Petroleum Science and Technology

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Experimental and simulation study of surfactant

flooding using a combined surfactant system for
enhanced oil recovery

Sombir Pannu, Ranjan Phukan & Pankaj Tiwari

To cite this article: Sombir Pannu, Ranjan Phukan & Pankaj Tiwari (2022) Experimental
and simulation study of surfactant flooding using a combined surfactant system for
enhanced oil recovery, Petroleum Science and Technology, 40:23, 2907-2924, DOI:
10.1080/10916466.2022.2052089

To link to this article: https://doi.org/10.1080/10916466.2022.2052089

Published online: 23 Mar 2022.

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PETROLEUM SCIENCE AND TECHNOLOGY
2022, VOL. 40, NO. 23, 2907–2924
https://doi.org/10.1080/10916466.2022.2052089

Experimental and simulation study of surfactant

flooding using a combined surfactant system for
enhanced oil recovery
Sombir Pannua , Ranjan Phukanb , and Pankaj Tiwaria
a
Department of Chemical Engineering, Indian Institute of Technology, Guwahati, India;
b
Department of Petroleum Technology, Dibrugarh University, Dibrugarh, Assam, India

ABSTRACT KEYWORDS
Oil recovery potential of surfactant flooding is restricted due combined surfactant
to the inability of single surfactant to achieve ultra-low inter- system; enhanced oil
facial tension (IFT) and strong water-wet conditions. To over- recovery; glycerol; interfacial
tension; MRST simulation;
come these limitations, surfactant mixtures are employed to wettability
achieve the desired enhanced oil recovery (EOR) properties. In
this study, the efficacy of a combined bio and synthetic sur-
factants system as a potential means of enhancing oil recov-
ery was examined. The surface, interfacial, and wettability
alteration properties of biosurfactant, synthetic surfactant, gly-
cerol, and their combined mixture were investigated. The
results revealed that the combined surfactant system had a
more pronounced effect on oil-water IFT and wettability alter-
ation compared to the individual solutions separately.
Ultralow IFT (0.005 mN/m) was obtainable using the combined
surfactant system. The core flooding experiments conducted
on Gray Berea sandstone cores using Assam crude oil showed
that an additional 15–20% of original oil in place (OOIP) could
be recovered with the combined surfactant system. Additionally,
simulation studies showed that on a field-scale incremental oil
recovery of 12–15% OOIP could achieve depending on the injec-
tion mode. Thus, the study revealed that through the unique
combination of bio and synthetic surfactants with glycerol, a
competent EOR fluid could be developed.

1. Introduction
Enhanced oil recovery (EOR) technologies are considered an essential
means of maximizing the recovery of oil in place from the reservoirs.
Among these EOR techniques, the chemical EOR methods have proven to
be very promising in recovering the residual oil due to their better effi-
ciency and technical feasibility. In chemical EOR, a vast range of chemical
agents, including surfactants, alkalis, polymers, and/or nanoparticles, are
used to increase the displacement and sweep efficiencies (Demirbas et al.

CONTACT Ranjan Phukan r.phukan@dibru.ac.in Department of Petroleum Technology, Dibrugarh

University, Assam, India; Pankaj Tiwari pankaj.tiwari@iitg.ac.in Department of Chemical Engineering, IIT
Guwahati, Assam, India.
ß 2022 Taylor & Francis Group, LLC
2908 S. PANNU ET AL.

