop
of crude oil was placed at the bottom of the plate. This contact
angle, is a receding contact angle and this test is referred to as the
“post-wettability” test. It should be noted that the post-wettability
contact angle would give a measure of the receding contact angle,
which would be lower than the advancing contact angles.
Adsorption. Surfactant solutions in the concentration range of
10−2 M were prepared with and without the presence of 0.3 M
Na2CO3. These solutions were then equilibrated with 10 g calcite
February 2008 SPE Reservoir Evaluation & Engineering
powder in 50-mL vials. The vials were corked and gently shaken
to make the calcite powder come thoroughly into contact with the
surfactant solution. The solutions were allowed to equilibrate with
the calcite powder for 48 hours, with periodic gentle shakings. The
slurry was then centrifuged at 1,200 rev/min for 20 minutes to
separate the solid particles from the liquid solution. The superna-
tant was carefully pipetted out while avoiding the solid particles.
The supernatant was then centrifuged again for 20 minutes to
obtain a particle-free supernatant. The pH of all the supernatant
solutions was measured. Ultraviolet spectrometry and titration
analysis were used to determine the residual surfactant concentra-
tion in the supernatant liquid. The adsorbed surfactant concentra-
tion was calculated by material balance. To study the effect of pH
on adsorption, the surfactant solution was prepared in different-pH
buffer solutions, and the same method was adopted to measure the
degree of adsorption. Similarly, experiments were performed at
different temperatures to study the effect of temperature. Also,
experiments were performed at different salinities to study the
effect of salinity on adsorption.
Spontaneous Imbibition. The cores were fully saturated with the
field brine and then injected with 5 pore volumes of the crude oil
to reach the residual water saturation (1−Soi in Table 2). They were
then aged in an oil bath at 80°C for 12 days, to render them oil-wet.
Each core was placed in an imbibition cell and surrounded by a
surfactant brine solution, as listed in Table 2. Most of the oil
drained from the core floated up and collected at the top of the
imbibition cell. The volume of the separated oil was monitored as
a function of time. In some cases, small oil drops took a long time
to rise to the top, causing a cloudy macroemulsion to form below
the separated oil phase. The amount of oil trapped in the macro-
emulsion phase was small in the beginning (because of less oil
recovered), high in the middle of the experiment (because of more
oil recovered), and again small toward the end (because of the long
time for settling). This emulsion oil content was of the order of 2
February 2008 SPE Reservoir Evaluation & Engineering
mL at its maximum, but was not included in the oil recovery
curves that would be discussed in the next section.
Experimental Results
Phase Behavior. Fig. 1 shows the phase behavior of a crude-oil/
brine (Na2CO3)/surfactant system for the alkyl-ethoxylated surfac-
tants. WOR is kept at 1:1 in all the cases shown. In these experi-
ments, WOR refers to the ratio of the starting water volume to oil
volume. The concentration of the surfactants used is kept constant
at 0.05 wt%, and the Na2CO3 concentration is increased from 0 to
1.2 M. The number underneath each test tube specifies the Na2CO3
concentration in the brine. As the caustic concentration increases,
the aqueous phase becomes cloudier, reaches a maximum cloudi-
ness, and then becomes clearer. A small, middle-phase microemul-
sion is also observed in the near-optimal region, similar to those
seen for alkyl-propoxylated surfactants (Seethepalli et al. 2004).
Because we are operating at a very dilute surfactant concentration
(0.05 wt%), the middle-phase microemulsion layer formed is often
thin and too small for any analysis. The aqueous phase becomes
clear at a higher Na2CO3 concentration,indicating Winsor Type
II+microemulsion. At this point, the system is in the over-
optimum-salinity regime.
IFT. Fig. 2 shows the IFT between the aqueous and the oleic
phases as a function of Na2CO3 concentration in these crude-oil/
brine (Na2CO3)/surfactant systems. The equilibrated tubes from
the phase behavior study are used to measure the equilibrium IFT
between the oil and the aqueous phase. The surfactant concentra-
tion is fixed at 0.05 wt%. The ethoxylated sulfates studied could
lower the IFT of the system to approximately 10−3 to 10−2 dynes/
cm. The lowest IFT samples corresponded to those with middle
phases, with two ethoxy groups. Thus, low tensions can be gen-
erated with anionic surfactants at very low concentrations.
Wettability. Wettability was evaluated by measuring water-oil
contact angles. All the contact-angle measurements for the anionic
surfactants were made at a surfactant concentration of 0.05 active
wt%, at the optimal salinity obtained from the IFT experiments.
Fig. 3 shows the contact angles measured after 24 and 48 hours for
the calcite plate with surfactant B-330 and 0.8 M Na2CO3, respec-
tively. The wettability varies along the surface of the plate because
of the nonuniformity in initial oil contact with the plate. This leads
to the range of contact angles observed after the surfactant treat-
ment, as can be seen from the different sections in Fig 3. Because
the droplets are small, the contact angle is measured by a goni-
ometer, which solves for the drop profile. The oil-aged plate
(Seethepalli et al. 2004) is immersed in brine, and the oil-water
contact line on the calcite plate is photographed to obtain these
121
 Fig. 1—Phase behavior of alkyl-ethoxy sulfates (a) CS-130 (b) CS- 230 (c) B-330 (d) B-27.

