Journal of Petroleum Science and Engineering 192 (2020) 107333

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Journal of Petroleum Science and Engineering

journal homepage: http://www.elsevier.com/locate/petrol

Core-scale modelling and numerical simulation of zwitterionic surfactant

flooding: Designing of chemical slug for enhanced oil recovery
Amit Kumar , Ajay Mandal *
Department of Petroleum Engineering, Indian Institute of Technology (Indian School of Mines), Dhanbad, 826004, India

A R T I C L E I N F O A B S T R A C T

Keywords: Surfactant flooding is a proven enhanced oil recovery method for the recovery of trapped crude oil from the pores
Enhanced oil recovery of the reservoir. In the present study, the applicability of a synthesized zwitterionic surfactant as an efficient EOR
Zwitterionic surfactant agent was tested, in terms of its interfacial tension reduction capability, emulsification behavior, and wettability
Core flooding
modification behavior. Core flooding experiments conducted in sandstone core with the injection of 0.3 pore
Simulation
CMG-STARS
volume of chemical slug after water flooding showed 20% of additional oil recovery. The core flooding exper­
iment was simulated using CMG-STARS simulator and history matching of relative permeability curve and its
interpolation parameters were done. The validated model closely represented the experimental core flooding
with very low error of 6%. The validated model helps in understanding the movement of crude oil and its
interaction with the injected surfactant slug in the porous media. The validated model was further used for
optimization of injected chemical slug by varying the parameters such as the surfactant concentration in the
injected slug, the volume of injected chemical slug, and the injection rate of chemical slug. Each parameter had
different effects on the oil recovery efficiency and cumulative oil recovery of more than 90% OOIP was obtained
using model with injection of 1 PV of chemical slug containing 100 ppm of surfactant with the injection rate of
0.3 mL/min. The simulation of core flooding helped in optimization of crude oil production by zwitterionic
surfactant and its implementation on field scale production by zwitterionic surfactant flooding.

1. Introduction
The production of crude oil by primary and secondary recovery
processes have low recovery efficiency and more than 50% of original
oil in place (OOIP) remains trapped in the pores of the reservoir after the
application of conventional techniques of oil recovery (Fink, 2015). The
production of the residual oil from the reservoir is achieved by appli­
cation of various enhanced oil recovery (EOR) techniques (Wang et al.,
2018). These techniques are majorly categorized as thermal, chemical,
and miscible EOR and the selection of a particular method depends on
the reservoir properties and subsurface conditions. Surfactant flooding,
a chemical EOR techniques, has been proven to mobilize the trapped
crude oil from the pores of the reservoir (Gbadamosi et al., 2019).
Surfactant flooding improves the pore-scale displacement of crude oil by
various mechanisms such as reduction of interfacial tension (IFT),
wettability alteration, and emulsification (Mandal, 2015; Sheng, 2015).
Reduction of IFT between the injected slug and trapped crude oil droplet
leads to the reduction of rigidity of oil-water interface, causing the
mobilization of crude oil by the pressure differential present in the
reservoir. The lowering of IFT also leads to the emulsification of trapped
crude oil, that forms an oil bank at the flood front (Bera et al., 2011).
Surfactant flooding also leads to the change of wetting state of reservoir
rock from oil-wet to water-wet. The change in wettability causes the
desorption of adhered crude oil droplets from the reservoir rock and
leads to their recovery.
The technological feasibility of a surfactant flooding is initially tested
by laboratory scale experiments. These experiments include testing of
surfactant’s ability to reduce the IFT, alter the wetting state of reservoir,
form stable emulsion, and recover oil in core flooding experiments. The
results obtained from the flooding experiments conducted at laboratory
scale are then simulated to determine the parameters required for
upscaling and simulating using models at the reservoir level (Pandey
et al., 2008). The application of simulation of fluid flow through the
porous reservoir has been applied in oil and gas industry since the 1950s
(Settari, 1993). Since then the applicability of reservoir simulation has
matured and is now used widely for field development, analysis and
comparison of different projects, and testing of cost effectiveness of a
particular process. Reservoir simulation has also improved in regards to

* Corresponding author.
E-mail address: ajay@iitism.ac.in (A. Mandal).