2015).In the surfactant-based chemical EOR process, surfactant injected

into an oil reservoir causes improvement in oil recovery through several
mechanisms, including a reduction in oil-water interfacial tension (IFT),
wettability alteration of rocks toward more water-wet conditions, and
trapped oil micro-emulsification. These mechanisms are responsible for
increasing the capillary number (Nc) during surfactant flooding and
reducing the residual oil saturation. The trapped oil can be mobilized and
produced if the Nc can be increased in an EOR process. However, a suffi-
ciently large Nc value in the range of 10
3 is necessary to mobilize the capil-
lary-held oil and lower the residual oil saturation to near zero (Amili and
Yortsos 2006). For reaching this value, the IFT should be reduced to as low as
10
2 to 10
5 mN/m. Most of these processes are designed to accomplish this
through the use of optimized surfactant formulations. Very often, a single
surfactant system is unable to achieve the required ultra-low IFTs. Therefore,
mixtures of surfactants are designed to achieve the desired objectives of
surfactant flooding. Mixed surfactant systems have been reported to have
better micellar and interfacial behavior due to synergism than those attainable
by the individual surfactants (El-Batanoney et al. 1999).
Owing to their superior interfacial properties, much attention has been
directed toward evaluating mixed surfactant systems for EOR in the past few
decades. Studies have shown that using combined bio and synthetic surfac-
tants can reduce the cost and environmental impact of using mixed surfactant
systems while at the same time maintaining the EOR effectiveness. The use of
biosurfactants has been reported to be largely impressive in recovering oil
from reservoirs through different mechanisms, including IFT reduction, wett-
ability alteration, and emulsification (Al-Sulaimani et al. 2010). Studies by
Daoshan et al. (2004) showed that using bio and synthetic surfactants could
produce a significant synergic effect for improving oil-water interfacial behav-
ior and reducing the cost of chemical flooding. Al-Sulaimani et al. (2012)
observed that the oil recovery performance of biosurfactant, produced by
Bacillus subtilis strain isolated from an oil-contaminated soil, was increased
upto 50% by mixing with chemical surfactants in equal ratio. In a similar
study, Al-Wahaibi et al. (2016) showed that blending chemical (ethoxylated
sulfonate) and bio (lipopeptide) surfactants resulted in a better reduction in
IFT compared to using each surfactant separately. Thus, there is sufficient
scope for combining bio and synthetic surfactants to enhance the performance
of surfactant flooding. However, detailed investigations on the combined effect
of bio and synthetic surfactants on EOR are very limited. The current work
presents a comprehensive investigation of using a unique combination of sur-
factant system for EOR that has not been reported in the earlier studies.
Based on the prospects of previous studies and the existing literature gap, a
new surfactant system was developed by combining a biosurfactant(of bacteria
 PETROLEUM SCIENCE AND TECHNOLOGY 2909

Table 1. Results of crude oil analyses.

Crude oil property Value
Density, kg/m3 920
API gravity 22.3
Viscosity, cP 1.55
Pour point (oC) 30
Asphaltene, % 0.79
Resin, % 5.59
Acid number, mg KOH/g 2.21

origin) with a synthetic surfactant in association with glycerol (a by-product

of biodiesel production). Glycerol was added to the surfactant blend to
improve the effectiveness of the chemical slug in displacing/recovering max-
imum residual oil. The objective was to investigate the potential of using the
combined surfactant system for further enhancing the oil recovery efficiency
during chemical flooding.

2. Experimental
2.1. Materials
Crude oil was collected from an oilfield of Assam, India. Detailed analyses
revealed that crude oil was medium gravity and of acidic nature (Table 1).
The formation water of the same oilfield was collected, cleaned, and ana-
lyzed for its physicochemical properties (Table 2). Based on the compos-
itional analysis of the formation water, synthetic formation brine (SFB) was
prepared with a salinity of 2989 mg/Land used as the aqueous medium.
Gray Berea sandstone cores with porosities around 20% and brine perme-
abilities in the range of 60–100m D were used for the wettability and core
flooding experiments. The bio-surfactant, Rhamnolipids (90%), was pur-
chased from Sigma Life Science (India). Rhamnolipid are glycolipids pro-
duced using the microbe Pseudomonas aeruginosa. It is highly
biodegradable and nontoxic. Rhamnolipids have very low CMC value of 5-
350 mg/L and can reduce the IFT between oil and water to <1 mN/m. The
synthetic surfactant, cetyltrimethylammonium ammoniumbromide (CTAB)
was procured from the Sisco Research Laboratories, India. Glycerol used in
this work was a by-product of biodiesel production and received from the
Bio-Energy research lab of the Department of Chemical Engineering,
Indian Institute of Technology Guwahati.

2.2. Methods
The methodology for selecting the combined surfactant system and estimating
its EOR potential is shown in Figure 1.
2910 S. PANNU ET AL.

Table 2. Properties of formation water.

