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Alkali Surfactant Polymer (ASP) Process for Shaley Formation with Pyrite

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SPE-190231-MS

Alkaline Surfactant Polymer ASP Process for Shaley Formation with Pyrite

L. Ding, China University of Petroleum; X. Zhai, SINOPEC; M. C. Puerto, C. A. Miller, and G. J. Hirasaki, Rice
University

Copyright 2018, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Improved Oil Recovery Conference held in Tulsa, Oklahoma, USA, 14-18 April 2018.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents
of the paper have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect
any position of the Society of Petroleum Engineers, its officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written
consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may
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Abstract
The ASP process may still be promising for surfactant flooding of shaley formations that have high
surfactant adsorption with conventional surfactant-polymer flooding. Positive sites on clays are sites where
anionic surfactant adsorption occurs in conventional surfactant flooding. High pH of alkali converts positive
clay sites to negative sites. In addition, sodium carbonate sequesters calcium ions due to the small solubility
product of calcium carbonate. If the formation has pyrite or siderite present, the core material in the
laboratory environment will likely have a coating of ferric oxide that contributes to the anionic surfactant
adsorption sites. Thus the test core should be restored to reducing conditions to better represent in situ
conditions.
The ASP process has two sources of surface active materials. One is injected synthetic surfactant and the
other is soap generated in-situ by reaction of alkali with naphthenic acids in crude oil. However, this adds to
the complexity of the process because the optimal salinity becomes a function of both the concentration of
injected surfactant and in-situ generated soap. Water soluble active soap number (WSASN) is used instead
of total acid number (TAN) to estimate the optimal salinity. When WSASN rather than TAN is used to
estimate the soap content, the logarithm of the optimal salinity is a linear function of the soap fraction. In
this presentation, we demonstrate the technology to estimate the optimal salinity of soap/surfactant mixtures
and use it to develop formulations with great potential to recover oil for a weakly consolidated sandstone
reservoir.
The potential of incremental oil recovery by the ASP formulation is evaluated by ASP flooding tests on
both quartz sand packs and formation material. The ASP formulation recovered more than 95% of the water
flooded residual oil using a 0.5 PV slug of either 0.3% or 0.5% NI blend surfactant. The sodium carbonate
concentration was 1.0% and the polymer concentration was 0.3%. Moreover, it is found from simulation
results that the development of soap/surfactant gradient in ASP flooding ensures the process passing through
the optimal condition, where minimum IFT and low residual oil saturation will be attained.

Introduction
As a cost-effective chemical EOR method, the original concept of alkali flooding is the reduction of oil/
water IFT by in-situ generation of soap, which is an anionic surfactant, sodium naphthenate (Jennings, 1975)
2 SPE-190231-MS