https://doi.org/10.1016/j.petrol.2020.107333
Received 10 March 2020; Received in revised form 20 April 2020; Accepted 22 April 2020
Available online 28 April 2020
0920-4105/© 2020 Elsevier B.V. All rights reserved.
A. Kumar and A. Mandal
the visualization of flow of the reservoir fluids through the porous media
(McVay et al., 1991). The advances in reservoir simulation include the
modelling of dual porous/permeable regions, studies of geomechanics of
reservoir, streamline simulation, and simulation of complex and tight
reservoirs (Bailey, 2019; Lo €f et al., 2008; Settari, 1993). Simulation of
EOR techniques such as steam, polymer, surfactant, and alkali injection
has been done to test the applicability of the respective EOR method to
recover the oil from the reservoir (Fadili et al., 2009; Lucia et al., 2013;
Shaharudin et al., 2013). Simulation also aids in the study of effect of
parameters such as composition of injected slug, volume of injected slug,
and injection rate to remove the uncertainties associated with the
application of chemical EOR in reservoirs (Wang et al., 2018). Popular
reservoir simulators widely used in research applications and petroleum
industry are Eclipse by Schlumberger, IMEX and STARS by CMG, and
UTCHEM by University of Texas at Austin (Rai et al., 2015). These
simulators can easily model the fluid flow at field and core scale, and
have in-built capabilities to model complex recovery processes such as
flooding of steam, solvents, air, and chemicals.
In present study, a core flooding experiment using surfactant slug
containing zwitterionic surfactant was simulated using CMG-STARS
simulator. The physicochemical properties of the zwitterionic surfac­
tant in terms of its IFT reduction capability, emulsification, and effec­
tiveness in wettability alteration have been discussed elaborately in our
previous work (Kumar and Mandal, 2018). The core flooding experi­
ment was initially modeled and the model was validated by history
matching of relative permeability curve and its interpolation parame­
ters. The validated model was then used for the optimization of injected
chemical slug by varying the parameters such as the surfactant con­
centration in the injected slug, volume of injected chemical slug, and
injection rate of chemical slug. The optimum chemical injection slug was
determined to achieve the maximum oil recovery.
2. Theory: Governing equations
STARS (Steam, Thermal, and Advanced Processes Reservoir Simu­
lator) is a commercial simulator by CMG (Computer Modelling Group),
which has the capabilities for modelling and simulation of complex and
advanced recovery processes involving injection of steam, solvents, air,
and chemicals. CMG STARS is a finite difference numerical simulator
that solves a set of conservation equations, consisting of material bal­
ance equations, flow equations, chemical reactions, heat exchange
equations, and phase equilibrium equations.
The basic governing equations relate the conservation of mass and
energy for the elementary volume or the region of interest, where the
change for each component in the volume is related to the fluids
entering and leaving the volume (Liu and Chen, 2018). The conservation
equation is defined as:
Rate of accumultion ¼ Net rate of inflow from adjacent regions
þ Net rate of addition from sources and sink (1)
The governing conservation equation is applied for each component
along with the energy of the system. The mass conservation equation for
component i is defined as:
nf
∂� � � X �
Vf ρw Sw wi þ ρo So xi þ ρg Sg yi þ Vv Adi ¼ Tw ρw wi ΔΦw þ To ρo xi ΔΦo
∂t k¼1
� X
nr
� and volumetric rate of reaction k respectively. HLo represents the heat
þ Tg ρg yi ΔΦg þ V s’ki ski rk
k¼1
nf
X � � Pnf
þ φDwi ρw Δwi þ φDoi ρo Δxi þ φDgi ρg Δyi þ ρw qwk wi þ ρo qok xi þ ρg qgk yi
k¼1
nf
X
þ δiw ρw qaqwk
k¼1
(2)
2
Journal of Petroleum Science and Engineering 192 (2020) 107333
where, ∂∂t ½Vf ðρw Sw wi þρo So xi þρg Sg yi Þ þVv Adi � is the accumulation term
for a flowing and adsorbed component i, with Vf signifying the total fluid
volume and Vv representing the void volume. ρ and S represent the
density and saturation of the respective phases, i.e. water, oil, and gas,
present in the volume and wi, xi, and yi represents the mole fraction of
component i in water, oil, and gas respectively. Tw ρw wi ΔΦw þ
To ρo xi ΔΦo þ Tg ρg yi ΔΦg þ φDwi ρw Δwi þ φDoi ρo Δxi þ φDgi ρg Δyi is the
flow term for the flowing component i, where T is the transmissibility of
the component between the two regions, thus accounting for the cross-
sectional area, distance between the elementary volumes, and the
permeability at the interface. Thus transmissibility, T, is related to
volumetric flow rate, v, as per the expression:
� �
krj
vj ¼ T ΔΦj j ¼ w; o; g (3)
μj rj
where, krj is the relative permeability, rj is the phase resistance factor
and μj is the viscosity of the phase j. ΔΦj is the potential difference of
phase j and its positive or negative value corresponds to the inflow or
outflow from the elementary volume. Dwi, Doi, and Dgi are the respective
dispersibility of the component in water, oil, and gas phases.
Pr
V nk¼1 ðs’ki ski Þrk is the reaction source/sink term for component i, and
ρw qwk wi þ ρo qok xi þ ρg qgk yi is well source/sink term for the flowing
component i. The well source/sink terms are the means for driving all
the processes, where qjk is the well rate of the respective phases in the
layer k and given by the expression:
�
qjk ¼ Ijk pwfk pk j ¼ w; o; g (4)
where, Ijk is the phase index related to the geometry, skin factor,
permeability, and layer thickness. pwfk is the flowing wellbore pressure
Pnf
and pk is the pressure of the volume. k¼1 ρw qaqwk is aquifer source/sink
term for water component, where qaqwk represents the volumetric flow
rate through the block face k to/from adjacent aquifer.
The energy conservation equation is defined as:
∂� �
V ρ S U þ ρo So Uo þ ρg Sg Ug þ Vv cs Us þ Vr Ur
�
∂t f w w w
nf
X � �
¼ Tw ρw Hw ΔΦw þ To ρo Ho ΔΦo þ Tg ρg Hg ΔΦg
k¼1
nf
X
þ KΔT þ ρw qwk Hw þ ρo qok Ho þ ρg qgk Hg þ V
k¼1
X
nr
� Hrk rk þ HLo þ HLv þ HLc
k¼1
nf
X
þ ðHACV þ HACD Þk (5)
k¼1
where, ∂∂t ½Vf ðρw Sw Uw þρo So Uo þρg Sg Ug Þ þVv cs Us þVr Ur � is the energy
accumulation term. Uj is the internal energy as a function of temperature
and phase composition. Tw ρw Hw ΔΦw þ To ρo Ho ΔΦo þ Tg ρg Hg ΔΦg þ KΔT
is the flow term of energy between two regions and ρw qwk Hw þ
ρo qok Ho þ ρg qgk Hg is the well source/sink term for energy. Hj denotes the
enthalpy of the respective phases. The reaction source/sink term for
Pr
energy is represented by V nk¼1 Hrk rk , where Hrk and rk are the enthalpy
transfer rate into the volume from the surrounding regions. HLv and HLc
are the heat transfer rate for convection model and constant heat
transfer model respectively. k¼1 ðHACV þ HACD Þk is the aquifer source/
sink term for energy, where HACV represents the heat transfer rate by
convection to/from the adjacent aquifer and HACD is the heat transfer