Parameter Value
pH 9.14
Viscosity, cp at 30 oC 0.91
Sodium, mg/L 1250
Chloride, mg/L 627
Bicarbonate, mg/L 987
Calcium, mg/L 45
Magnesium, mg/L 12
Sulfate, mg/L 68
Salinity, mg/L 2989

2.2.1. Thermal stability analysis

Surfactants used for flooding must be thermally stable under reservoir con-
ditions. A thermogravimetri canalyzer (TGA, make: Netzsch,
model:TG209F1) was used to measure the thermal stability of the surfac-
tants. Around 10 mg surfactant sample was placed in the alumina crucible
and scanned in the temperature range of 30–700  C at a constant heating
rate of 10  C/min.

2.2.2. Aqueous stability test

The solubility and stability of the surfactants with glycerol in SFB were
assessed with the aqueous stability tests. Rhamnolipids (0.5 wt%) and
CTAB (0.5 wt%) were added to SFB at different glycerol concentrations
(ranging from 0 to 4 wt%) in 50 ml centrifuge tubes and mixed intimately
for 6 hours in a TarsonsRotospin. The test tubes were kept in an oven
(maintained at 70  C) for 7 days and observed for any kind of cloudiness or
precipitation.

2.2.3. Surface tension and IFT measurements

An automatic surface tensiometer (Make: Kyowa, model: DY100) was used
to determine the surface tension of the surfactant solutions using the
Wilhelmy method. The spinning drop tensiometer (Make:Kruss, Model:
Site 100) was utilized to measure the oil-water IFT. The temperature of the
system was fixed at 70  C. The length to diameter ratio of the oil droplet
was kept greater than 4 for IFT measurements by maintaining a constant
rotational speed of 6000 rpm (Phukan et al. 2019b).

2.2.4. Wettabilityanalysis
The reservoir rock wettability was measured by determining the contact
angle between the aqueous surfactant solution and the core surface with
the Goniometer drop shape analysis system (DSAS), Holmarc. Core disk or
slices were prepared, cleaned, polished, and saturated with crude oil at res-
ervoir temperature (70  C) in an oven for 2 weeks. The core was placed in
 PETROLEUM SCIENCE AND TECHNOLOGY 2911

Figure 1. Methodology adopted for selecting the combined surfactant system and estimating
oil recovery potential.

the DSAS and about 10 ml of the aqueous chemical solution was dropped
on the surface of the core sample using a 0.5 mm needle. The inbuilt soft-
ware of the DSAS measured the contact angle approximately 15 minutes
after the droplet was placed.

2.2.5. Core flooding experiments

A lab-scale core flooding system was used to conduct the core flooding
experiments as described in our previous study (Phukan et al. 2019a).

2.3. Simulation studies

The simulation work was performed to predict the oil recovery performance
of surfactant flooding in an actual reservoir using a combined surfactant sys-
tem. To verify the impact of the surfactant injection in the field-scale,
2912 S. PANNU ET AL.

Figure 2. TGA curves of rhamnolipids, glycerol, and CTAB samples.

MATLAB Reservoir Simulation Toolbox (MRST) EOR-surfactant module was

used in this study.

3. Results and discussion

3.1. Experimental study
3.1.1. Thermal stability of surfactants
Surfactants must be stable and should not decompose under the high-tem-
perature conditions of the reservoir for their desired performance. So, the
chosen surfactants (rhamnolipidsand CTAB) and glycerol were subjected to
thermal stability analysis. Figure 2 shows the TGA graph depicting the
change in weight loss as a function of the temperature. The graphs show
that glycerol started decomposing beyond 170  C, and rhamno lipids were
found to be almost stable till 200  C. The temperature of Assam oil reser-
voirs is generally less than 90  C (Phukan et al. 2020). Thus, both rhamno-
lipids and glycerol are expected to be thermally stable in the reservoir
without any possible weight loss. The thermal stability of CTAB for the
same oilfield was analyzed by previous authors and found to be stable
under reservoir conditions (Saha et al. 2018).
As the glycerol was a by-product, its characteristics were identified using
FTIR spectroscopy study. The spectra were recorded from 500 to
4000 cm
1 and obtained peaks matched against standard glycerol database.
C–H, OH, and CO were the major functional groups present in the spectra
of glycerol, along with aromatics and nitrogen (Figure 3). The peaks
obtained at 2927 cm
1 indicated the presence of single bond alkanes
whereas peaks at 2879 cm
1 accounted for the –CH2 functional group. The
 PETROLEUM SCIENCE AND TECHNOLOGY 2913

Figure 3. FTIR spectra of glycerol and aged glycerol samples.