data. The surfactant and Na2CO3 are then added to get a surfactant
solution at its optimal salinity. When exposed to the surfactant/
brine solution, much of the oil is released from the plate because
of lower IFT, and the advancing contact angle decreases with time,
stabilizing at a value of approximately 48 to 98°, depending on the
drop size. For the case of surfactant B-27, a post-wettability test
was performed to get the final wettability state of the calcite slab.
The contact angle at the end of wettability tests is listed in Table 4
for all of the ethoxylated sulfates studied. Most of the ethoxy sul-
fates altered the wettability of the oil-wet carbonate surface to
intermediately to moderately water-wet states.
Adsorption. Anionic surfactants adsorb on the calcite surface and
are lost in the process of surfactant flooding. Adsorption of sur-
factants plays an important role in determining the economic suc-
cess of the surfactant brine imbibition process. Adsorption of sur-
factants has been measured on the calcite powders. Table 5 shows
the adsorption densities for the alkyl-ethoxylated surfactants in the

Fig. 2—IFT for alkyl-ethoxy sulfates at varying salinity.

122 February 2008 SPE Reservoir Evaluation & Engineering


Fig. 3—Oil droplets in surfactant solution for 0.05 wt% B-330
and 0.8 M Na2CO3, after (a) 24 hours (b) 48 hours (left: entire
plate approximately 1 cm wide; middle and right: smaller sec-
tions of the plate, scale bar approximately 0.2 mm).
absence and presence of Na2CO3. These adsorption values are
similar to those found for sodium dodecyl sulfate on calcite and
dolomite surfaces by Tabatabal et al. (1993) and Seethepalli et al.
(2004). In one case, negative adsorption was found; this was also
reported earlier by Somasundaran and Agar (1967). Anionic sur-
factants can be repelled near the negatively charged calcite surface
at that pH. They accumulate in the bulk solution, thereby increas-
ing the local surfactant concentration. This leads to the negative
adsorption numbers by titration calculations. Within the accuracy
of our measurements, our observations imply negligible or zero
adsorption on the calcite surface.
Fig. 4 shows the effect of pH on the adsorption density of
anionic surfactants on calcite mineral. Somasundaran and Agar
(1967) found that the point of zero charge for the calcite was
approximately 8.2. Increasing pH beyond this level causes the
surface to acquire negative charges and repel the like-charged-
anionic-polar head group of the surfactant. Thus, the adsorption of
anionic surfactants can be suppressed by the use of the potential
determining ions CO32− (Tabatabal et al. 1993). According to the
Derjaguin-Landau-Verway-Overbeek theory, the higher electro-
lyte concentration lowers the Debye screening length, which im-
plies a higher shielding effect and lesser repulsion between the
adsorbed molecules. Hence, increasing the salinity would increase
the adsorption of surfactants on the mineral surface. Fig. 5 shows
an increase in adsorption experimentally for the increase of salinity
(achieved by increasing the NaCl concentration). Multivalent ions
would further reduce the thickness of the electric double layer,
decrease the repulsion, and thus, increase the adsorption.
Fig. 6 shows the effect of temperature on surfactant adsorption.
Increasing temperature increases the enthalpy and entropy of the
system. If the adsorption is enthalpy-driven, as is the case with
surfactants with a low density of adsorption, then increasing tem-
perature also increases the adsorption density. On the other hand,
if the adsorption of surfactants is entropy driven, as is the case with
surfactants with high density of adsorption, increasing the tem-
perature would lead to a decrease in adsorption (Somasundaran
and Agar 1967). Fig. 6 shows that for surfactants with a low
density of adsorption, an increase in the temperature leads to an
increase in the adsorption density, whereas for surfactants with a
February 2008 SPE Reservoir Evaluation & Engineering
high density of adsorption, an increase in temperature leads to a
decrease in the adsorption density.
Imbibition. Fig. 7 shows oil recovery in four imbibition experi-
ments. For our parametric study, an Alf-38 system with 0.3 M
Na2CO3 with a 10:1 WOR (ratio of surrounding surfactant water
volume to oil volume inside the core) was taken as the base case.
This imbibition experiment was conducted in our previous work
(Seethepalli et al. 2004) and repeated in this work with Core 6 (in
Table 2) to study the repeatability of these experiments. To exam-
ine the extent of wettability alteration in the interior of the core,
one of the cores (Core 7 in Table 2) was cleaved axially to expose
the inside surface. This cleaved core was immersed in brine (with-
out surfactant or Na2CO3). In the last experiment (Core 5 in Table
2), a core was surrounded by 0.2 M Na2CO3 solution to study the
amount of oil recovery by an alkaline solution without any sur-
factant. In all the results shown, the oil recovery includes only the
separated oil phase (i.e., the amount of oil trapped in the macro-
emulsion phase was not included). Fig. 7 shows that oil recovery
from the Alf-38 system is repeatable and gives approximately 42%
of OOIP recovery in 50 days of imbibition, approximately 60% in
200 days. Approximately half of the recoverable oil is recovered in