(Cooke et al., 1974) (Jennings et al., 1974). On one hand, numerous studies show that reaching ultralow
IFT usually requires injection of relatively fresh water (<1% electrolytes) with a low concentration of alkali
because the in-situ generated soap is usually very hydrophobic (Rubin & Wasan, 1992) (Hirasaki et al.,
2011). On the other hand, the interactions of alkali with the reservoir rock, oil and brine may result in a
large retardation of alkali propagation if the alkali concentration is too low (deZabala et al., 1982). This
dilemma can be addressed by addition of a more hydrophilic synthetic surfactant with the alkaline solution
(Nelson et al., 1984), such that the optimal salinity of the mixtures of in-situ generated soap and injected
surfactant can be tailored effectively to a desired level, which is known as the Alkaline/Surfactant/Polymer
(ASP) flooding process. So far, many ASP pilot tests (Sheng, 2014) (Olajire, 2014) have been reported in
the literature, among which Daqing ASP is generally acknowledged to be one of the most successful ASP
applications for improving oil recovery. The reported incremental oil recovery rate varied from 10% to 30%
OOIP with respect to ASP field tests of different scales (Stoll et al., 2011) (Guo et al., 2017) (Chang et al.,
2006) (Sheng, 2014).
ASP flooding may be quite promising for sandstone reservoirs with high remaining oil saturation, high
permeability and high porosity, low salinity as well as low hardness, low oil viscosity and low clay contents
(Lake et al., 2014) (Pope, 2011) (Sheng, 2014). However, ASP process was recently reported to be applied
to viscous oil (Kumar & Mohanty, 2010), low permeability (Ghosh et al., 2017), high salinity (Levitt et
al., 2012), high hardness (Sharma, 2014) carbonate reservoirs and high clay content sandstone reservoirs
(Rohilla et al., 2016). For clay-rich shaley formation that have high surfactant adsorption with conventional
surfactant-polymer flooding, the ASP process may still be promising. This is primarily because the positive
sites on clays are sites where anionic surfactant adsorption occur in conventional surfactant flooding, and
high pH of alkali converts positive clay sites to negative sites and thereby reducing anionic surfactant
adsorption on clays (Hirasaki & Zhang, 2004). Moreover, sodium carbonate sequesters calcium ions due to
the small solubility product of calcium carbonate (Hirasaki et al., 2011).
ASP flooding in shaley formation with pyrite and (or) siderite may be unfavorable in laboratory
conditions if the sand is not restored to reducing conditions. If the formation has pyrite or siderite, the core
material in the laboratory environment will likely have a coating of ferric oxide that contributes to the anionic
surfactant adsorption sites, which will result in severe surfactant retardation (Wang, 1993). Moreover, the
ferric oxide has large surface area and is known to contribute to oil wetness (Hirasaki, 1990) (Wang, 1994).
Illite and smectite also have large surface area and will likely be oil wet if they are coated with iron oxides.
Then, the oxidized formation may act as an oil wet formation that requires high capillary number to displace
the trapped oil (Lake et al., 2014). Thus, the test core (at aerobic condition) should be restored to reducing
conditions to better represent the in-situ anaerobic reservoir conditions before coreflooding.
The ASP process has two sources of surface active materials (Liu et al., 2008) (Liu et al., 2010). One is
the injected synthetic surfactant, which is typically more hydrophilic, and the other is soap generated in-situ
by reaction of alkali with naphthenic acids in crude oil, which is generally more hydrophobic. However, this
adds to the complexity of the process because the optimal salinity becomes a function of soap/surfactant
ratio, i.e., soap number, surfactant concentration and water oil ratio (WOR). Therefore, optimal salinity
of alkali/surfactant/crude oil system as a function of soap fraction is of great importance in formulation
design of ASP flooding process (Mohammadi et al., 2008). Consequently, designing an ASP process needs
extensively time-consuming phase behavior tests and tedious IFT measurements. As mentioned earlier,
soap can be regarded as an anionic surfactant. If the amount of active soap in crude oil can be accurately
determined, then, the classical mole fraction ‘mixing rule’ (Bourrel & Schechter, 1988) (Salager et al., 1979)
can be applied to estimate the optimal salinity of surfactant/soap mixtures. Traditionally, total acid number
(TAN) was used to estimate the amount of soap in crude oil. However, the experimental data deviated
significantly from the mixing rule when TAN is used for the soap content (Liu et al., 2010). This is because
certain acid components in crude oil can consume alkali but may not be surface active at reservoir conditions.
SPE-190231-MS 3

Recently, Liu (Liu et al., 2010) proposed a method to quantitatively determine the amount of soap in
crude oil, i.e., total soap number (TSN), by potentiometric titration. The soap number was then applied to the
mole fraction ‘mixing rule’ to estimate the optimal salinity of mixtures of surfactant and soap. It was found
that a better agreement between the mole fraction mixing rule and experimental data can be obtained when
TSN rather than TAN was used; however, the logarithm of optimal salinity was still not a linear function
of the soap fraction, even if the TSN was used. It was recently found that the water soluble active soap
number (WSASN), i.e., the amount of soap that can partition between oleic and aqueous phases at reservoir
condition, was able to provide a more precise estimate of the amount of active soap in crude oil (Ding et
al., 2016). This finding will be beneficial for designing a successful ASP process.
In this study, we demonstrate the technology to estimate the optimal salinity of soap/surfactant mixtures
and use it to develop formulations with great potential to recover oil for a weakly consolidated sandstone
reservoir with clay and pyrite. The method of restoring such oxygen-contaminated formation core material
to its original, anaerobic, reduced state is also proposed.

Experimental Section
Reservoir properties, Core Materials and Crude Oil properties
The targeted reservoir is a weakly consolidated sandstone reservoir located in USA. The reservoir
temperature is 54°C and the formation brine has low salinity (30,000 mg/L Total Dissolved Substance
(TDS)) with small amount of divalent ions. Thus, a synthetic brine prepared by sodium chloride with the
same TDS is used as formation brine. A relative fresh water (TDS~300 mg/L) is available for injection of
the chemical slug. From the X-Ray Diffraction data, the formation core material contains 4-35% of clays
(illite and smectite) and 0-2% pyrite. The cation exchange capacity is 0.05-0.97 meq/ml. The crude oil has
a viscosity of 8 cp at reservoir temperature. The TAN, TSN and WSASN are 0.84, 0.60, and 0.35 mg KOH/
g respectively (Ding et al., 2016).