FTIR spectrum showed O–H stretching at 3286 cm
1. Extension of the CN

group was also reported in the 1400–1420 cm
1 region. Stretching of the
primary alcohol group was observed at 1107 cm
1. Thus the presence of
the noted groups supported that the by-product of bio-diesel production
possessed glycerol characteristics (Danish et al. 2017). The figure also shows
the FTIR spectra of two-week aged glycerol sample (at 70  C) which also
confirmed its thermal stability under reservoir conditions.

3.1.2. Aqueous stability of surfactants with glycerol in synthetic formation

brine
Figure 4 illustrates the aqueous stability tests for 0.5 wt% rhamnolipids and
0.5 wt% CTAB in SFB at different glycerol concentrations (0–4 wt%) main-
tained at 70  C. It can be observed that at higher glycerol concentrations
(3.5 wt% and above), the components were unstable displaying clear signs
of cloudiness. However, at or below 3 wt% glycerol no cloudiness was noted
confirming the solubility with the surfactant blend in SFB at reservoir tem-
perature. This observation affirmed that the surfactant solutions with con-
centration  0.5 wt% will have no instability issues when mixed with
glycerol (3 wt%) in SFB aqueous phase.

3.1.3. Surface tension and IFT behavior of surfactants

The surface tensions of glycerol, CTAB, and rhamnolipids solutions were
measured at ambient temperature and plotted as a function of their concen-
trations (Figure 5). The surface tension decreases with increasing surfactant
concentration, as the surfactant molecules get adsorbed on the liquid-gas
2914 S. PANNU ET AL.

Figure 4. Aqueous stability tests for 0.5 wt% rhamnolipids and 0.5 wt% CTAB at varying con-
centrations of glycerol (0–4 wt%) in synthetic formation brine (2989 mg/L salinity) at 70 oC.

interface until they reach a minimum at the CMC value. The CMC of glycerol
was found to be 0.8 wt% with the lowest surface tension value of 25.89 mN/m
which is appreciably lower than the surface tension of only formation brine
( 72 mN/m). The CMCs of the surfactants namely CTAB and rhamnolipids
were found to be 0.05 wt%, and 0.02 wt% with surface tension values of
39.37 mN/m and 33.04 mN/m, respectively.
The equilibrium oil-water IFT of glycerol was measured at reservoir tem-
perature (70  C) for different concentrations and plotted as shown in
Figure 6a. With the initial increase in the concentration, a reduction in oil-
water IFT was observed until the lowest IFT (0.093 mN/m) was reached at
its CMC (0.8 wt%). Thereafter, no further reduction in the equilibrium IFT
values was observed as the glycerol concentration was increased. The
results of the surface tension and IFT measurements of glycerol revealed its
surface-active and interfacial properties, thereby highlighting its potential
use as an EOR fluid. The attributes that make this by-product of biodiesel
production an attractive option for EOR applications are its low cost and
its ability to act as a carbon source in the reservoir for insitu microbes to
produce biosurfactants. Additionally, the combined use of glycerol with
surfactant solutions has also been reported to improve oil recovery due to
glycerol’s ability to act as a viscosifying agent and as a sacrificial adsorbate
to reduce the surfactant adsorption by reservoir rock (Curbelo et al. 2020).
Further, the interfacial characteristics of the biosurfactant in association
with glycerol were evaluated. For this purpose, the equilibrium oil-water
IFTs of rhamnolipids at various concentrations in the presence of glycerol
(at its CMC) were measured. Figure 6b shows that as the concentration of
rhamnolipids was increased, the IFT initially decreased reaching the lowest
IFT at CMC (0.02 wt%) and then slightly increased. Thus in the presence
of glycerol, the bio-surfactant (rhamnolipids) could achieve an equilibrium
 PETROLEUM SCIENCE AND TECHNOLOGY 2915

Figure 5. Surface tension versus concentrations of different surfactants at ambient temperature.