less than 30 days. Fig. 7 also shows that little oil (<5% of OOIP)
is recovered from the cleaved core by brine, indicating that the
oil-aging method (and time used for aging cores) leads to uniform
wettability alteration to the oil-wet regime throughout the core.
The use of Na2CO3 leads to the generation of in-situ soap and, as
reported in our previous work, a reduction of IFT (to a value of
approximately 0.1 dynes/cm). This low IFT mobilizes some of the
oil and leads to a recovery of 9% of OOIP, as seen in Fig. 7.
Effect of WOR and Surfactant Concentration. Previous stud-
ies (Seethepalli et al. 2004; Hirasaki and Zhang 2004) have shown
that WOR plays a critical role in determining the optimal salinity
of the system. Hence, to study the effect of WOR, an oil-wet core
(Core 1 in Table 2) was immersed in a surfactant solution with a
WOR of 3:1, as compared to the base case (Core 6 in Table 2),
where the WOR was kept at 10:1. Fig. 8 shows that the oil recov-
ery decreases with a decrease in WOR. WOR affects the synthetic-
surfactant-to-in-situ-soap ratio, which alters the IFT and the con-
tact angle of the system—which, in turn, influence oil recovery. In
another core (Core 2 in Table 2), the imbibing solution was 0.2-
wt% Alf-38 surfactant in 0.3 M Na2CO3. Fig. 8 shows that in-
creasing the surfactant concentration increases the initial rate of oil
recovery slightly, but it does not affect the long-term recovery at
the laboratory scale. On the basis of our previous work (Adibhatla
et al. 2005), the rate of oil recovery by surfactant brine imbibition
process is a gravity-driven process, but it is initially diffusion-
limited. Increasing the surfactant concentration increases the rate
of surfactant diffusion into the core. It enhances the initial rate of
recovery, but it does not affect the final recovery. The salinity used
in the Core 2 experiment was the optimal salinity for 0.05-wt%
surfactant and may not be the optimal salinity for this higher
concentration.
Effect of Initial Gas Saturation. In the target reservoirs, after
primary production, there is always some gas present. This affects
the performance of the surfactant-brine process and was tested by
imbibition experiments. An oil-wet core at the residual water satu-
ration (Core 3 in Table 2) was flooded by N2 gas until the residual
oil saturation was achieved at a pressure drop of 40 psi/ft. The core
was then flooded again by the crude oil to reach the residual gas
123
 Fig. 4—Effect of pH on adsorption of alkyl-ethoxy sulfates and Alf-63.
saturation. The residual gas saturation thus obtained was 9%, as
listed in Table 2, Core 3. This core was then immersed in the base
case surfactant solution. Fig. 9 shows that the presence of a small
amount of initial gas does not significantly affect the rate of oil
recovery. In another core (Core 4 in Table 2), the oil-saturated core
(with residual water) was flooded by N2 gas and then directly used
for imbibition studies. In this case, the initial gas saturation was
measured to be 24%. The oil recovery rate for surfactant-brine
imbibition for this system is much lower, as shown in Fig. 9. The
presence of initial gas in the core affects the rate of recovery
because of a significant decrease in the oil relative permeability.
Effect of Surfactant Type. Other surfactants, which gave fa-
vorable wettability alteration (final contact angle <90°, toward
water-wet regime) and low IFT, were also tested for oil recovery.
Fig. 10 shows recovery rates for different surfactants at 0.05 wt%
and their optimal salinity. The cores used for these experiments are
listed in Table 2 as Cores 6 and 8 through 11. The concentration
of Na2CO3 used is also listed in Table 2, and it corresponds to their
optimal salinity. Fig. 10 shows that recovery rates for Alf-38,
B-330, and CS-230 are almost identical, in line with their behavior
in phase behavior, IFT, and wettability alteration studies. AOS is
Fig. 5—Effect of salinity on density of anionic surfactants on calcite mineral.
124
a surfactant for application in high-temperature reservoirs, and it
gives a final recovery of 21% of OOIP after 50 days of imbibition.
Surfactant 5166 gives low IFT approximately 10−3 dynes/cm, but
it does not alter the wettability to water-wet regime. Fig. 10 shows
that it gives a final recovery of 19% of OOIP after 50 days of
imbibition.
Capillary vs. Gravity Scaling. A 7-md core (Core 12 in Table
2) was immersed in the base-case surfactant solution to study the
effect of permeability. Fig. 11 compares the rate of recovery for
the 7-md core with that of the 150-md core (Core 6). It can be seen
that approximately 12% of OOIP is recovered in 120 days. As the
matrix permeability decreases, so does the oil recovery by imbi-
bition. The oil recovery for a 150-md core is then “estimated” from
the results of the 7-md core using capillary and gravity scaling
groups. For capillarity scaling, the recovery time from 7 md was
multiplied by the capillarity dimensionless scaling factor
冑 冑 k7
␾7*
␾150 L2c,150
k150 L2c,7
to scale up recoveries from a 150 md core if
the process was capillarity driven. Similarly for gravity scaling of
the 7-md core to 150-md core, the recovery times from the 7-md
February 2008 SPE Reservoir Evaluation & Engineering
 Fig. 6—Effect of temperature on the density of adsorption for anionic surfactants on calcite mineral.