Materials, Equipment and Procedures

Materials. The salts, alkali, surfactants and polymer used in this study are listed in Table 1. Sodium
carbonate is used because it was readily available and is a weak alkali. The polymer used here is partially
hydrolyzed polyacrylamide (HPAM) with 16 million molecular weight. IOS15-18 is an Internal Olefin
Sulfonate surfactant, while Neodol 67 is a C16-17, 7PO Sulfate surfactant.
Equipment and Procedures. The ASP formulation was selected based on surfactant solubility tests, alkali/
surfactant/crude oil phase behavior tests and IFT measurements, polymer viscosity measurements, and
alkali/surfactant/polymer compatibility tests. In surfactant solubility tests, alkali/surfactant/crude oil phase
behavior tests and IFT measurements, sodium carbonate solution is the only brine tested. In this paper, the
optimal salinity refers to the sodium carbonate concentration where minimum IFT is obtained from IFT
measurement or where the solubilization of oil and water in middle phase microemulsions are equal from
phase behavior tests (Healy & Reed, 1974) (Healy et al., 1976).
4 SPE-190231-MS

Table 1—Chemicals

The injected formulation should be clear; otherwise, it may plug the formation. 1:4 weight ratio of O332
and A771 surfactants blend (NI blend) was reported to have good surfactant solubility behavior and are
compatible with HPAM polymer at low ionic strength, and therefore were under evaluation (Liu et al., 2008)
(Liu et al., 2010). Samples with different sodium carbonate concentrations and surfactant concentrations
were prepared in 20 ml ampules and placed in water bath at 54°C. Clarity of these samples was checked
every two days. Viscosity measurements with different polymer concentration and salinity were conducted
using a Brookfield viscometer (Model: DV-1). The compatibility tests were prepared by mixing the HPAM
polymer, selected alkali/surfactant formulation and formation brine to see if there is phase separation under
54°C.
Phase behavior samples with different WORs, sodium carbonate and surfactant concentrations) were
prepared in pipettes (from Fisher Scientific) sealed at the bottom. After filled, pipettes were sealed at the
top using acetylene torch, these samples were shaken for 48 hours on an automatic rotator. Then, they were
equilibrated at 54°C. The procedure of preparing samples for IFT measurement are similar to those for phase
behavior samples except that these samples were prepared in 17 ml glass vials (from Thermo Scientific).
Then, all samples were left for equilibrium at reservoir temperature (54°C). After reaching equilibrium,
the aqueous phases were sampled using a glass syringe with a long needle at 54°C, and then collected
individually in glass vials for IFT measurement by a spinning drop tensiometer (TX 550) at 54°C. In all
test cases, alkali is adequate to neutralize all acid components in crude oil, and the excess alkali in brine
is considered to increase the ionic strength.
After the ASP formulation has been chosen, sandpack flooding tests on both silica sand and formation
core material were performed to evaluate its effectiveness in displacing water flooded residual oil under
reservoir temperature. It is also worth noted that the formation core material should be cleaned and restored
to reducing condition before conducting the flooding tests. The apparatus for water flooding and chemical
flooding is illustrated in Figure 1. A one-foot-long glass sand pack with one-inch inner diameter from SGI
(Specialty Glass Inc.) was used. The pressure limit of this glass sand pack is about 30 psi, and thus a 25 psi
relief valve was installed before the inlet. A pressure transducer (from EXTECH) connected to a computer
is used to record the pressure drop across the glass sand pack. Effluents were collected every 0.1 PV and
0.05 PV during water flooding and chemical flooding, respectively.
SPE-190231-MS 5

Figure 1—Schematic of sandpack flooding apparatus

Results and Discussion

Surfactant Solubility Tests and ASP Compatibility Tests
The solubility tests indicate that the NI blend surfactant can be further studied if 1.5% or 1.0% Na2CO3 is
proposed for injection. Moreover, no phase separation occurred when 1.0%/1.5% Na2CO3, 0.3% (or less) NI
blend surfactant and 0.3% HPAM polymer are prepared using the injection brine and mixed with formation
brine after 30 days. Thus, the NI blend is suitable for further investigation.

Phase Behavior Tests

The optimal salinity of soap (without added surfactants) is 0.9% Na2CO3 defined by equilibrium IFT
measurement of pre-equilibrated alkali/crude oil samples, which is consistent with the alkali/crude oil phase
behavior tests (Ding et al., 2016). The phase behavior samples of Na2CO3/NI blend/crude oil, containing
fixed Na2CO3 concentration at WORs of 1, 3 and 5 were prepared and equilibrated at 54°C. The sodium
carbonate concentrations studied here are 1.5 wt. %, and 1 wt. %, where in each scan of phase behavior
samples, the surfactant concentrations are changing while sodium carbonate concentration and WOR are
fixed. After 30 days, no further change of samples was detected and these samples were regarded as in
equilibrium. Figure 2(a) and (b) are pictures of phase behavior samples with 0.25-0.025 wt.% NI blend
(active concentration for overall system, i.e., both aqueous phase and oleic phase) and 1.5 wt.% or 1.0 wt.
% Na2CO3 (concentration in aqueous phase) mixed with crude oil at a WOR of 5 and equilibrated at 54°C
for 30 days.
As indicated in Figure 2(a) and (b), the appearance of phase behavior samples is generally that of a
conventional Winsor I, III, and II microemulsion sequence. For phase behavior samples with 0.25-0.025%
NI blend and 1.5 wt. % Na2CO3 at WOR=5, the optimal condition refers to the condition where the water
solubilization parameter Vo/Vs and oil solubilization parameter Vw/Vs in middle phase microemulsion are
equal, which is around 0.05% NI blend (the third sample from the right, Figure 2(a), at Xsoap=0.57).
6 SPE-190231-MS