Figure 6. Equilibrium oil-water IFT curves: (a) With varying glycerol concentration, (b) 0.8 wt%
glycerol (fixed) þ varying rhamnolipids concentration, and (c) 0.8 wt% glycerol (fixed) þ
0.02 wt% Rh (fixed) þ varying CTAB concentration.

oil-water IFT as low as 0.082 mN/m. The association of glycerol caused the
adsorbed surfactant molecules at the oil-water interface to be arranged in
the best possible way which allowed further lowering of IFT to the lowest
level. Henceforth, the impact of adding the synthetic surfactant (CTAB) to
the mixture of 0.02 wt% rhamnolipids þ 0.8 wt% glycerol on the oil-water
IFT was investigated. As shown in Figure 6c, the equilibrium oil-water IFT
was further reduced upon adding CTAB to the mixed solution. Thus, syn-
ergism of the three components namely rhamnolipids, CTAB, and glycerol
was reflected. Interestingly, ultra-low IFT could be attained with their asso-
ciation and the lowest IFT (0.005 mN/m) was achieved with the combined
system comprising of 0.02 wt% rhamnolipids þ 0.8 wt% glycerol þ
0.05 wt% CTAB. A plausible reason for achieving ultra-lower oil-water IFT
was their synergistic behavior which was feasible due to the change in the
molecular arrangement at the interface that the bio-surfactant undergoes
when mixed with synthetic surfactant in the presence of glycerol (Al-
Sulaimani et al. 2012). After reaching the lowest values at the optimum
concentrations, a slight increase in the IFT values was observed due to
molecular redistribution of surfactant at the oil-water interface.
2916 S. PANNU ET AL.

Figure 7. (a)–(e) shows the variation of contact angles of oil-saturated Berea core samples with
different formulations. (f) is the schematic showing contact angle (⍜) measurement method for
rock surface-brine-oil system.

3.1.4. Measurement of contact angle

Favorable wettability alteration of reservoir rocks toward more water wet-
ness plays a crucial role during surfactant flooding in improving oil recov-
ery due to mobilization of the adherent oil. In this study, the wettability
alteration of oil-saturated core samples by the different surfactant systems
was analyzed based on contact angle measurements. Figure 7f shows the
method of contact angle (⍜) measurement. Rock wettability is classified as:
 
water-wet when 0 <⍜ < < , intermediate-wet when 75 <⍜ < 105 , and
 
oil-wet when 105 <⍜ < 180 . The contact angles of the core samples
obtained for the different solutions are illustrated in Figure 7a–e. The con-
 
tact angle with SFB was found to be 74 ± 2 , indicating that the saturated
core sample was water-wet. For 0.8 wt% glycerol, 0.05 wt% CTAB, and
 
0.02 wt% Rh solutions the contact angles formed were reduced to 28 ± 2 ,
   
31 ± 2 , and 62 ± 2 , respectively. This suggested that all the surfactant
solutions could suitably alter the wettability of the core sample to more
water-wet conditions. However, the obtained results show that for the
crude oil-rock-surfactant system, the largest alteration in wettability was
observed for the combined surfactant system (0.02 wt% rhamnolipids þ
 
0.8 wt% glycerol þ 0.05 wt% CTAB) with ⍜ ¼ 20 ± 2 . Thus, it was con-
cluded that the combined surfactant system had greater potential in favor-
ably altering the wettability of the core sample than each of the surfactant
solutions separately.

3.1.5. Core flooding experiments

Cylindrical Berea sandstone cores of identical dimensions and properties
(3.9 cm in diameter, 11 cm in length, and 20% porosity) were used in the
core flooding experiments. Three experiments namely core flood I, II, and
III were conducted to make a comparative assessment of the oil recovery
performances by secondary water flooding, secondary surfactant flooding,
 PETROLEUM SCIENCE AND TECHNOLOGY 2917

Table 3. Summary of experimental details and results of the core flooding experiments.
Fluid Recovery
Saturation (%) Injection (PV) (% OOIP)
Core Flooding Injection Total Recovery
flood schemes mode Soi Swi WF EOR WF EOR (% OOIP)
I Water flooding Secondary 80.74 19.26 1.8 – 34.15 – 34.15
II Surfactant flooding Secondary 78.22 21.78 – 1.8 – 53.39 53.39
III Tertiary surfactant Tertiary 82.31 17.69 0.9 0.9 33.76 15.27 49.03
flooding
The values are in bold to provide a comparative assessment of the total/cumulative oil recovery obtained from
the different injection schemes during core flooding experiments.

