SPE-174572-MS

Comprehensive Effects on the Propagation of Surfactant and Polymer Flow

in Carbonate Porous Media
Dongqing Cao, Jinxun Wang, Ming Han, and Amar J. Alshehri, Saudi Aramco

Copyright 2015, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Enhanced Oil Recovery Conference held in Kuala Lumpur, Malaysia, 11–13 August 2015.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
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Abstract
Chemical propagation in an Enhanced Oil Recovery (EOR) process involves various fluid-rock interac-
tions, such as adsorption, dispersion, inaccessible pore volume (IPV), viscous fingering and chromato-
graphic separation. In this paper, comprehensive effects on the propagation of surfactant and polymer in
carbonate porous media were investigated experimentally and analytically in order to study the mecha-
nism and quantify the contribution of each effect.
Single phase flow tests of surfactant, polymer and surfactant-polymer mixture were conducted on
reservoir carbonate core plugs at reservoir conditions (high temperature and high salinity). A convection-
dispersion model was used to interpret the effluent chemical concentration profiles. The effect of different
factors on chemical propagation was taken into account in the model. The dynamic adsorptions of two
amphoteric surfactants at 2,000 mg/L concentration were 0.21 and 0.17 mg/g-rock, respectively. The
dynamic adsorptions of a sulfonated polymer at 2,000 and 5,000 mg/L were 0.11 and 0.17 mg/g-rock,
respectively. Surfactant and polymer were co-injected to evaluate their competitive adsorption, and the
surfactant adsorption was reduced by about 50%. The dispersion coefficient of the chemicals in carbonate
cores was in the magnitude of 10–3 cm2/s. Both dispersion and adsorption caused chemical concentration
reduction during the propagation in porous media. IPV and viscous fingering occurred during polymer
injection or the subsequente water injection. IPV affected the calculation of adsorption/desorption process
of polymer injection and IPV value cannot be solely determined by the model simulation. Chromato-
graphic separation took place in the surfactant/polymer co-injection scheme, which was predicted by the
model as well. The model results were compared with the chemical flood simulator of UTCHEM.
Introduction
Chemical Enhanced Oil Recovery (EOR) technologies have been studied and applied in the field for
decades (Lake 1989; Green and Willhite 1998). Most of the field applications were implemented in
sandstone reservoirs (Clark et al. 1993; Wang et al. 1998). Recent years, great interests have been shifted
towards carbonate reseroirs (Tabary et al. 2009; Han et al. 2012; Levitt et al. 2012; Han et al. 2013). In
a Chemical EOR process such as polymer and/or surfactant EOR processes, chemicals are injected into
the porous media and interact with the rock surfaces either sandstone or carbonate reservoirs. Consider-
able efforts have been made to study the chemical EOR fluid flow in porous media (Dauben et al. 1967;
2 SPE-174572-MS