Figure 2(a)—Phase Behavior of NI Blend, WOR=5, 1.5% Na2CO3, equilibrated at 54°C for 30 days

Figure 2(b)—Phase Behavior of NI Blend, WOR=5, 1.0% Na2CO3, equilibrated at 54°C for 30 days

For phase behavior samples with 0.25-0.025% NI blend and 1.0 wt. % Na2CO3 at WOR=5, the middle
phase microemulsion is undetectable. However, Winsor I microemulsion is observed at 0.025% NI blend
(The second sample from the right, Figure 2(b), at Xsoap=0.71), while Windsor II microemulsion is clearly
detected at samples with zero surfactant concentration (The first sample from the right, Figure 2(b), Xsoap=1).
Therefore, the optimal condition may be located between Xsoap=1 and Xsoap=0.71, which can be further
proved by the mole fraction mixing rule correlation in the next section.

Mole Fraction Mixing Rule Correlation

As mentioned earlier, the optimal salinity of an alkali/surfactant/crude oil system is a function of soap/
surfactant ratio. Since soap is also an anionic surfactant, it is reasonable to assume that the blend of soap
and synthetic anionic surfactant in alkali/surfactant/crude oil system might follow the same mixing rule, as
shown in Equations 1 and 2.
SPE-190231-MS 7

(1)

(2)

where Optmix, Optsurfactant, Optsoap are the optimum salinity of the surfactant/soap mixture, surfactant and soap,
respectively, and Xsoap is the mole fraction of soap.
Because O332 and A771 are inherently a mixture of surfactants and an accurate value of its molecular
weight is difficult to determine, it is assumed that the fractions of surfactants with different carbon chain
lengths are equal and then their average molecular weight are 333 and 743, respectively (Barnes et al.,
2010). The average molecular weight for NI blend is subsequently calculated at 661. Moreover, the molar
fraction of soap can be calculated by WSASN (0.35 mg KOH/g oil). Consequently, the molar fraction of
soap at different surfactant concentrations and WORs can be calculated (Equation 2).
Figure 3 is to compare the experimental results and mole-fraction mixing rule about phase behavior of
Na2CO3/NI blend/crude oil system when the Xsoap is determined by WSASN. The straight line in Figure 3
represents Equation 1, while the markers represent experimental results of phase behavior tests. The markers
in purple, blue and red indicate optimal, under-optimal and over-optimal condition of Na2CO3/NI blend/
crude oil system, respectively. At large and small values of soap ratio, optimal salinity approaches those
of the soap alone (0.9% Na2CO3) and surfactant alone (3.4% Na2CO3). The optimal salinity of NI blend is
extrapolated from experimental results, which is consistent with the value in reference (Barnes et al., 2010).
This extrapolated value represents the optimal salinity of NI blend in the absence of soap. When sodium
carbonate is present, the optimal salinity will be the optimal salinity of soap/surfactant mixture, represented
by the dashed line. When surfactant concentration is large enough, the optimal salinity of soap/surfactant
mixture is close to the optimal salinity of surfactant alone, which is consistent with the first two points with
small soap fraction in Figure 3.
As indicated in Figure 3, the mixing rule is found to work reasonably well to predict the phase behavior
of alkali/surfactant/crude oil system. When WSASN is used to estimate the soap content, the logarithm of
the optimal salinity is a linear function of the soap fraction. Typically, designing an ASP flooding process
requires extensive phase behavior tests, which are extremely time-consuming. The finding that the optimal
salinity of Alkali/Surfactant/Crude oil system can be predicted by the mixing rule when WSASN is used to
quantitatively determine the amount of soap will be beneficial to design a successful ASP process.