rate by conduction to/from the adjacent aquifer.
The governing equations for mass and energy represented as Equ. 2
and 5 respectively are associated with the individual components
A. Kumar and A. Mandal
present in all the phases in the model. The interaction of the components
between the phases is considered in the compositional model. However,
for simplification of calculations and reduction of computation process,
the black oil model is mostly considered. In a black oil model, the
respective phases are assumed to have no interaction among themselves
(Mesbah et al., 2012). CMG-GEM simulator offers the capability to
model a compositional model, whereas the black oil model is simulated
using CMG-IMEX simulator. The advanced studies on the black oil model
are simulated using CMG-STARS simulator.
Apart from the basic conservation equations, CMG STARS also uti­
lizes various correlations, most important among which is Corey’s cor­
relation, used for generating relative permeability curve, which specifies
the rock-fluid interaction data. Corey’s correlation is preferred for
generating the relative permeability curves when detailed studies
required for determining the relative permeability behavior could not be
performed. Corey’s correlations are given as (Corey, 1977):
� �Nw
Krw ¼ Krwiro
Sw Swcrit
(6)
1:0 Swcrit Soirw
� �Now
Krow ¼ Krocw
So Sorw
1:0 Swcon Sorw
� �Nog
Sl Sorg Swcon
Krog ¼ Krogcg
1:0 Sgcon Sorg Swcon
� �Ng
Sg Sgcrit
Krg ¼ Krgcl
1:0 Sgcrit Soirg Swcon
where, Krw is water phase relative permeability for water-oil table, Krow
is oil phase relative permeability for water-oil table, Krog is liquid phase
relative permeability for liquid-oil table, Krg is gas phase relative
permeability for liquid-gas table, Swcon is connate water saturation, Swcrit
is critical water saturation, Soirw is irreducible oil saturation for water-oil
table, Sorw is residual oil saturation for water-oil table, Soirg is irreducible
oil saturation for liquid-gas table, Sorg is residual oil saturation for liquid-
gas table, Sgcon is connate gas saturation, Sgcrit is critical gas saturation,
Krocw is Kro at connate water saturation, Krwiro is Krw at irreducible oil
saturation, Krgcl is Krg at connate liquid saturation, Krogcg is Krog at
connate gas saturation, Nw is exponent for calculating Krw from Krwiro,
Now is exponent for calculating Krow from Krocw, Nog is exponent for
calculating Krog from Krogcg, and Ng is exponent for calculating Krg from
Krgcl. Equations (6) and (7) are used for generation of water-oil relative
permeability table, and equations (8) and (9) are used for generation of
liquid-gas relative permeability table.
CMG-STARS uses interpolation of relative permeability curves for
different flow behaviors of fluids that occur due to change in the phys­
icochemical properties of aqueous phase caused by the presence of
surfactant, polymer, and alkali. The relative permeability data is inter­
polated between two sets, A and B, which respectively corresponds to
high and ultralow IFT relative permeability curves (Cheng et al., 2019).
The interpolated relative permeability data as the function of capillary
number is obtained as (Hakiki et al., 2015):
krw ¼ krwA :ð1 wtrÞ þ krwB :wtr
kro ¼ kroA :ð1 oilÞ þ kroB :oil
krg ¼ krgA :ð1 gasÞ þ krgB :gas
where; wtr ¼ ratwWRCV
oil ¼ ratnOCRV
gas ¼ ratnGVRV
ratw and ratn are the values of the dimensionless interpolation
Journal of Petroleum Science and Engineering 192 (2020) 107333
parameters, with values varying between 0 and 1. WRCV, OCRV, and
GCRV are the curvature interpolation parameters, with the default value
of 1. The values of interpolation parameters are related to the capillary
number as:
log10 ðNc Þ DTRAPWA
ratw ¼ (16)
DTRAPWB DTRAPWA
log10 ðNc Þ DTRAPNA
ratn ¼ (17)
DTRAPNB DTRAPNA
where, DTRAPWA and DTRAPNA are interpolation parameters repre­
senting low capillary number for high IFT value and high capillary
number for ultralow IFT value respectively, for wetting phase.
DTRAPNA and DTRAPNB are similar interpolation terms for non-wetting
phase. Thus, using one relative permeability dataset for high IFT value in
case of water flooding, and another relative permeability dataset for
ultralow IFT value in case of surfactant flooding, the relative perme­
ability for intermediate IFT values is interpolated and used while
simulation.
(7) 3. Experimental
3.1. Materials required
(8)
A carboxybetaine based zwitterionic surfactant, N-hexadecyl-N,N-
dimethyl-2-ammonio-1-ethanecarbonate (C16DmCB), was selected for
the core flooding experiment and subsequent simulation studies. NaCl
(9)
(purity > 99%) and Na2CO3 (purity > 99%), bought from SRL Chem­
icals, were used to maintain the salinity and alkalinity of the injected
chemical slug. Crude oil of 33.28 � API gravity was used as oleic phase for
saturation of core samples. The crude oil had a kinematic viscosity of 15
cSt at 30 � C and total acid number of 0.84 mg of KOH/g. The injected
brines and chemical slugs were prepared using de-ionized water.
3.2. Surfactant characterization
The selected zwitterionic surfactant C16DmCB was characterized in
terms of its IFT reduction capability by Dataphysics SVT20 spinning
drop tensiometer. The wettability modification property of the surfac­
tant was tested by sessile drop method using Kruss DSA25 drop shape
analyser. UV analysis method was used to determine the adsorption
behavior on the sandstone rock surface, which is comprised of nega­
tively charged minerals such as quartz, kaolinite, and illite. The details
of these characterizations have been reported in our previous works
(Kumar and Mandal, 2019a, 2018).
3.3. Core flooding procedure
The core flooding of surfactant slug was done on a sandstone core
sample of length 8.75 cm and diameter 3.65 cm, obtained from Cambay
basin. The schematic of the flooding experimental setup has been shown
in Fig. 1. The core sample was assumed to be homogeneous after visual
inspection, as the core sample had no bands or layers, suggesting no
(10) variation in its lithology. The porosity of the core was calculated as 12%
using the weight of the core before and after brine saturation. The ab­
(11) solute permeability of the core sample was calculated as 319 mD by the
injection of brine solution at steady flow rate. The injection of brine into
(12) the core was followed by the injection of crude oil to achieve the connate
water saturation in the core sample as 20%. The flooding sequence for
(13) measurement of efficiency of surfactant flooding includes the initial
flooding of core using brine solution till no oil is produced. The chemical
(14) slug containing surfactant is then flooded, followed by chase water
flooding. The flow rate of the injected fluid was kept at 0.2 mL/min for
(15) all the steps of the flooding sequence. The cumulative oil recovery is
plotted against the volume of injected fluid to get the production profile
of the core flooding experiment.
3
A. Kumar and A. Mandal Journal of Petroleum Science and Engineering 192 (2020) 107333