core were multiplied by gravitational dimensionless scaling factor
k7 ␾150L150
to scale up recoveries from a 150-md core if the
␾7L7* k150
process was gravity driven. Fig. 11 shows that the 150-md core
recoveries are much higher than those estimated with capillarity
scaling (Eq. 1). Scaling the imbibition time using Eq. 3, as a
gravity-dominated process, gives recovery estimates that match the
150-md, 22%-porosity core experimental results, as shown in Fig.
11. This indicates that the surfactant-brine-imbibition process is
gravity-dominated.
Effect of Core Size. The dimensionless time for a gravity-
driven process (as given by Eq. 3) can be increased by decreasing
the length of the core, which can lead to a higher oil recovery rate.
An oil-wet core was cut into half horizontally (Core 14 in Table 2).
In another experiment, an oil-wet core was cleaved into half ver-
tically (Core 15 in Table 2) for imbibition experiments. We be-
lieved it would lower the effective diffusion length for the surfac-
tant and enhance the rate of recovery. The oil recovery for these
experiments is plotted in Fig. 12. Decreasing the fracture length
and decreasing the effective diffusion length increases the rate of
oil recovery. Hence, in an oil-wet, naturally fractured reservoir,
smaller fracture spacing and height would lead to an increase in the
rate of oil recovery by the surfactant-brine-imbibition process.
Numerical Simulation
The surfactant-brine-imbibition process can be effective in recov-
ering oil from oil-wet fractured carbonates. Different parameters
like WOR, IFT, wettability alteration, surfactant concentration,
fracture dimensions, and rock and fluid properties affect the

Fig. 7—Surfactant-brine imbibition: effect of surfactant concentration and WOR.