and tertiary surfactant flooding respectively. The total volume of fluid

injected in all the core floods was maintained constant at 1.8 pore volume
(PV). In core flood III, the tertiary surfactant injection scheme was imple-
mented in which 0.9 PV of SFB injection was followed by 0.9 PV injection
of the formulated combined surfactant system solution (0.02 wt% rhamnoli-
pids þ 0.8 wt% glycerol þ 0.05 wt% CTAB). A summary of the experimen-
tal details and results of the core floods are presented in Table 3.
The cumulative oil recovery and pressure drop (DP) data versus PV of
fluid injected for core flood I is shown in Figure 8a. In this core flood, sec-
ondary water flooding was performed by injecting 1.8 PV of SFB into the
oil-saturated core plug, resulting in an ultimate oil recovery of 34.15%
OOIP. The oil recovery continuously increased with SFB injection upto
about 1 PV during the initial injection period. Thereafter, no further
increase in oil recovery was observed and the cumulative oil recovery curve
levelled off till the end of injection. Most of the oil displacement from the
core plug took place during the initial period as the DP curve rose due to
the formation of the oil bank. The peak DP value of 6.3 psi was observed at
around 0.6 PV of SFB injection. After the breakthrough of the oil bank and
the injected SFB, the DP across the core plug reached a steadystate toward
the end of injection.
In core flood II, a similar injection scheme was followed as core flood I.
However, instead of SFB injection, the formulated combined surfactant
solution was used for injection in the secondary surfactant flooding mode.
A higher cumulative oil recovery of 53.39% OOIP was obtained after inject-
ing the same 1.8 PV of surfactant solution, as shown in Figure 8b.
Although a similar trend of the DP curve was observed, a higher DP peak
(8.2 psi) indicated the mobilization of some extra oil during the surfactant
flooding process. A steeper oil recovery curve also indicated that injection
of the composite surfactant solution resulted in better mobilization and dis-
placement of oil from the core. The additional oil recovery by surfactant
flooding was possible due to the lowering of oil-water IFT (Phukan et al.
2019, 2020) and favorably wettability alteration of the core surface to a
more water-wet state.
2918 S. PANNU ET AL.

Figure 8. Cumulative oil recovery and pressure drop versus pore volume of fluid injected dur-
ing (a) Secondary water flooding, (b) Secondary surfactant flooding, and (c) Tertiary surfac-
tant flooding.

Core flood III was conducted to investigate the oil recovery performance
of the tertiary surfactant flooding with the same formulated combined sur-
factant system as the chemical slug. The oil recovered by secondary water
flooding was 33.76%OOIP and additional oil recovery of 15.27%OOIP was
obtained by tertiary surfactant flooding as shown in Figure 8c. The DP
curve shows that during secondary water flooding, the DP across the core
build-up following the oil displacement by brine and after the formation of
the oil bank. Thereafter, DP decreased to finally achieve a steady-state value
toward the end of water flooding. During the tertiary surfactant flooding,
the formation of another DP peak was observed which corresponded to the
formation of a second oil bank. This oil bank was formed due to the
mobilization of the residual oil in the water flooded core by the combined
surfactant solution. A comparison of core flood II and III shows that the
ultimate oil recovery by surfactant flooding was higher in the secondary
mode (53.39%OOIP) compared to the tertiary mode (49.03%OOIP). The
better oil recovery in the secondary injection mode of surfactant flooding
can be related to the presence of higher saturation oil in the core when the
surfactant flooding began. With higher saturation of oil, the injected surfac-
tant slug could mobilize a greater volume of the oil from the core and thus
more oil was recovered. On the other hand, in the tertiary mode, the pres-
ence of high water saturation in the water flooded core resulted in the par-
tial water blockage preventing part of the residual oil in the pore spaces
from coming into contact with surfactant solution (water shielding effect).
Figure 8b and c also show that the peak recovery in the tertiary mode
reached at a later time (1.6 PV) compared to the secondary mode (1PV).
In other words, the production of oil required a shorter period in second-
ary mode than in tertiary mode.