Figure 3—Optimal Salinity Curve as a Function of Soap Fraction (NI Blend)

8 SPE-190231-MS

IFT Measurements
Ultralow IFT is always necessary to increase the capillary number to the value that corresponding to near
zero residual oil saturation (Lake et al., 2014). The equilibrium IFT of pre-equilibrated samples is measured
in this study. Samples for IFT measurements were first prepared and equilibrated at 54°C until equilibrium.
After 30 days, no further change of sample appearence was detected and these samples were regarded as in
equilibrium. Colloidal dispersion (Liu et al., 2008) was found to influence the IFT and was hypothesized to
be the soap-and-oil-rich microemulsion. Because the presence of colloidal dispersion, oil may be obscured
by the darker substance. Liu (Liu et al., 2008) proposed a method to measure the interfacial tension if too
much colloidal dispersion was presented. Basically, one need to remove some colloidal dispersion and let the
sample re-equilibrated in spinning tube overnight to decrease the time needed to reach equilibrium during
IFT measurement. This protocol is used for IFT measurements disclosed in this article, and the procedures
can be found in Appendix A in reference (Liu et al., 2008). Consequently, the equilibrium IFT of crude
oil against the Na2CO3/NI Blend as a function of soap fraction can be plotted, as elucidated in Figure 4(a)
and (b).

Figure 4(a)—Equilibrium IFT as a Function of Soap Fraction and WORs, 1.5% Na2CO3
SPE-190231-MS 9

Figure 4(b)—IFT as a Function of Soap Fraction, NI Blend, 1.0% Na2CO3

It is found that ultralow IFT (<10−2 mN/m) can be achieved at optimal condition defined by phase behavior
tests. It can also be seen from Figure 4(b) that the equilibrium IFT for samples with similar soap/surfactant
ratios but different WORs and surfactant concentration are almost equal. Thus, equilibrium IFT is almost
only a function of soap fraction.

Viscosity Measurements and Chemical Consumption Tests

Generally, polymer flooding will not reduce the water flooded residual oil saturation (Needham & Doe,
1987) (Lake et al., 2014) except at certain conditions (Wang et al., 2001) (Koh et al., 2017) (Qi et al., 2017).
However, the viscosity of aqueous phase determines the water to oil mobility ratio, which is very important
for a successful ASP process (Hirasaki et al., 2011). The viscosity of aqueous phase solution as functions
of polymer concentration and shear rate can be found in Figure 5. For flow in porous media, the equivalent
shear rate can be used as a criterion to select polymer concentration. However, filtration ratio, filter ratio
and polymer inaccessible pore volume (IPV) were not studied in this paper.

Figure 5—Viscosity Measurements, 1.0% Na2CO3+2% NaCl

10 SPE-190231-MS

The challenge of ASP flooding process also depends on the simultaneous propagation of surfactant
and alkali in the reservoir (Hirasaki et al., 2011) (Lake et al., 2014). Thus, it is important to measure
the chemical consumptions, i.e., alkali consumption and surfactant adsorption, etc. However, because
the surface area of silica sand is small and the presence of alkali can significantly reduce the surfactant
adsorption, therefore, the alkali consumption and surfactant adsorption on silica sand are negligible. For
flooding test on formation core material, surfactant adsorption and alkali consumption are not negligible
and may result in severe retardation and chromatographic separation. Therefore, the composition and size
of the ASP slug should be carefully designed to avoid deleterious chromatographic separation. Sacrificial
agent such as low molecular weight polyacrylate (Shamsijazeyi et al., 2014) can also be applied to reduce
surfactant adsorption. However, this information is not included in this paper.

Silica Sand Pack Flooding Experiments

The potential of incremental oil recovery by the ASP formulation is evaluated by flooding test on silica
sand under reservoir condition. Table 2 provides the properties of the sandpack. The sandpack was initially
saturated with oil at 54°C at a high pressure drop in order to reduce water amount to the irreducible
saturation. The end point oil relative permeability was measured at the end stage of oil flooding, which was
0.92. After oil saturation, the sand pack was left to equilibrate for about 3 days. After aging, brine (3% NaCl)
was injected at 0.432 ml/min (4 ft./day) until no oil was coming out, which took about two pore volumes
(PV). The sandpack flooding, i.e., water flooding and chemical flooding, was conducted horizontally.

Table 2—Parameters of Silica Sandpack for ASP Flooding

During water flooding, water breakthroughs at around 0.44 PV, and about 64% OOIP oil is recovered
after water flooding. The residual oil saturation is 36% and the end point water relative permeability is
0.14. Based on Buckley-Leverett theory (Buckley & Leverett, 1942) (Welge, 1952) for one dimensional,
two phase immiscible displacement, the Corey components (Corey, 1954) for water ( ) and oil ( )
relative permeability curves can be estimated, which are 2.0 and 1.5 respectively and these values will be
used in the ASP simulation. After water flooding, ASP process was implemented on the sandpack. A 0.56
PV slug of ASP solution followed by 0.75 PV of polymer drive was injected into the sandpack at 0.108 ml/
min (1 ft./d) in order to mimic real field injection velocities.
It was found that high recovery of water-flooded residual oil could be expected for a wide range of near-
optimal and under-optimal conditions (Liu et al., 2010). A key factor leading to this good performance is the
development of a soap/surfactant ratio gradient, which ensures that a displacement front with ultralow
IFT forms and propagates through the porous media. This gradient increases the robustness of the ASP
process and is applied to design the alkali and surfactant concentration as well as slug size for a robust ASP
formulation in this paper.
SPE-190231-MS 11