February 2008 SPE Reservoir Evaluation & Engineering 125

 Fig. 8—Surfactant-brine imbibition: repeat experiment, Na2CO3, and brine.

amount and the rate of oil recovery. To better understand the rates
of recovery, a 3D, finite-volume, two-phase, four-component, im-
plicit numerical simulator was developed. The details of the simu-
lator are explained in previous work (Adibhatla et al. 2005). The
laboratory cores used are homogeneous and cylindrical; hence, the
problem is assumed to be axisymmetric. Experimental imbibition
data are compared with the results from the numerical simulator.
The numerical simulator is then used to understand the process of
oil recovery and scaleup.
Comparison With Experimental Data. Fig. 13 shows the com-
parison between numerical simulation and imbibition experiments
for Cores 6 and 12. Estimates of oil in macroemulsion are shown
as vertical bars in these plots. If this emulsion oil is included, then
the simulation results match closely the experimental data. The
relative permeability parameters in the numerical model were ad-
justed to get this match. The in-situ velocity profiles (not shown
here) indicate that water imbibes from the sides and that oil leaves
from the top. The change in wettability increases oil relative per-
meability and enhances the oil drainage.
When the oil-wet cores are initially immersed in an imbibition
cell and surrounded by a brine solution, the brine does not go in
immediately because the entry capillary pressure with the connate
brine exceeds the gravitational force [i.e., the macroscopic bond
number, N−1B (given by Eq. 1) is greater than 1]. As the surfactant
diffuses into the core, the IFT and the wettability of the core
change. As the IFT is lowered, capillary pressure falls, and N−1 B
decreases. When it becomes less than 1, water starts invading the
core from the bottom and the sides. Also, as the wettability is
altered, the capillary pressure changes from negative to positive,
but it leads to little countercurrent imbibition because the magni-
tude of capillary pressure is low. As the wettability is altered, the

Fig. 9—Surfactant-brine imbibition: effect of initial gas saturation.