Bae et al. 1977; Lawson 1978; Cohen et al. 1986; Wang et al. 2000; Liu et al. 2003; Solairaj et al. 2012;
Zhou et al. 2012; Wang et al. 2015). The following discussion provides an overview of several factors that
impact a chemical EOR process including fluid-rock interactions, dispersion and reservoir heterogeneity.
When chemicals flow through reservoir cores, part of the chemicals adsorb onto the rock surfaces
owing to the chemical-rock interaction that results in the decreasing the chemical concentration. There-
fore, chemical adsorption is an important parameter for both technical and economic concerns. Another
important factor is hydrodynamic dispersion which refers to the macroscopic outcome of the mixing of
one fluid in a second miscible fluid during flow through porous media and includes mechanical dispersion
and molecular diffusion. Molecular diffusion is mainly caused by concentration gradient and is usually
much smaller than mechanical dispersion. Microscopic heterogeneities of reservoir rock result in varia-
tions in fluid velocity and some additional mixing known as mechanical dispersion. Dispersion dilutes the
chemical slug and causes the slug to lose its effectiveness. Viscous fingering occurs when a more viscous
fluid is displaced by a less vicious fluid. The unfavorable viscosity ratio makes finger-shaped intrusions
of the displacing fluid to the displaced fluid zone. The inaccessible pore volume (IPV) is the volume of
pore space that the polymer cannot enter. Polymer molecules are much larger than those of water. When
polymer is injected into the reservoir, it does not invade all the pores and therefore propagates faster than
water in the reservoir. Chromatographic separation may occur when polymer is injected with other
chemicals.
These factors are coupled with each other during the chemical propagation in the reservoir and that
complicates the fluid-flow process. Coreflooding method is a useful tool to investigate these factors. Zhou
et al. (2012) and Wang et al. (2015) have investigated the dynamic adsorption of surfactant and polymer
on carbonate core plugs from Saudi Arabia. The studies showed positive results for several surfactant and
polymer candidates at reservoir conditions. Additional work is presented here based on the previsous
studies using both experimental and analytical methods.
In this paper, fluid-flow of surfactants and polymers in carbonate reservoir core plugs was studied. Five
coreflooding tests were conducted at reservoir conditions. The dynamic adsorption was then calculated
from effluent concentrations. The convection-dispersion model was used to interpret the experiment
effluent concentration profile curve. The dispersion, adsorption, inaccessible pore volume and chromato-
graphic separation were estimated.
Methodology
Brines and chemicals
Two types of brine were used in the tests. One was synthetic connate water with total dissolved solids
(TDS) of 229,870 mg/L, which was used to saturate dry core samples. The other brine was the synthetic
seawater with 57,670 mg/L TDS. It was used as the injection water and to prepare the chemical solutions.
Table 1 shows the ion compositions of the two brines.

Table 1—Composition of connate water and QSW

ⴙ
Iron Na , mg/L Ca2ⴙ, mg/L Mg2ⴙ, mg/L Clⴚ, mg/L HCO3ⴚ, mg/L SO4ⴚ, mg/L TDS, mg/L

Connate water 66,052 19,008 2,239 140,580 384 1,620 229,870

Seawater 18,300 650 2,110 32,200 120 4,290 57,670

Surfactants and polymers were used as the chemicals of the chemical EOR process. The surfactants
were amphoteric surfactant OCT-1 and OCT-4 with 50% purification, provided by Oil Chem. The
polymers were sulfonated polyacrylamide PST-10 and PST-9 with 89.53% purification, provided by SNF
Floerger. All these chemicals showed good compatibility with the two brines of interest.
SPE-174572-MS 3

Core plugs
Carbonate reservoir core plugs were used in the coreflooding tests. Gas permeability, pore volume and
porosity of the core plugs were determined by routine core analysis. The core samples were saturated with
connate water under vacuum. The saturated core plugs were then submerged in the connate water to
establish the ionic equilibrium between rock and brine. Table 2 gives the detailed information of the core
plugs.

Table 2—Core plug and test information

Group Test No. Core ID Length, cm Diameter, cm Porosity Air perm., md Chemical, wt.%

Surfactant 1 328 4.430 3.780 0.271 148 0.2% OCT-1

2 65 3.897 3.775 0.248 425 0.2% OCT-4
Polymer 3 96 4.007 3.775 0.230 582 0.2% PST-10
4 58 3.785 3.774 0.256 660 0.5% PST-10
Co-injection 5 135 4.424 3.768 0.275 445 0.2% surfactant⫹0.2% polymer