The injection scheme and formulation of ASP slug and polymer slug are listed in Table 3. The injected
formulation is at under-optimal but close to optimal condition, therefore, a soap/surfactant gradient is
expected to be developed. The polymer concentration in ASP slug and polymer slug is 0.3%, and the
viscosity of injection formulation is 36 cp at shear rate of 13 s−1 (Equivalent shear rate at injection velocity
of 1 ft./day on 10 Darcy sandpack) (Sheng, 2011) at 54°C. The polymer concentration was chosen such that
the mobility of ASP slug and polymer slug would be lower than total mobility of the oil bank formed due
to re-mobilization of the residual oil.

Table 3—Composition of ASP Slug for Silica Sandpack Flooding

Photos shown in Figure 6 are to illustrate how the oil bank forms and propagates during chemical
flooding. A well formed oil bank is developed. Behind the displacement front, the residual oil saturation is
almost zero. The effluent samples were centrifuged at 3000 rpm for 30 minutes in a centrifuge (Eppendorf,
3000) in order to break the emulsion. Then, the oil cut and cumulative oil recovery as a function of the
volume of fluid injected can be determined, as shown in Figure 7. The effluents at different pore volumes
during chemical flooding is shown in Figure 8.

Figure 6—Photos of Silica Sandpack during ASP flooding at Different Injection Pore Volumes
12 SPE-190231-MS

Figure 7—Cumulative Oil Recovery and Oil Cut History during ASP Flooding on Silica Sandpack

Figure 8—Effluents during ASP Flooding on Silica Sandpack

The oil bank breakthroughs at around 0.56 PV while the surfactant breakthroughs at approximately 0.84
PV because Winsor I microemulsion can be found at that time. Moreover, alkali breakthroughs at 0.79 PV
from pH measurement. A very high oil recovery of approximately 95% water flooded residual oil (ROIP)
was obtained with a significant oil fractional flow at 75% in the oil bank. The remaining oil saturation at the
end of the chemical flood was approximately 2% OOIP. Oil bank breakthrough even ahead of the surfactant/
soap, which is desirable because the oil produced before surfactant/soap breakthrough is clean and free of
emulsion problems.
The pressure drop during chemical flooding is also important, because the pressure gradient should not be
exceeding the formation fracture pressure. The history of pressure drop is shown in Figure 9. The pressure
drop increased with the injection because the surfactant slug and polymer drive were designed to have a
favorable mobility ratio. The pressure became stable and did not increase significantly after the surfactant
breakthroughs because the whole sand pack was occupied by the chemical formulations which have nearly
identical viscosities.
SPE-190231-MS 13

Figure 9—Pressure Drop during ASP Flooding on Silica Sandpack

One Dimensional Simulation

An in-house developed, one dimensional, two phases, multi componential and explicit finite difference
simulator is used to history match the ASP flooding result and investigate the mechanism. The synergistic
effect of synthetic surfactant and soap (mole fraction mixing rule for soap/surfactant mixtures) is important
for the success of ASP process and is incorporated into this simulator. The description of this mathematical
model such as assumption, calculation procedure and other detailed information can be found in references
(Liu et al., 2008) (Liu et al., 2010). Moreover, the equivalent salinity of 1% Na2CO3 is found to be almost
equal to 1% NaCl based on preliminary phase behavior experiments, which is taken as another assumption
in the simulator.
The input parameters for ASP flooding simulation is given in Table 4. The initial condition for ASP
flooding simulation will be water (3% NaCl) flooded residual oil saturation. The value of dt/dx2 is 0.5,
because this conforms to the Courant-Friedrichs-Lewy (CFL) stability condition (Aziz & Settari, 1986)
(Mattax, 1990). Similarly, the choice of 100 grid blocks reflects the smallest number of which the solution
does not change significantly with increasing number of grid blocks. A typical range of Peclet number is
50-500 and the value of 50 is used in the simulation (Hirasaki et al., 2011). 0.56 PV of ASP slug containing
1.0 wt. % Na2CO3, 0.3 wt. % NI blend surfactant and 0.3 wt. % polymer is injected, followed by 1 PV of
polymer slug containing 0.3 wt. % polymer.
14 SPE-190231-MS

Table 4—Input Parameters for ASP Flooding Simulation on Silica Sand

Figure 10 is to compare the simulation results and experimental results during ASP flooding. The
simulation results matches with the experimental results quite well. It can be seen that the calculated
breakthrough time of oil bank, oil cut history and cumulative oil recovery by this simulator are
consistent with the experimental results. For mechanistic chemical flooding simulators, such as UTCHEM
(Mohammadi et al., 2008) and MoReS (Farajzadeh, 2012), acid number is often used as an input parameter
to estimate the amount of soap. The WSASN will provide a more reasonable approach for mechanistic
simulation of ASP process.