Fig. 1. Core flooding experimental setup.

3.4. Simulation methodology

The core flooding experiment was simulated using 1-D model in

CMG-STARS. 1-D model was selected for simulation as in core flooding,
the flow of fluids in radial direction is negligible in comparison to the
flow of fluids in axial direction of core. The simulation of core flooding
requires the building of model that accurately represents the core sam­
ple, fluids present in the core and the movement of fluids through the
pores of the core. The data representing the basic properties of the model
are categorized into sections such as rock data, fluid data, rock-fluid
interaction data, initial conditions, and well data. The accuracy of
these data defines the closeness of model to the real core flooding. The
model dimensions were taken as per the dimensions measured for the
core sample. The rock properties which include porosity and perme­
ability were also taken as per the measured value of the core. The fluid
properties incorporated in the simulation model include the density and
viscosity of the aqueous phase and oleic phase, which were determined
during the core flooding experiment. The relative permeability curves
were generated using Corey’s correlation and saturation endpoints of
water-oil table were determined from the results of water flooding. The
Fig. 2. Relative permeability curves of set 1, for high IFT, and set 2, for ul­
effect of IFT reduction by surfactant was incorporated by using two sets
tralow IFT.
of relative permeability curves. The relative permeability curve gener­
ated using Corey’s correlation was used as Set 1, with the value of
slug. The effect of surfactant concentration in the injected slug, volume
interpolation parameter as 5 for both wetting and non-wetting phases.
of injected slug, and the injection rate was tested and the optimized
Set 1 of relative permeability data corresponds to the high IFT between
chemical injection slug was determined by the comparison of the pro­
brine solution and crude oil. Set 2 of relative permeability data corre­
duction profile of the simulation models with the combination of the
sponds to ultralow IFT between surfactant solution and crude oil, with
tested parameters.
the value of interpolation parameter as 2 for both wetting and non-
wetting phases. Fig. 2 shows the relative permeability data sets used
for the base model. However, the values of all parameters cannot be 4. Results and discussion
determined and the initial assumptions for the unknown parameters
were taken. The result obtained by using the base-data set consisting of 4.1. Rock-fluid properties of surfactant
measured and assumed values was validated by history matching of
production profile from the model to the actual production profile of the The zwitterionic surfactant, C16DmCB, has excellent IFT reduction
core flooding experiment. History matching of simulation model was capability at low CMC of 50 ppm. In our previous work, a comparative
done using CMG-CMOST and values of parameters, whose values were test of physicochemical properties of zwitterionic surfactants with
initially assumed for the base model, were determined by the simulation varying carbon chain length was conducted and it was found that
of 600 models with different combinations of values of these parameters. selected surfactant, C16DmCB, is better than the surfactants with chain
The different values of the parameters were generated by CMG’s pro­ lengths of 12, 14, and 18 carbons (Kumar and Mandal, 2018). It has been
prietary optimizer DECE (Designed Exploration and Controlled Evolu­ found that the surfactant, C16DmCB, has lower CMC, better salt toler­
tion). The model with the set of values of the parameters with the least ance, and better IFT reduction capability, in comparison to other sur­
deviation of simulated result and experimental result was regarded as factants. The zwitterionic surfactant was also found to be efficient in
the validated model and further used for tuning of injected chemical wettability alteration of oil-wet sandstone rock to preferentially
water-wet state with minimal loss to surfactant concentration due to