Coreflooding procedures
Single-phase flow tests of chemical solution were conducted on carbonate core plugs at 100˚C and
3100 psi pore pressure. A FDES-645 coreflooding system from Coretest System with horizontally
oriented core holder was used for the coreflooding tests. A Quizix pump drived the injection fluids in
piston accumulators into the core samples. The confining pressure and pore pressure were set by the
computer control system. The injection pressure, differential pressure and flow rate were recorded
automatically. The produced fluid was collected by the fractional collector at constant volume or time
interval. The core flooding test procedure is as follows,
1. Fill the accumulators with seawater and chemical solutions. Pre-flush the lines and fill the lines
with seawater.
2. Load the core sample into core holder and connect the lines. Set the confining pressure of the core
holder as 1,400 psi. Set the back pressure and temperature. Inject the seawater at 1.0 cc/min to set
up the pore pressure during heating. The confining pressure will increase automatically.
3. Inject the surfactant or polymer solution at 0.5 cc/min. Around 5 pore volumes (PV) of chemical
solution was injected to ensure the equilibrium of the flow. Collect the produced fluid in 10 cc
tubes by fractional collector at constant time interval.
4. Inject seawater at flow rate of 0.5 cc/min after chemical slug. The injected seawater flushes out the
mobile chemical solution in the pore space, leaving only absorbed chemicals in the core. Collect
the produced fluid in tubes by fractional collector at constant time interval.
Determination of effluent concentration
The concentration of the effluent in the tubes from the coreflooding test was measured by TOC-VCPH,
made by Shimadzu, Japan, and titration method. In the TOC method, the total carbon (TC) concentration
was first measured by total combustion of the samples. By subjecting the oxidized sample to the sparging
process, the inorganic carbon (IC) concentration in the sample was detected. The total organic carbon
(TOC) concentration was then calculated by subtracting the IC concentration from the obtained TC
concentration. The polymer and surfactant are organic. The TOC is linear to the concentration of polymer
or surfactant at very low concentration. A calibration curve was first obtained by determining the TOC
values of several known concentration solutions. The concentration of the effluent samples was calculated
by interpolation on the TOC calibration curve. An effluent concentration-injection pore volume curve was
then plotted.
4 SPE-174572-MS

In the titration method, a two-phase method was used to determine the effluent surfactant concentra-
tion. The amphoteric surfactant was first converted into cationic surfactant by acidifying process with
HCl. Excess anionic surfactant sodium dodecyl sulfate (SDS) was then added to the test sample to
neutralize the positive charge of the test sample. The amount of excess anionic surfactant SDS was then
quantitatively determined by a titration with standard cationic surfactant Hyamine-1622 in the presence
of dimidium bromide and chloroform. The concentration of the test sample was determined based on
Hyamine-1622 used in the titration.

Determination of dynamic adsorption

The term ‘adsorption’ could be referred to as the term ‘retention’ since there might be physical
retention in a core. We will use ‘adsorption’ in the following discussion for the possible adsorption/
retention process. The calculation of dynamic adsorption was conducted in two steps. First, the amount
of chemical adsorption during the chemical injection is obtained. In this process, the chemical concen-
tration in the core plug increases with the chemical injection, so does the chemical adsorption. After plenty
of chemical injection, the chemical concentration and adsorption will reach equilibrium. Second, the
chemical desorption during the subsequent water injection is obtained. The injection water decreases the
chemical concentration in the core plug. Desorption of chemical may occure during this process. The
dynamic adsorption is the total adsorption minus by the desortion.
Adsorption was calculated from the frontal region of effluent concentration curve during the chemical
injection by Eq. (1). It was assumed that the entire pore volume was uniformly occupied by injected
chemical after the effluent chemical concentration reached to a constant value. The chemical absorbed was
the chemical injected minus by the total chemical produced and those left in the pore space.
(1)

where minj is the mass of chemical injected into the core, mg; Vinj is chemical injection volume, ml;
Cinj is chemical injection concentration, mg/L; mprod is the chemical produced during the chemical
injection period, mg; Vi is the volume of effluent in ith tube, ml; Ci is the concentration of effluent in ith
tube, mg/L; mpore is the chemical left in the pore space, mg; PV is pore volume, ml; ⌫ads is the chemical
adsorption on unit mass of rock during chemical injection period, mg/g-rock; and mcore is the mass of dry
core plug, g.
Desorption of chemical was calculated from the tail concentration curve during the subsequente water
injection by Eq. (2). Assuming the chemicals produced at the end of the subsequente water flooding were
negligible, the chemical desorpted is the chemical produced minus the chemical left in the pore space.
(2)

where ⌫des is the chemical desorption from unit mass of rock during subsequente water injection,
mg/g-rock; mprod’ is the chemical produced during the subsequente water injection, mg.
The dynamic adsorption during the whole process was Eq. (3).
(3)

where ⌫dyn is the chemical dynamic adsorption during the whole injction, mg/g-rock.