Figure 10—Comparison of effluent oil fraction and Incremental Oil Recovery history for ASP Flooding on Silica Sand

Figure 11 is for depicting the concentration profiles of alkali, polymer, naphthenic acid, synthetic
surfactant and soap at 0.4 PV. From this plot, it can be seen that the soap front is ahead of the surfactant
even without considering the surfactant adsorption, which is probably because soap partition into and
SPE-190231-MS 15

propagate in the oil phase. Consequently, ahead of alkali and surfactant front, there is the type II (over-
optimum) region because soap is dominant and local salinity is higher than the optimum salinity of soap. In
this region, the soap to surfactant ratio is very high. Well behind the surfactant front, there is a type I (under-
optimum) region because surfactant is dominant when little or no natural soap resides in this region. Here
the local salinity is lower than the optimum salinity of surfactant. In the type I region, the soap to surfactant
ratio is very small. Thus, a soap/surfactant ratio gradient is generated.
Figure 12 is for disclosing the IFT and oil concentration profiles at 0.4 PV. In this figure, the initial oil
saturation is the water flood residual oil saturation (35%). The residual oil saturation after ASP flooding
was close to zero and an oil bank is generated. The minimum low tension is found at the location where the
optimal salinity of local soap-to-surfactant ratio is corresponding to its local salinity. Therefore, the soap/
surfactant ratio gradient assures that the process passes through the optimum region of minimum IFT where
low residual oil saturation will be attained.

Figure 11—The concentration profiles of alkali, polymer, naphthenic acid, synthetic surfactant and soap at 0.4 PV
16 SPE-190231-MS

Figure 12—IFT and Oil Saturation Profiles at 0.4 PV

Formation Core Restoration

When field core is used, the core needs to be cleaned initially and then flushed with sodium dithionite and
sodium sulfite to restore it to reducing condition (Hirasaki, 1990) (Wang, 1994). The weakly consolidated
formation core material is packed into the glass sandpack, and the procedure of core cleaning is conducted
by continuous injection of toluene. After injecting about 10 PV of toluene, the effluent appears clear. Then,
THF was injected and the effluents becoming dark black again, which confirms that cleaning cores using
toluene alone is insufficient. Finally, methanol is injected to displace the THF (Hirasaki, 1990) (Rohilla
et al., 2016). This flushing method for core cleaning has been proved to be able to preserve the original
core wettability.
The restoration of core material to reservoir condition is next conducted by continuous flush of formation
brine (3% NaCl) with 0.3% sodium sulfite and 0.1% sodium dithionite. The 3% NaCl is used to prevent
swelling of clay while sodium sulfite and sodium dithionite are used as oxygen scavenger and reducing
agent, respectively (Hirasaki G. J., 1990). Effluents are collected every 0.2 PV, while an electrode (from
HACH) is used to measure the redox potential of effluents and the other electrode (from Metrohm) is used
to measure the pH of effluents. The pH and redox potential of effluents during reduction are elucidated in
Figure 13. At around 4.63 PV, the pH and redox potential starts to decrease, while at around 5.37 PV, the pH
reaches its minimum and then raise gradually to the pH value of the injection solution. Moreover, the color
of effluents between 5.37 PV and 5.92 PV (Figure 14) turned from almost clear to yellow after exposure
to air, which may indicate the oxidation of Fe2+ to Fe3+.
SPE-190231-MS 17

Figure 13—Redox Potential and pH Variation during Reduction, Neutralization and Restoration of Formation Core Sample

Figure 14—Photos of Effluents during Reduction and Restoration of Formation Core Sample

After shut in overnight, the effluent pH decreased again, which may indicate that additional reaction
occurred in the core before reaching equilibrium. The byproduct of reduction process is hydronium ions,
which may persist in the formation material and contribute to alkali consumption and retardation. Therefore,
formation brine (3% NaCl) with 1% NaHCO3 and 0.3% Na2SO3 is used to neutralize the core material.
Moreover, the alkalinity of the formation core needs to be restored by flushing with formation brine (3%
NaCl) with 0.3% Na2SO3. After the pH of effluents getting equal to the pH of injection solution, the
restoration process is stopped.