4
A. Kumar and A. Mandal Journal of Petroleum Science and Engineering 192 (2020) 107333

adsorption on rock surface. The wettability alteration efficiency and the

adsorption behavior of zwitterionic surfactant have also been explained
in detail in our previous work (Kumar and Mandal, 2019a). It has also
been found that the zwitterionic surfactants has better interface activity
in comparison to anionic and cationic surfactants (Kumar and Mandal,
2017). The ultra-low IFT achieved by the surfactant and its adsorption
behavior as per Langmuir isotherm model have been incorporated in the
simulation model as the properties of surfactant. These values have been
shown in Table 1.

4.2. Core flooding experiment

The production profile obtained by the core flooding of surfactant

slug has been shown in Fig. 3. It can be seen from the figure that the
cumulative oil production had reached a plateau and the water cut of the
produced fluids had reached close to 100% during the initial brine
flooding. The cumulative oil recovery after the initial water flooding was
found to be 54% and the residual oil saturation of the core was 37%. This Fig. 3. Production profile of surfactant flooding.
lower oil recovery and high residual saturation were caused due to the
high IFT between the crude oil and brine solution and the trapping of
crude oil in the pores of the core (Sheng, 2011). When surfactant slug is
injected in the core, the IFT between the surfactant solution and trapped
crude oil is reduced to ultralow value (Husein et al., 2018; Kumar and
Mandal, 2018). The reduction of IFT of oleic-aqueous interface is caused
by the alignment of surfactant molecules at the interface, where the
adsorbed surfactant molecules are arranged such that the hydrophobic
tail of surfactant molecule is oriented towards the crude oil and the
zwitterionic hydrophilic head of surfactant is oriented towards the
aqueous phase (Wu et al., 2016). The carbon chain of surfactant forms
attractive bonds with the non-polar oil components and the hydrophilic
head of surfactant forms attractive bonds with the polar water mole­
cules. Thus, the presence of surfactant molecules reduces the unbal­
anced forces between the oil and water molecules present at the
interface, leading to reduction of IFT of the interface (Kumar and
Mandal, 2019b). The injection of surfactant also leads to wettability
alteration of core sample to preferentially water-wet condition, leading
to increase in the mobility of trapped crude oil. The increase in ease of
mobility of crude oil and reduction of IFT also causes the emulsification
of trapped crude oil droplets into microemulsion, which forms oil bank Fig. 4. 3-Dimensional model of core sample showing initial oil saturation.
at the flood front. The production of oil bank leads to the increase in oil
recovery and can be seen as the sharp increase in the cumulative oil
volume of the core sample. As shown in the figure, the model had same
recovery shown in the figure. The injection of surfactant slug is followed
oil saturation in all the grids before the starting of the flooding sequence.
by the injection of chase water that pushes the injected surfactant slug
After the sequential flooding of core model with brine, surfactant
through the core. During the chase water flooding, the cumulative oil
solution, and chase water, the oil produced from the producer well was
production again forms a plateau with the production of 100% water as
produced fluid. After the chase water flooding, the additional oil re­
covery by the injection of surfactant slug was found to be 20% and the
residual oil saturation had reduced to 21%. Thus, the application of
zwitterionic surfactant for the production of crude oil can be regarded as
an efficient EOR technique.

4.3. Model validation through history matching

The 3-D model representing the core has been shown in Fig. 4, with
the direction of fluid flow being from injector well to producer well. The
model was divided into 100 � 1 � 1 grids, with each grid having di­
mensions of 0.0875 cm in I direction, and 3.234728 cm in both J and K
directions, thus the total volume of model was equivalent to the bulk

Table 1
Rock-fluid properties of zwitterionic surfactant.
Properties of surfactant Value

IFT at oil and surfactant solution at CMC 0.01 mN/m

Adsorption maxima of surfactant 0.401 mg/g
Wettability modification Oil-wet to water-wet
Fig. 5. Production profiles obtained from simulation and experimental result.