Model for surfactant flow

The transport of a chemical solution in brine saturated porous media can be described by the
convection-dispersion model. The flow in the core sample was one-dimensional and single phase. The
fluid was assumed to be incompressible. The surfactant and polymer were assumed to be not volume-
occupying (Sorbie et al. 1987; Vossoughi et al. 1984; Dang et al. 2011).
SPE-174572-MS 5

For the surfactant flow, the adsorption and dispersion need to be included in the model which can be
written as:
(4)

where V is the superficial velocity at position x, cm/s; A is cross section area, cm2; ⌬t is time interval,
s; C is concentration of chemicals, g/cm3; ␸ is porosity, fractional; ␳ is the density of dry core sample,
g/cm3; K is dispersion coefficient, cm2/s; q is the source or sink flow rate, cm3/s; ⌫ is the adsorption of
chemical, g/g.
Assuming the adsorption was a function of concentration C only, the dimensionless form of the above
equation was Eq. (5), assuming no source or sink.
(5)

where tD is time in PV’s; X is fractional length; CD is concentration as a fraction of injection

concentration; Npe is Peclet number; FR is retardation number. The dimensionless forms are given by Eq.
(6).
(6)

Model for polymer flow

For the polymer flow, the molecule of polymer was usually large and cannot enter some small pores
in the core sample. So there would be an inaccessible pore volume (IPV) for polymer. The effective
porosity of polymer was noted as ␸p. The model would change to Eq. (7). (Sorbie et al. 1987; Vossoughi
et al. 1984)
(7)

where f is ratio of polymer effective porosity to total porosity; ␸p is effective porosity of polymer.
When the viscosity of displacing fluid was higher than the displaced fluid, the flow could be described
by the model above. But for the subsequente water injection, the viscosity ratio was not favorable and
viscous fingering should be taken into account. To macroscopically describe the viscous fingering, a
fractional flow term was introduced into the convection term in the model. This ensured that the finger
zone would grow linearly with time t, rather than with t1/2 as in pure dispersion (Blunt and Christie 1994).
The fractional flow model assumed the polymer solution and brine are two different phases, and the flow
was analogous to two-phase flow. The fractional flow of polymer phase was given by certain mixing rule
between polymer and water. The model is as Eq. (8).
(8)

where Sp is saturation of the assumed polymer phase, fractional, given by Sp⫽C/Co; fp is fractional
flow of the assumed polymer phase, fractional, given by fp⫽Qp/Q.
The fractional flow of polymer was given by expression of Eq. (9). (Vossoughi et al. 1984)
(9)

where S is the volume fraction of injection polymer solution, fractional; M is viscosity ratio of injection
polymer solution to brine; r is the parameter for the mixing rule of water and polymer
Boundary condtion and solving process
In the coreflooding test, the core was horizontal oriented. The inlet end boundary was a constant flow
rate injection of chemical solution or brine. The literature reported that the Dirichlet boundary condition,
6 SPE-174572-MS

which specifies the chemical concentration at the inlet, could result in the mass balance error in the
calculation (Brigham 1974). So the mix boundary condition was used, which gave constant amount of
chemical flow into the inlet. The outlet end boundary was a constant flow rate of effluent. Assuming there
was no dispersion at the outlet face of the core sample, the Neuman boundary condition was applied at
the outlet boundary (Camilleri et al. 1987).
(10)

Before the chemical injection, the core was saturated with brine, so the initial condition was
(11)