126 February 2008 SPE Reservoir Evaluation & Engineering

 Fig. 10—Surfactant-brine imbibition: effect of different surfactants.
relative permeability of the oil phase increases, and it enhances the
rate of oil recovery.
Effect of Wettability Alteration. The effect of wettability alter-
ation on the oil recovery rate was studied by changing the contact
angle from the initial value of 180° to final values of 180° (no
wettability alteration), 90° (intermediate-wet), 75° (actual wetta-
bility for Alf-38), and 0° (strongly water-wet). IFT was the same
in all of these cases. By increasing the extent of wettability alter-
ation, it was observed that the oil recovery rate increased, as shown
in Fig. 14. Because the process is mostly gravity-driven, Eq. 3
suggests that as the oil permeability increases, dimensionless time
increases, which results in an increase in oil recovery. Hence, for
a given time, as the block becomes more water-wet, the oil recov-
ery increases. Oil is recovered in all these cases because of low
tension, but increasing the extent of wettability alteration increases
the rate of oil recovery.
Fig. 11—Surfactant-brine imbibition: effect of permeability, scaling with gravity and capillarity.
February 2008 SPE Reservoir Evaluation & Engineering
Scaleup. A simulator with parameters that matched the laboratory-
scale data was used to estimate oil production in reservoir-scale
matrix blocks. The reservoir dimensions used were 1000 m length
and 300 m width, with 10-m-high fractures. The fracture spacing
along the length was varied from 1 to 10 m. It was assumed that
the matrix is homogeneous. The surfactant water was injected
through a horizontal injector well at the bottom of the reservoir,
and similarly, a horizontal producer well at the top of the reservoir
was used to collect the oil recovered. These two horizontal wells
were assumed to be connected to all of the fractures, which were
perpendicular to the wells. In the simulations, the fractures were
assumed to be of infinite permeability and were always filled with
the surfactant solution. This is an ideal case, but it can indicate the
scaleup of the laboratory results. The properties of the reservoir
were assumed to be 150 md permeability, 15% porosity, 5 cp oil
viscosity, and 0.85 g/ml oil density. Initial oil saturation inside the
reservoir was 0.72, and total oil recoverable by secondary produc-
127
 Fig. 12—Surfactant-brine imbibition: effect of fracture length and diffusion length.
tion (corresponding to Soi/Sor) was approximately 1.4 million bbl.
The simulation was carried for 30 years of production.
Fig. 15 shows the oil production rate by the surfactant brine
process for fracture spacing of 1 and 10 m along with the cumu-
lative oil production. For a fracture spacing of 1 m, more than 500
bbl of oil is produced per day for 3 years, and the production
declines after that. In that 3-year period, approximately 50% of the
recoverable oil is recovered. Increasing the fracture spacing lowers
the recovery rates. For fracture spacing of 10 m in the same res-
ervoir, the oil production decreases to 200 to 300 BOPD for the
first 3 years, by end of which approximately 25% of the recover-
able oil is recovered. Waterflooding would produce no oil from
such a fractured oil-wet reservoir. Surfactant-aided gravity drain-
age can recover a large fraction of the oil in less than 30 years if
the fracture spacing is small.
Further investigation is needed to evaluate the effectiveness of
this process in realistic heterogeneous naturally fractured reser-
voirs. Our simulation includes diffusion: We anticipate that at the
core scale, numerical dispersion is small and diffusion is properly
represented. At the field scale, diffusive effects may be overesti-
mated in our simulations because of the excessive numerical dis-
persion. We will study this effect more carefully and report on it
in a future publication.
Fig. 13—Simulation of imbibition experiments of Cores 6 and 12.
128
Conclusions
In surfactant-aided gravity drainage of fractured reservoirs, sur-
factant diffuses into the matrix, lowering IFT and contact angle,
which decreases capillary pressure and increases oil relative per-
meability, enabling gravity to drain up the oil. On the basis of this
study, the following can be concluded:
• Anionic surfactants can lower IFT to 10−2 dynes/cm range and
alter wettability to intermediate/water-wet regime at very low
concentrations (approximately 0.05 wt%).
• Adsorption of anionic surfactants on calcite decreases with an
increase in pH and a decrease in salinity. Adsorption of these
solutions on calcite mineral can increase or decrease with an
increase in temperature, depending on whether adsorption is
enthalpy-driven or entropy-driven.
• Laboratory-scale surfactant brine imbibition experiments give
high oil recovery (20 to 42% of OOIP in 50 days, up to 60% in
200 days) for initially oil-wet cores through wettability alteration
and IFT reduction. The experimental results are reproducible.
• Limestone cores are rendered oil-wet uniformly by the current
oil-aging process.
• IFT and wettability alterations are not linear functions of sur-
factant concentration. Hence, higher surfactant concentration
need not translate into an enhanced rate of oil recovery.
Fig. 14—Surfactant-brine imbibition simulation: effect of extent
of wettability alteration.
February 2008 SPE Reservoir Evaluation & Engineering
 Fig. 15—Production from 1000×300-m fractured oil-wet reservoir, with fracture spacing of 10 and 1 m.