3.2. Simulation study

In this section, surfactant flooding with the combined surfactant system
was further assessed by reservoir simulation with the MRST EOR module
 PETROLEUM SCIENCE AND TECHNOLOGY 2919

Figure 9. Simulated views of (a) Reservoir rock grid, (b) Porosity distribution, and (c) Location
of injection well and producing well.

to analyze its applications in an actual reservoir. The objective of the simu-

lation study was also to validate the results obtained from the experimental
studies and to predict the performance of surfactant flooding on the
field–scale. The surfactant module uses a structured grid of dimension
20  15. The reservoir rock and porosity distribution are represented in
Figure 9a and b. The reservoir rock unit dimension was set equivalent to
200 m physical aspect. The depth of the well was taken at 2500 m. Thus,
the depth of the reservoir block was from 2500 to 2625 m. The porosity of
the well was defined between 0.05–0.21% instead of constant porosity, con-
sidering the heterogeneous conditions of the reservoir. The total pore vol-
ume of the rock was calculated in MATLAB and found to be 8.922e þ 9 m3.
Fluids were injected at a rate of 1000 m3/day for 14,960 days. The injection
well and the production well were located diagonally to each other. Whereas
the injection well was in the bottom layer, the producer well was located at
the top layer. The specific well pattern was selected to keep the system simi-
lar to the core flooding setup. For a better comparison with the core flood-
ing experiment, a single injection-production well setup was used in the
simulation as shown in Figure 9c.

3.2.1. Simulation runs

In all the simulation runs, the cumulative fluid injection was maintained
constant at 14.96e þ 06 m3 which amounted to 1.7 PV of the reservoir. In
the surfactant module, surfactant concentration and IFT values were set at
0.3 wt% and 0.005 mN/m, respectively. The particular value of IFT was
chosen to make it comparable with the value obtained for the selected
combined surfactant system in the experimental study.
Figure 10a–c shows the distribution of the simulated oil saturation after
secondary water flooding, secondary surfactant flooding, and tertiary sur-
factant flooding respectively. After 14,960 days of secondary water flooding,
the average residual oil saturation was around 70% (Table 4). Thus, a sig-
nificant amount of residual oil was left behind unrecovered. Most of the
residual oils were concentrated near the production well and in the upper
2920 S. PANNU ET AL.

Figure 10. Simulated oil saturation after (a) Secondary water flooding, (b) Secondary surfactant
flooding, and (c) Tertiary surfactant flooding. Simulated cumulative oil productions vs time for
(d) Secondary water flooding, (e) Secondary surfactant flooding, and (f) Tertiary surfactant flood-
ing. Simulated oil surface production rates vs time for (g) Secondary water flooding, (h)
Secondary surfactant flooding, and (i) Tertiary surfactant flooding.

Table 4. Oil production and residual oil saturation at different surfactant concentration.
Surfactant
concentration Injection OOIP Cumulative oil Oil Remaining Residual oil
(wt%) mode (m3) recovered (m3) recovery (%) oil (m3) saturation (%)
0 Secondary 7.14e þ 06 2.13e þ 06 29.78 5.01e þ 06 70.22
0.01 Secondary 7.14e þ 06 2.15e þ 06 30.07 4.99e þ 06 69.93
0.05 Secondary 7.14e þ 06 2.43e þ 06 34.02 4.71e þ 06 65.98
0.30 Secondary 7.14e þ 06 3.18e þ 06 44.48 3.96e þ 06 55.52
1 Secondary 7.14e þ 06 3.21e þ 06 44.90 3.93e þ 06 55.10
0.30 Tertiary 7.14e þ 06 2.99e þ 06 41.81 4.16e þ 06 58.19
The values are in bold to provide a comparative assessment of the total/cumulative oil recovery obtained from
the different injection schemes during core flooding experiments.