The equations were solved numerically by the Crank-Nicolson finite difference method. For each time
step, the concentration of chemical in each cell was obtained from the concentration value of former time
step by solving one linear system of equations. The input parameters for the calculation were routine core
parameters, injection slug information and adsorption parameters. The unknown parameters were those
associated with dispersion, IPV and viscous fingering. Conduct times of runs of the calculation with
different unknown parameters and get the effluent concentration profile curve that fits best with the
experimental results.
Results and Discusstion
Experimental results
Three groups of single phase flow tests were conducted at reservoir conditions: 1) surfactant injection, 2)
polymer injection, and 3) surfactant/polymer (SP) co-injection. Two surfactants were used in Group 1 at
2,000 mg/L as shown in Table 2. One polymer was used in Group 2 tests at two different concentrations
of 2000 mg/L and 5,000 mg/L. One SP co-injection test was conducted using a mixture of 2000 mg/L
surfactant and 2,000 mg/L polymer.
By the material balance between the chemical injection and production, the dynamic adsorption was
calculated as in Table 3. For surfactant OCT-1 and OCT-4, the dynamic adsorption at reservoir condition
was 0.208 and 0.169 mg/g-rock. Surfactant adsorption depends to a large extent on the type of surfactant,
the mineralogical characteristics and surface charge of the rock. The carbonate rock is usually positively
charged in water near neutral pH. Cationic surfactants exhibit significantly less adsorption on carbonate
minerals than anionic surfactants (Ahmadall et al. 1993). Both surfactants in this study were amphoteric,
and showed low adsorption on the carbonate rock. A desorption process was also observed during the
subsequente water injection (Zhou et al. 2012). The term ‘adsorption’ could be referred as the term
‘retention’ since there might be physical retention in a core. The physical retention may or may not exist
in a given experiment and detection of it may be very difficult.

Table 3—Dynamic adsorption results

Chemical injection volume, Subsequente water injection
Test number PV volume, PV ⌫ads, mg/g-rock ⌫des, mg/g-rock ⌫dyn, mg/g-rock

Test 1 4.75 4 0.2760 0.0678 0.2082

Test 2 5 4 0.2421 0.0735 0.1686
Test 3 5.3 4.7 0.1436 0.0348 0.1088
Test 4 5 5 0.1601 ⫺0.0125 0.1726
Test 5 Total 5 7 0.1440 ⫺0.0168 0.1607
Test 5 Surfactant 5 7 0.1704 0.0885 0.0820
SPE-174572-MS 7

The dynamic adsorptions of 2000 and 5000 mg/L polymers were 0.109 and 0.173 mg/g-rock,
respectively. If we assume that the pore volume is fully occupied by the polymer solution, the polymer
desorption during the subsequente water injection is negative for Test 4 as shown in Table 4. So there
should be an inaccessible pore volume for the polymer solution. When calculating the surfactant left in
the pore, mpore, the pore volume should be the polymer accessible pore volume. This will be discussed in
next section. Polymer retention includes adsorption, mechanical trapping, and hydrodynamic retention
(Willhite and Dominguez 1977). Usually, polymer adsorption is considered irreversible. However, the
retention could be reversible because small amounts of polymer could be removed from porous rock by
exposure to water or brine injection.

Table 4 —Parameters for model interpretation

Test number IPV ⌫ads, mg/g-rock ⌫des, mg/g-rock ⌫dyn, mg/g-rock Adsorption Desorption Npe

b d b d

Test 1 ⫺ 0.2760 0.0678 0.2082 100 0.1657 100 0.0406 10.0

Test 2 ⫺ 0.2421 0.0735 0.1686 100 0.1453 100 0.0441 8.0
Test 3 0.2 0.1357 0.0349 0.1007 100 0.1077 100 0.0422 6.8
Test 4 0.2 0.2893 0.1166 0.1726 100 0.08680 100 0.03490 7.5
Test 4 0.3 0.3538 0.1812 0.1726 100 0.10614 100 0.05436 7.7
Test 4 0.1 0.2247 0.0520 0.1726 100 0.06743 100 0.01560 7.6
Test 5 Surfactant ⫺ 0.1704 0.0885 0.0820 100 0.1022 100 0.0531 7
Test 5 Polymer 0.3 0.1096 0.0315 0.0781 100 0.0658 100 0.0189 7