• Small initial gas saturation does not significantly affect the rate Imbibition. Paper SPE 97687 presented at the SPE International Im-
of oil recovery in the imbibition process, but larger gas satura- proved Oil Recovery Conference in Asia Pacific, Kuala Lumpur, 5–6
tion decreases the oil recovery rate. December. DOI: 10.2118/97687-MS.
• As the core permeability decreases, the rate of oil recovery re- Akbar, M., Vissapragada, B., Alghamdi, A.H., et al. 2000. A Snapshot of
duces, and this reduction can be scaled by the gravitational di- Carbonate Reservoir Evaluation. Oilfield Review 12 (4): 20–21.
mensionless time. Allan, J. and Sun, S.Q. 2003. Controls on Recovery Factor in Fractured
• At the field scale, 50% of the recoverable oil is recovered in Reservoirs: Lessons Learned From 100 Fractured Fields. Paper SPE
approximately 3 years if the fracture spacing is 1 m, and 25% if 84590 presented at the SPE Annual Technical Conference and Exhi-
10 m, in the example simulated. bition, Denver, 5–8 October. DOI: 10.2118/84590-MS.
• Decreasing fracture spacing and height, increasing permeability, Austad, T. and Milter, J. 1997. Spontaneous Imbibition of Water Into Low
and increasing the extent of wettability alteration increases the Permeable Chalk at Different Wettabilities Using Surfactants. Paper
rate of oil recovery from surfactant-aided gravity drainage. SPE 37236 presented at the SPE International Symposium on Oilfield
Chemistry, Houston, 18–21 February. DOI: 10.2118/37236-MS.
Nomenclature Bragg, J.R., Gale, W.W., McElhannon, W.A. Jr., et al. 1982. Loudon
d ⳱ diameter of the core, m Surfactant Flood Pilot Test. Paper SPE 10862 presented at the SPE
g ⳱ gravitational constant⳱9.8 m/s2 Enhanced Oil Recovery Symposium, Tulsa, 4–7 April. DOI: 10.2118/
k ⳱ absolute permeability, D 10862-MS.
kro0 ⳱ endpoint relative permeability of oil Chillenger, G.V. and Yen, T.F. 1983. Some Notes On Wettability and
Relative Permeability Of Carbonate Rocks. II. Energy and Sources 7
LC ⳱ characteristic length for capillary driven imbibition, m
(1): 67–75.
L ⳱ length of the core, m
Cuiec, L.E., Bourbiaux, B., and Kalaydjian, F. 1994. Oil Recovery by
B ⳱ macroscopic inverse bond number
N−1
Imbibition in Low-Permeability Chalk. SPEFE 9 (3): 200–208. SPE-
Soi ⳱ initial oil saturation 20259-PA. DOI: 10.2118/20259-PA.
Sor ⳱ residual oil saturation Du Prey, L. and Lefebvre, E. 1978. Gravity and Capillary Effects on
tDg ⳱ dimensionless time for gravity driven flow Imbibition in Porous Media. SPEJ 18 (3): 195–206. SPE-6192-PA.
t ⳱ time, s DOI: 10.2118/6192-PA.
tPc ⳱ dimensionless time for capillarity-driven flow Falls, A.H., Thigpen, D.R., Nelson, R.C., et al. 1994. A Field Test of
⌬ ⳱ difference Operator Cosurfactant-Enhanced Alkaline Flooding. SPERE 9 (3): 217–223.
␾ ⳱ porosity SPE-24117-PA. DOI: 10.2118/24117-PA.
␴ ⳱ IFT Hagoort, J. 1980. Oil Recovery by Gravity Drainage. SPEJ 20 (3): 139–
␮i ⳱ viscosity of ith phase 150. SPE-7424-PA. DOI: 10.2118/7424-PA.
␳i ⳱ density of ith phase Hirasaki, G. and Zhang, D.L. 2004. Surface Chemistry of Oil Recovery
␪ ⳱ contact angle From Fractured, Oil-Wet, Carbonate Formation. SPEJ 9 (2): 151–162.
SPE-88365-PA. DOI: 10.2118/88365-PA.
Acknowledgments John, A., Han, C., Delshad, M., Pope, G.A., and Sepehrnoori, K. 2005. A
New Generation Chemical-Flooding Simulator. SPEJ 10 (2): 206–216.
The authors thank the National Energy Technology Laboratory of SPE-89436-PA. DOI: 10.2118/89436-PA.
the US Department of Energy (DE-FC26-02NT15322) for the Kalpakci, B., Arf, T.G., Barker, J.W., et al. 1990. The Low-Tension Poly-
funding of this work. mer Flood Approach to Cost-Effective Chemical EOR. Paper SPE
20220 presented at the SPE/DOE Enhanced Oil Recovery Symposium,
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SI Metric Conversion Factors
cp × 1.0* E−03 ⳱ Pa⭈s
dyne × 1.0* E−02 ⳱ mN
°F (°F−32)/1.8 ⳱ °C
*Conversion factor is exact.
Bhargaw Adibhatla is a senior research engineer at ExxonMobil
in Houston. E-mail: bhargaw@gmail.com. His research interests
are surface science and enhanced oil recovery. He holds a
BTech degree from IIT, Delhi and a PhD degree from the Uni-
versity of Houston, both in chemical engineering. Kishore K.
Mohanty is a professor at the University of Houston. E-mail:
mohanty@uh.edu. His research interests are improved oil re-
covery, transport in porous media, nanotechnology, and for-
mation evaluation. He holds a BTech degree from IIT, Kanpur
and a PhD degree from the University of Minnesota, both in
chemical engineering. He was the Executive Editor of the SPE
Journal in 2001–2002.
February 2008 SPE Reservoir Evaluation & Engineering