5
A. Kumar and A. Mandal Journal of Petroleum Science and Engineering 192 (2020) 107333

plotted as shown in Fig. 5. The oil production data obtained from the
simulation were compared with the oil production profile obtained after
core flooding experiment. It can be seen from the figure that the result
obtained by the simulation of the model does not match with the
experimental result. This signifies that the initial values of the param­
eters that were assumed didn’t represent the actual conditions and
history matching is required for determination of the values of those
parameters. The parameters whose values were determined by history
matching using CMG-CMOST have been shown in Table 2 along with
their assumed and history matched values.
The parameters SwCon, SoRes, KroCon, KrwRes, Nw, and No corre­
sponds to the Corey’s correlation parameters of the set 1 of relative
permeability curves, and the parameters WettingInterpolator and Non­
wettingInterpolator correspond to the interpolation parameters for wet­
ting and non-wetting phases of set 2 of the relative permeability curves.
The error between the experimental and simulation result for the
different models with different values of the parameters generated by
CMG’s DECE optimizer have been shown in Fig. 6. The error between the
experimental and simulated result for different values of parameters has Fig. 6. Error (%) between simulation and experimental data for
been shown in supplementary data Fig. S1. It can be seen from the figure different models.
that within the 600 sets of values of the parameters, the history matched
values of the parameters had the least error between the simulated
model and experimental data. The production profile of the different
models along with the history matched model and experimental result
has been shown in Fig. 7. It can be seen from the figure that the pro­
duction profile of the history matched model matches closely to the
production profile obtained from the core flooding experiment. The low
error of 6% between the history matched model and experiment signifies
that the history matched model can be regarded as the validated model
and can be further used for the optimization of the injected slug.

4.4. Study of validated model

Fig. 8 shows the production profile of the validated model. It can be

seen from the figure that the production profile of the simulation model
follows the similar trend as obtained for the core flooding experiment as
shown in Fig. 3. The cumulative oil recovery had reached a plateau after
the injection of initial brine and the average oil saturation of the core
was 34% before the injection of the surfactant slug. The oil saturation
map of the core before the injection of the surfactant slug has been
shown in Fig. 9 (a). After the injection of surfactant slug, an increase in Fig. 7. Production profiles of different models obtained by history matching.
the cumulative oil production from the core can be seen, which was the
result of IFT reduction, emulsification, and wettability alteration by the
surfactant in the injected slug. The reduction of IFT, formation of
microemulsions, and wettability alteration leads to the movement of
residual oil through the pores of the core and forms an oil bank at the
flood front. The formation of oil bank at the flood front can be seen from
the oil saturation map shown in Fig. 9 (b). It can be seen from the figure
that there exists a region with higher oil saturation at the flood front
followed by a region with lower oil saturation. This flood front is pushed
towards the outlet after the injection of surfactant slug is followed by
chase water flooding. Fig. 9 (c) shows that the region behind the sur­
factant slug has very low residual oil saturation and Fig. 9 (d) shows the

Table 2
Set of parameters for history matching.
Parameters Initial Lower Upper History
value limit limit matched value

SwCon 0.203374 0.2 0.3 0.21975

SoRes 0.365511 0.3 0.4 0.306
KroCon 0.9 0.1 1 0.748
KrwRes 1 0.1 1 0.928
Nw 3 2.5 5 4.085 Fig. 8. Production profile of history matched simulation model.
No 3 2.5 5 2.06
WettingInterpolator 2 4.9 0.1 0.604
NonwettingInterpolator 2 4.9 0.1 4.708

6
A. Kumar and A. Mandal Journal of Petroleum Science and Engineering 192 (2020) 107333

Fig. 9. Oil saturation map of core (a) before the injection of surfactant slug, (b) after injection of surfactant slug, (c) during chase water flooding, (d) at the end
of flooding.

Fig. 10. Surfactant concentration map of the core (a) before the injection of surfactant slug, (b) after injection of surfactant slug, (c) during chase water flooding, (d)
at the end of flooding.