Table 5—Fractional flow model parameters

Test No. r ␮p ␮w

Test 3 2 1.0 0.3

Test 4 40 1.2 0.3

For the SP co-injection scheme, the total SP adsorption was 0.161 mg/g-rock and the adsorption of
surfactant was 0.082 mg/g-rock. Assuming the total adsorption of polymer and surfactant mixture was
equivalent to the adsorption of surfactant if only surfactant is injected, the surfactant adsorption was
reduced by 48.2% due to the co-injection of polymer.
The breakthrough time for the two surfactant flow tests was at 0.8 PV and 0.7 PV. The polymer broke
through at 0.4 PV and 0.5 PV, which was a little earlier than the surfactants. The polymer could not enter
all the pores of the core, so it propagated faster and broke through earlier. This was also found in the SP
co-injection scheme.
Propagation of surfactant in porous media
The propagation of surfactant in porous media was simulated by the convection-dispersion model. The
effluent concentration profiles of the surfactant injection tests were fitted to determine the adsorption and
dispersion papameters.
The adsorption of surfactant was a key factor governing the convection-dispersion process. Trogus et
al. (1977) proposed a kinetic model. When the adsorption occurred rapidly as compared to convection and
dispersion, the model yielded to the Langmuir isotherm and could be written as follows (Dang et al. 2011).
(12)

where b and d are parameters for adsorption.

8 SPE-174572-MS

Both surfactant adsorption and desorption processes were described by the above model. By changing
the values of b and d, different amount of adsorption and desorption can be described. The parameter b
was assumed to be 100 in the following calculations. Based on the equation above and the experimental
adsorption and desorption results, the parameter d was calculated as shown in Table 4. In the Langmuir
model, the ratio of d to b was the maximum adsorption value ⌫max. In the two surfactant flow tests, the
maximum adsorption in adsorption and desorption process ranged from 0.5 mg/g-rock to 1.5 mg/g-rock.
The full set of transport parameters required to depict the surfactant flow includes flow rate (convec-
tion), dispersion, adsorption, as well as the injection slug information. By changing the only unknown
parameter Npe, the effluent concentration profile could be fitted. The input parameters for the calculations
are presented in Table 4 and the model simulation result of Test 1 is shown in Fig. 1. The dispersion
coefficient can be calculated by the Npe at the best fitting. The dispersion coefficients for the two
surfactant flow tests were 0.001214 and 0.001463 cm2/s, respectively.

Figure 1—Effluent concentration profile and model fitting result of Test 1 for surfactant OCT-1 of 2,000 mg/L.

Propagation of polymer in porous media

As shown in the experimental results, the inaccessible pore volume should be included in the propagation
of polymer. A typical value of 0.2 was selected for the interpretation of effluent concentration profile.
With the method described in the previous section, the adsorption, desorption and dynamic adsorption
were calculated as in Table 4. The parameters describing the polymer flow were all known except for the
dispersion coefficient Npe. By the fitting process, Npe of the two tests were 6.8 and 7.5. The dispersion
coefficients were 0.002383 and 0.001835 cm2/s, respectively.
The model simulation result of the 5,000 mg/L polymer injection test is shown in Fig. 2. The frontal
part of the effluent concentration was fitted well by the model. For the subsequente water injection, which
was water displacing polymer, the fitting was not good, especially for Test 4 with higher polymer
concentration. This may be because of the adverse mobility ratio between water and polymer. To fit this
concentration tail, viscous fingering was taken into account. Fig. 3 presents the simulation result including
viscous fingering. The concentration tail was fitted by the model with r, ␮p and ␮w of 40, 1.2 and 0.3,
respectively. But these values were physically unreasonable.
SPE-174572-MS 9

Figure 2—Effluent concentration profile and model fitting result of Test 4 for polymer PST-10 of 5,000 mg/L.

Figure 3—Effluent concentration profile and model fitting result of Test 4 for polymer PST-10 of 5,000 mg/L including fingering.

Propagation of SP system in porous media

For the SP co-injection scheme, we interpreted the effluent concentration profile of polymer and surfactant
separately. The concentration of polymer was the total concentration subtracted by surfactant concentra-
tion. Figs. 4 and 5 show the experimental and simulation results. The simulation results fit the experi-
mental data well. The dispersion coefficient was 0.001717 cm2/s, which was consistent with the early
results. Fig. 6 shows the concentration profile along the core plug at 1 PV injection. We can notice that
the polymer concentration was higher than the surfactant. Surfactant and polymer both were 2000 mg/L
at injection end. During the propagation in the cores, the two chemicals behaved quite differently. Polymer
flowed faster than the surfactant due to the IPV and had lower adsorption, which resulted in the
concentration difference along the core sample.
10 SPE-174572-MS

Figure 4 —Effluent concentration profile of surfactant and model fitting result of Test 5 for S/P co-injection.