Formation Core Flooding

The formation core material should be cleaned and restored to reservoir condition before conducting any
flooding tests. Moreover, the permeability measurement and flooding tests also need to be conducted at
anaerobic condition. The procedure is similar to that described using silica sand except that all liquids are
added with 0.3% sodium sulfite to remove oxygen and maintain the anaerobic condition during the water
flooding and chemical flooding process.
18 SPE-190231-MS

Table 5 provides the properties of the formation core sandpack. The sandpack was initially saturated with
oil at 54°C. The initial oil saturation was 0.80 and the end point oil relative permeability was measured at
the end stage of oil flooding, which was 1. After oil saturation, the sandpack was left to equilibrate for about
3 days. After aging, brine (3% NaCl+0.3% Na2SO3) was injected at 0.432 ml/min (4 ft./day) until no oil
was coming out, which also took about two PV. The sandpack flooding, i.e., water flooding and chemical
flooding, were conducted horizontally.

Table 5—Parameters of Sandpack, Formation Core Material

During water flooding, water breakthroughs at around 0.41 PV, and about 62% OOIP oil is recovered after
water flooding. The residual oil saturation is 38% and the end point water relative permeability is 0.24. After
water flooding, ASP process was implemented on the sandpack. A 0.53 PV slug of ASP solution followed
by 1.85 PV of polymer drive was injected into the sandpack at 0.108 ml/min (1 ft./d). The formulation
of ASP slug and polymer slug is shown in Table 6. Due to insufficient data of surfactant adsorption, the
surfactant concentration in ASP slug had been raised to 0.5%, making this flooding test quite conservative.

Table 6—Evaluated ASP Formulation, Formation Core Material

The appearance of glass sand pack at different stages of chemical flooding is shown in Figure 15 (front
view). A clear oil bank is developed with oil fractional flow at 75% in the oil bank, and the final oil recovery
reaches 99% OOIP (>99% ROIP).
SPE-190231-MS 19

Figure 15—Photos of ASP Flooding on Formation Core Sample (front view)

From Figure 15, we can see that the chemical formulation prefers to flow through the upper part of the
sandpack rather than the lower part. Correspondingly, there is an elongated tail in oil cut history. Presumably,
the chemical formulation would go downward if this segregation were resulted from gravity difference.
Moreover, mobility control is sufficient because the chemical formulation has a viscosity much higher than
that of oil. The relative permeability of water and oil may become higher at ultralow IFT and high capillary
number, but should not change the water/oil mobility ratio significantly. Therefore, our hypothesis is that the
formation core in sandpack may be heterogeneous, and the upper part of the sandpack may have a relatively
higher permeability. This may have occurred due to gravity settling of the sand.
The oil cut and cumulative oil recovery as a function of the volume of fluid injected is exhibited in Figure
16, while the effluents at different pore volumes during chemical flooding is shown in Figure 17.
20 SPE-190231-MS

Figure 16—Cumulative Oil Recovery and Oil Cut during ASP Flooding on Formation Core Sample

Figure 17—Effluents of ASP Flooding on Formation Core Sample

The oil bank breakthroughs at around 0.63 PV. Moreover, the alkali breakthroughs at 0.86 PV from
pH measurements, while the surfactant breakthroughs at approximately 0.91 PV because Winsor I
microemulsion can be found in the aqueous phase. It should be noted that the breakthrough time of surfactant
and alkali on formation core material are later than that conducted on silica sand, which indicate that the
surfactant adsorption and alkali consumption on formation core material are significant. The history of
pressure drop is shown in Figure 18.
SPE-190231-MS 21

Figure 18—Pressure Drop during ASP Flood on Formation Core Sample

Conclusions
1. It is found that when Water Soluble Active Soap Number (WSASN) was used to quantitatively
determine the soap number, the mixing rule is followed reasonably well to predict the optimal salinity
and phase behavior of Na2CO3/Surfactant/Crude oil system;
2. Ultralow IFT (<10−3 mN/m) can be achieved near optimal condition; the optimal condition of pre-
equilibrated Na2CO3/NI Blend/crude oil system is found to be only a function of soap fraction for
samples with different surfactant concentrations and WORs;
3. The desirable ASP formulation is developed based on mole fraction mixing rule correlation. The ASP
formulation recovered more than 95% of the water flooded residual oil using a 0.5 PV slug of either
0.3% or 0.5% NI blend on both silica sand and formation material;
4. The simulation results match the experimental results well; The WSASN (instead of the TAN) will
provide a more reasonable approach for mechanistic simulation of ASP process;
5. The procedure of restoring pyrite-containing formation core materials to reservoir condition is
demonstrated.

Acknowledgements
Financial supports from Chinese Scholarship Council (201206450036) and Rice University Consortium for
Processes in Porous Media are greatly acknowledged.

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