7
A. Kumar and A. Mandal Journal of Petroleum Science and Engineering 192 (2020) 107333

core had an average residual oil saturation of 21% at the end of the
flooding sequence.
Fig. 8 also shows the concentration of surfactant at the inlet and
outlet of the core during the flooding sequence. It can be seen from the
figure that the increase in oil production had occurred after 29 min of
injection of surfactant slug, concurrent to the arrival of the surfactant
slug at the outlet of the core. This signifies that the increase in the oil
production had occurred due to the presence of surfactant in the system.
It can also be seen from the figure that the surfactant concentration at
the outlet is lower than the surfactant concentration at the inlet. This
loss of the surfactant concentration occurs due to the adsorption of
surfactant in the core (Belhaj et al., 2020; Kumar and Mandal, 2019a).
The concentration maps of the surfactant in the core at different stages
of the flooding sequence have been shown in Fig. 10. It can be seen from
Fig. 10 (a) and (b) that before the injection of surfactant slug, the con­
centration of surfactant in the core was zero, which increases after the
injection of the surfactant slug. It can also be seen from Fig. 10 (b) that
the concentration of surfactant molecules at the flood front is lower than
the injected surfactant concentration. This reduction of surfactant con­
centration occurs due to simultaneous occurrence of the phenomenon of
adsorption and diffusion of surfactant molecules. The adsorption of
surfactant molecules occurs excessively at the flood front as the sur­
factant slug interacts with virgin rock surface. Further reduction of
surfactant concentration at the flood front occurs due to the diffusion of
surfactant molecules into the brine solution ahead of the flood front.
Fig. 10 (c) shows the surfactant concentration map during chase water
flooding, where it can be seen that the surfactant concentration at the
mid-section of the core is more than the front and rear sections of the
core. The front sections of the core had significantly more adsorption
leading to reduction of surfactant concentration, whereas the adsorption
phenomenon had reached an equilibrium at the mid-section of the core.
This causes a reduction in further loss of the surfactant from the injected
slug. The surfactant concentration at the rear section is low due to the
injection of chase water flooding, which causes the desorption of
adsorbed surfactant molecules into the aqueous phase. This desorption
of surfactant can also be seen from Fig. 10 (d) where the surfactant
molecules have mostly desorbed at the end of the flooding sequence.
4.5. Numerical optimization of chemical slug
The optimization of chemical injection scheme is required before its
application as an efficient EOR agent that gets the most oil recovery from
pilot tests and field applications. The adjustment of chemical slug in­
cludes changing parameters such as surfactant concentration in the
injected slug, size of injected slug, and injection flow rate of slug
(Sulaiman and Lee, 2012). The changes made to these parameters affect
the oil recovery by affecting the capillary forces acting in the reservoir
and retention of surfactant in the system. The values of parameters that
were varied to study their respective effects has been shown in Table 3.
4.5.1. Effect of surfactant concentration
The surfactant concentration in the injected slug is the most impor­
tant parameter that needs to be optimized due to its CMC. Injection of
surfactant at concentration lower than its CMC will lead to insignificant
flooding efficiency of the injected slug. Injection of chemical slug with
high surfactant concentration will lead to excess cost of operation.
Adsorption of surfactant on the reservoir rock is another factor that leads
to reduction of surfactant concentration in the injected slug and subse­
quently leading to reduction of efficiency of the injected slug. Fig. 11
shows the production profile of simulation runs with variation of the
surfactant concentration in the injected slug. The cumulative oil re­
covery of the respective cases has been shown in Table 3. It can be seen
from the figure that continuing with brine flooding, without the injec­
tion of surfactant slug, have negligible increment in oil recovery.
However, injecting surfactant at concentration lower than its CMC also
has similar insignificant increment in oil production. It can be seen from
the figure that injecting chemical slug with surfactant concentration
lower than its CMC causes a marginal increment of oil recovery over the
brine flooding. However, injecting the surfactant at its CMC is also not
recommended as it does not lead to maximum oil recovery due to the
loss of surfactant to adsorption on the rock surface. The surfactant
concentration at inlet and outlet of the simulation models are shown in
Fig. 12. It can be seen from the figure that the surfactant concentration at
the outlet has reduced for all models. However, the model with injected
surfactant concentration at CMC (50 ppm) has reduced below CMC at
the outlet, leading to its lower oil recovery in comparison to oil recovery
from simulation models with higher surfactant concentration in the
injected slug. The reduced efficiency of injected chemical slug with
surfactant at its CMC can also be seen from Fig. 13, where the loss of
surfactant had caused the IFT to increase at the outlet. Thus, the injected
slug must contain the surfactant concentration greater than its CMC.
However, greater surfactant concentration may not always lead to
greater oil recovery. This can also be seen from Table 3, where injection
of surfactant solution at 100 ppm had more oil recovery in comparison
to the base case of injection of 195 ppm. The lower oil recovery from the
model with injection of 195 ppm is caused due to increase in IFT be­
tween the surfactant and crude oil at higher concentration. This increase
in IFT is caused due to extraction of surfactant molecules from the oil-

Table 3
Design of parametric variation and result.
Run Parameters Cumulative oil
No. recovery (%
Surfactant Injected slug Injection rate
OOIP)
concentration volume (PV) (mL/min)
(ppm)

Base Case
1 195 0.3 0.2 73
Variation of surfactant concentration
2 0 0.3 0.2 58
3 25 0.3 0.2 58
4 50 0.3 0.2 73
5 100 0.3 0.2 75
Variation of injected slug volume
6 195 0.5 0.2 76
7 195 1.0 0.2 83
Variation of injection rate
8 195 0.3 0.05 60
9 195 0.3 0.1 71
Fig. 11. Production profile of simulation models with varying surfactant
10 195 0.3 0.3 79
concentrations.

8
A. Kumar and A. Mandal
Fig. 12. Surfactant concentration at inlet and outlet of simulation models with
varying surfactant concentrations.
Fig. 13. IFT between the injected slug and crude oil at inlet and outlet of
simulation models with varying surfactant concentrations.
water interface into the oleic phase (Cort� es et al., 2018). Thus, the
reduction of surfactant molecules at the oil-water interface causes the
increase of IFT. This relation of IFT with oil recovery can also be seen
from Fig. 13, where the lowest IFT at the outlet is obtained for model
with injection of 100 ppm surfactant concentration, thus leading to
maximum oil recovery.
4.5.2. Effect of injected slug volume
The effect of variation of the injected slug volume has been shown in
Fig. 14. It can be seen from the figure that increase in injected slug
volume had led to increase in the cumulative oil recovery from the
model. The injection of lower slug volume leads to lower oil production
as the surfactant molecules are adsorbed at the virgin rock surface, thus
the surfactant concentration in the injected slug is continuously reduced
with the movement of flood front towards the outlet. This reduction of
surfactant concentration at the outlet has been represented in Fig. 15. It
can be seen from the figure that the surfactant concentration at the
outlet was higher for the simulation model with greater injected slug
volume. The increase of injected slug volume led to greater surfactant
concentration at the outlet as the loss of surfactant is reduced with
additional injection of chemical slug due to the existence of adsorption
maxima for surfactant. Thus, the loss of surfactant was reduced and
9
Journal of Petroleum Science and Engineering 192 (2020) 107333
Fig. 14. Production profile of simulation models with varying injected
slug volume.
Fig. 15. Surfactant concentration at inlet and outlet of simulation models with
varying injected slug volume.
more surfactant reached the outlet leading to increase in the oil recovery
of the model. However, greater injected slug volume also leads to in­
crease in cost of the injection operation. Thus, the selection of volume of
injected slug is mostly dependent on several other relevant factors such
as cost, extent of reservoir, injection pattern, etc.
4.5.3. Effect of injection rate
The injection rate is another important parameter that is optimized
as greater injection rate leads to early breakthrough of the injected slug.
However, the increase of injection rate also requires additional opera­
tional facilities which may lead to increase in the operational cost of the
injection process. Fig. 16 shows the production profile of the simulation
models with varying injection rates. It can be seen from the figure that
the increase of injection had led to increase in the cumulative oil pro­
duction. It can also be seen that the increase in oil production occurred
earlier for model with the highest injection rate and the model with
lowest injection rate of 0.05 mL/min had the increase of oil production
after injection of around 3 PV of injected slug. The effect of increase in
injection rate can also be seen from Fig. 17, where the simulation model
with the highest injection rate of 0.3 mL/min causes the surfactant to
A. Kumar and A. Mandal Journal of Petroleum Science and Engineering 192 (2020) 107333