Figure 5—Effluent concentration profile of polymer and model fitting result of Test 5 for S/P co-injection.
SPE-174572-MS 11

Figure 6 —Concentration profile along the core at 1PV S/P co-injection.

There is usually a synergy effect for the SP co-injection system. The co-injection does much more
favors on the oil recovery than the sum of individual injection does. But the chromatographic separation
makes the synergy between the two chemicals not as well as we imaged. Moreover, polymer and
surfactant interact with each other when they are mixed together. These interactions are usually concen-
tration dependent. The concentration difference during propagation may cause unpredictable results. So
it is necessary to estimate the chromatographic separation during the design of the co-injection project.

Discussion
Dispersion and adsorption The propagation of surfactant solution in porous media was mainly affected
by two factors, dispersion and adsorption. We performed several runs of model calculation, in which
different factors were considered separately. Table 6 shows the parameters for the calculations (Ex.1). A
5.0 PV surfactant slug was injected into a 4 cm long core sample. The adsorption and dispersion were
equivalent to those in Test 1. Fig. 7 shows the effluent concentration profiles of different runs.

Table 6 —Example of convection-dispersion model

Adsorption Desorption L, cm D, cm ␸ ␳, g/cm3 C, wt.% Chemical slug, PV Npe

b d b d

Exa. 1 100 0.15 100 0.03

Exa. 2 1000 0.375 1000 0.075 4.00 3.78 0.25 2.01 0.2 5 10
Exa. 3 10 0.1275 10 0.0255
12 SPE-174572-MS

Figure 7—Example of convection-dispersion model.

The blue line was the base case with no dispersion and adsorption. The flow was piston-like and the
chemical breakthrough occurred at exact 1.0 PV of fluid injection and the subsequente water breakthrough
occurred at 6.0 PV of injection. The red line was the case taking into account of dispersion. Npe was the
ratio of convection to dispersion during the propagation of chemical in porous media. The dispersion of
chemical resulted in a transition zoon at the flow front, in which the concentration of chemical varied from
zero to initial injection concentration, rather than a shock as in the base case. Meanwhile, the chemical
propagated faster by the dispersion than the case without dispersion, which resulted in earlier break-
through than the base case. The adsorption also has influence on the propagation of chemical. Unlike
dispersion, the adsorption of surfactant resulted in the loss of chemical and retarded the travel of
concentration wave. This is shown by the right shift of the effluent concentration profile (green line).
Furthermore, when the reversible adsorption was included in the model, the effluent concentration profile
would shift further to the right. But the total area under the curve was the same for the two conditions.
Fig. 8 presents the concentration profiles along the core at 1.0 PV of chemical injection for the four
different simulation scenarios mentioned above. After 1.0 PV of injection, the concentration of chemical
at different part of the core was lower than the injection concentration. The dispersion diluted the injected
chemical and adsorption lowered the concentration even further. When chemical EOR is applied, the size
of the chemical slug is usually less than one pore volume of the reservoir. Therefore, the dispersion and
adsorption of chemical need to be carefully considered in the pilot design.
SPE-174572-MS 13

Figure 8 —Concentration profile along the core at 1PV chemical injection.

It was reported that the type and shape of the adsorption curve had controlling influences on the
transport behavior in a single phase flow (Trogus et al. 1977; Wu et al. 1997). With the above same
example, the effect of adsorption on the chemical propagation was analyzed by changing the Langmuir
parameters, as shown in Table 6 (Ex. 2 and Ex. 3). Fig. 9 shows the calculated effluent concentration
profiles for the three cases with different adsorption parameters. These three examples had the same
adsorption value at chemical concentration of 2,000 mg/L. But the maximum adsorptions were different,
which were 1.5, 0.375 and 12.75 mg/g-rock. It was noticed that the effluent concentration profile became
steeper when the maximum adsorption was lower. And the decreasing of maximum adsorption had larger
effect on the shape of the effluent concentration profile than the increasing of maximum adsorption.