part of the reservoir. However, the simulated oil distribution after second-
ary surfactant flooding (Figure 10b) and tertiary surfactant flooding (Figure
10c) show that residual oil saturation in the reservoir had been reduced
appreciably after their application compared to secondary water flooding.
After secondary and tertiary surfactant flooding, the average residual oil
saturation decreased to around 55% and 58%, respectively (Table 4). The
cumulative oil productions as a function of time for the three processes are
shown in Figure 10d–f. These cumulative oil recoveries were 2.126e þ 06
m3, 3.176e þ 06 m3, and 2.985e þ 06 m3 which amounted to oil recovery
factors of 29.78%, 44.48%, and 41.81% OOIP, respectively, for the three
 PETROLEUM SCIENCE AND TECHNOLOGY 2921

injection processes (Table 4). Thus, field-scale simulation results showed

that secondary surfactant flooding resulted in the best oil recovery, which
was consistent with the findings of the core flooding experiments.
Moreover, the higher oil recoveries by surfactant flooding compared to
water flooding supported the experimental observations about the com-
bined surfactant system’s potential to improve the oil recovery efficiency.
The simulated oil surface production rates curves for the three processes
are also presented in Figure 10. During the initial stage of secondary water
flooding, the oil production rate dropped sharply and then rose as the
waterfront approached pushing the oil toward the producing well (Figure
10g). The production rate was high till 3000 days as the oil was produced
by the displacing water phase. Thereafter, the oil rate declined as residual
oil saturation was reached and no more oil was recovered by the injected
fluid. As depicted in Figure 10i, during the tertiary surfactant flooding, a
sudden increase in oil production rate was observed at 7000 days as the
injected surfactant system created the oil bank due to the mobilization of
residual oil. However, in secondary injection mode, the surfactant solution
injected from the start of the flooding process restricted the sudden drop
in the oil production rate after 4000 days, and an almost constant decline
in the oil production rate was observed as shown in Figure 10h.

4. Conclusions
In this study, the performance of combined bio (rhamnolipids) and syn-
thetic (CTAB) surfactants in association with glycerol (a by-product of bio-
diesel production) was investigated for its potential use as an EOR fluid.
Based on the findings, the following conclusions were drawn.

1. The results of the surface tension and IFT measurements revealed the sur-
face-active and interfacial properties of the glycerol. Glycerol displayed the
minimum IFT of 0.093 mN/m at its CMC, which was further reduced to
0.082 mN/m when mixed with the rhamnolipids (at CMC). Interestingly,
the oil-water IFT was favorably reduced to ultra-low value (0.005 mN/m)
for the combined surfactant system combined (0.02wt% rhamnolipids þ
0.8wt% glycerol þ 0.05 wt% CTAB). This was possible due to the syner-
gism achieved among all the components.
2. The contact angle measurements showed that each component of the com-
bined system could change the wettability of the oil-saturated rock surface
to more water-wet conditions. However, maximum water-wetness (⍜ ¼
 
20 ± 2 ) of the rock surface was observed when all the three components
were combined in the correct proportions for synergism.
2922 S. PANNU ET AL.

3. Core flooding experiments showed that compared to secondary water

flooding additional 19.24% and 14.88% OOIP could be recovered by sec-
ondary and tertiary surfactant flooding respectively using the com-
bined system.
4. The simulation studies also confirmed that on the field-scale also higher
oil recovery was possible by secondary surfactant flooding.
5. Thus, the study demonstrated that surfactant flooding with the combined
bio and synthetic surfactant with glycerol has the potential capability to
improve oil recovery considerably. The competence of glycerol in producing
in-situ biosurfactants and reducing surfactant adsorption onto reservoir
rock can be investigated in the future.

Acknowledgments
The authors would like to acknowledge the Department of Chemical Engineering, Indian
Institute of Technology, Guwahati, India, and the Department of Petroleum Technology,
Dibrugarh University, India for the assistance provided in this study.

Disclosure statement
The authors declare that they have no competing interests.

Author’s contribution
All authors contributed equally to this work.

ORCID
Sombir Pannu http://orcid.org/0000-0002-6429-9588
Ranjan Phukan http://orcid.org/0000-0002-2115-168X
Pankaj Tiwari http://orcid.org/0000-0003-2578-3462

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Nomenclature
CMC critical micelle concentration
CTAB cetyltrimethylammonium ammoniumbromide
DSAS goniometer drop shape analysis system
EOR enhanced oil recovery
FTIR Fourier transform infrared spectroscopy
IFT interfacial tension
MRST MATLAB reservoir simulation toolbox
Nc capillary number
OOIP original oil in place
2924 S. PANNU ET AL.

PV pore volume
SFB synthetic formation brine
Soi initial oil saturation
Swi initial water saturation
TGA thermogravimetricanalyzer
WF water flooding
mD milli Darcy
⍜ contact angle
DP pressure drop