Table 4
Cumulative oil recoveries of simulation models with varying values of tested
parameters.
Run Parameters Cumulative oil
No. recovery (%
Surfactant Injected slug Injection rate
OOIP)
concentration volume (PV) (mL/min)
(ppm)

1 50 0.3 0.1 59
2 50 0.3 0.2 73
3 50 0.3 0.3 78
4 50 0.5 0.1 66
5 50 0.5 0.2 79
6 50 0.5 0.3 81
7 50 1 0.1 76
8 50 1 0.2 83
9 50 1 0.3 87
10 100 0.3 0.1 68
11 100 0.3 0.2 75
12 100 0.3 0.3 79
13 100 0.5 0.1 72
14 100 0.5 0.2 79
15 100 0.5 0.3 82
16 100 1 0.1 75
17 100 1 0.2 85
Fig. 16. Production profile of simulation models with varying injection rate.
18 100 1 0.3 91
19 195 0.3 0.1 71
20 195 0.3 0.2 73
21 195 0.3 0.3 78
22 195 0.5 0.1 73
23 195 0.5 0.2 76
24 195 0.5 0.3 83
25 195 1 0.1 74
26 195 1 0.2 83
27 195 1 0.3 93

with 195 ppm of surfactant concentration was injected with the injec­
tion rate of 0.3 mL/min. However, by injecting chemical slug with 100
ppm of surfactant concentration, 91% OOIP can be recovered which
may be more economical due to lower requirement of surfactant.
Similarly, more than 85% OOIP can be recovered by either reducing the
injection rate to 0.2 mL/min or reducing the surfactant concentration in
the injected slug to 50 ppm. Thus, factoring in the operating expenditure
(OPEX) of the injection operation and cost of produced crude oil, the
values of parameters should be selected to maximize the oil production
from the reservoir.

Fig. 17. Surfactant concentration at inlet and outlet of simulation models with
varying injection rate.
reach the outlet after injection of 0.5 PV of fluid and the decrease of
injection rate causes the breakthrough to occur at later stage. However,
a very high injection rate cannot be selected as it causes an increase of
pressure in the reservoir, which had to be kept below the fracture
pressure of the reservoir.
4.5.4. Optimized chemical slug
The study of effect of different parameters showed that the oil re­
covery is affected by variation of every parameter. However, each
parameter does not have similar effect on the increase in the oil recovery
efficiency and selecting the highest value for the parameters may not be
economical. Thus, a comparison of all simulation models with the
combinations of different values of the parameters is required to get the
optimized chemical injection slug. However, the values of parameters
that had insignificant effect on the oil recovery efficiencies, such as
lower surfactant concentrations and lower injection rates were not
considered for comparison. Table 4 shows the cumulative oil recovery of
27 simulation models with the combinations of the values of the tested
parameters. It can be seen from the table that the highest oil recovery of
93% OOIP was obtained for the model in which 1 PV of chemical slug
5. Conclusions
A core flooding experiment with injection of zwitterionic surfactant
slug was simulated using CMG-STARS simulator. The history matching
of relative permeability curve and its interpolation parameters were
done to validate the model which most closely represents the experi­
mental core flooding. The production profile of the validated model,
determined after the history matching, had a very low error of 6% with
the experimental production profile. The history matched model was
further used for optimization of injected chemical slug. The optimized
chemical slug was obtained by varying the parameters such as the sur­
factant concentration in the injected slug, volume of injected chemical
slug, and injection rate of chemical slug. Each tested parameter had
different effect on the oil recovery efficiency of the chemical slug and
cumulative oil production of more than 90% OOIP was obtained for
model with injection of 1 PV of chemical slug containing 100 ppm of
surfactant concentration with injection rate of 0.3 mL/min. However,
these values of parameters can change on the basis of required OPEX and
crude oil prices during the injection operation.
Declaration of competing interest
The authors declare no competing financial and commercial interest.

10
A. Kumar and A. Mandal
CRediT authorship contribution statement
Amit Kumar: Conceptualization, Methodology, Software, Investi­
gation, Visualization, Writing - original draft. Ajay Mandal: Visualiza­
tion, Writing - review & editing, Supervision.
Acknowledgement
The authors would like to thanks the Department of Petroleum En­
gineering, IIT(ISM), Dhanbad for providing the facilities to carry out the
required testing of the samples.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.petrol.2020.107333.
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