Figure 9 —Fitting results for different maximum adsorption.

14 SPE-174572-MS

IPV Besides the dispersion and adsorption, the polymer flow in the reservoir was additionally affected
by the IPV. The change of IPV could result in the change of adsorption and desorption, but not dynamic
adsorption. In the model fitting process of the polymer flow, the value of IPV was hypothetical. To
estimate the effect of IPV, another two values, 0.3 and 0.1, were used to calculate the adsorption and
desorption as shown in Table 4. Model simulations were performed for Test 4 using three different IPV
values of 0.1, 0.2 and 0.3. As shown in Fig. 10, the effluent concentration profiles were very close, andthe
three lines overlap as one line.

Figure 10 —Fitting results for different IPV.

The term f·(1⫹⭸⌫/⭸C·␳/␸p) in Eq. (7) was usually referred to as retardation factor FR. There were two
competing effects on the retardation factor: retention, tending to make FR ⬎ 1, and inaccessible pore
volume, which tended to make FR ⬍ 1. The increasing of retention could be cancelled by the increasing
of inaccessible pore volume. Therefore, similar fitting results might be obtained with different combina-
tions of retention and inaccessible pore volume. The IPV value cannot be solely determined by this model
simulation method. Traditionally, IPV is experimentally determined by the breakthrough time difference
between polymer and tracer. This is based on the assumption of the absence of polymer adsorption.
Superposition model based on the analytical solution of flow equation is another option. Similarly,
elimination of adsorption and properly estimated dispersion are critical to this method (Pancharoen et al.
2010).
Comparasion with UTCHEM The modeling results in this study were compared with those by
UTCHEM. Fig. 11 shows the comparison results for Test 1. Two runs of UTCHEM were conducted, using
the adsorption and dynamic adsorption as input respectively. For the run using dynamic adsorption data,
the total adsorption is the same with our model fitting. But UTCHEM uses an irreversible adsorption
model, the adsorption-desorption process of the test cannot be described. For the run using adsorption
data, the frontal part of the effluent concentration profile slightly shifts to the left side of our model fitting.
Theoretically, the two lines should be the same. This may be caused by the model assumption and solving
process of the two methods.
SPE-174572-MS 15

Figure 11—Comparison between the model in this study and UTCHEM.

Conclusions
1. The dynamic adsorptions of two amphoteric surfactants at 2,000 mg/L on carbonate core samples
were 0.208 and 0.168 mg/g-rock. The dynamic adsorptions of polymer PST-10 at 2,000 and 5,000
mg/L were 0.109 mg/g-rock and 0.173 mg/g-rock, respectively. The surfactant adsorption was
reduced by about 50% for the SP co-injection scheme. The adsorption during chemical injection
and the desorption during subsequente water injection were also calculated.
2. The convection-dispersion model was used to interpret the experimental effluent concentration
profile. The Langmuir type isotherm was used to describe the adsorption-desorption process. For
polymer injection, IPV and viscous fingering were also included. The model was solved numer-
ically by the Crank-Nicolson finite difference method, and the results were compared with those
by UTCHEM.
3. The dispersion coefficient of surfactant in carbonate cores was determined in the order of 10–3
cm2/s. Both dispersion and adsorption caused chemical concentration reduction during the prop-
agation in the reservoir. The adsorption has a controlling influence on the chemical flow in porous
media.
4. Inaccessible pore volume needs to be taken into account for the adsorption and desorption
calculations in the presence of polymer. Different IPV resulted in different adsorption and
desorption values, and very close effluent concentration profiles could be obtain. Viscous finger-
ing occurred during the subsequente water injection following high concentration polymer injec-
tion.
5. The chromatographic separation occurred during the SP co-injection scheme. It is necessary to
estimate this phenomenon during the design of field project.

Acknowledgement
The anthors would like to thank Saudi Aramco and the management of EXPEC Advanced Research
Center for granting permission to present this paper.
16 SPE-174572-MS

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