SPE-195039-MS

Compositional Modeling and Calibration of ASP Carbonate Corefloods

Mohammed T. Al-Muraryi, KOC; Shawket G. Ghedan, CMG, Now with Dragon Oil Limited; Fraser Skoreyko, CMG;
Abrahim A. Hassan, Ricardo Lara, and Ali Qubian, KOC

Copyright 2019, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE Middle East Oil and Gas Show and Conference held in Manama, Bahrain, 18-21 March 2019.

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
The shortage and high cost of CO2 and/or Hydrocarbon gases, in some areas, makes chemical EOR a
practical option for tertiary oil recovery. Alkaline, Surfactant and Polymer, ASP, formulations continue to
evolve to withstand challenges in relation to reservoir heterogeneity, complex mineralogy, high temperature
and high formation water salinity of carbonate reservoirs. Such advanced ASP formulations have been
considered to evaluate the performance of tertiary oil recovery process in a Kuwaiti carbonate reservoir.
Successful performance has been seen in the lab through the evaluation of ASP coreflood experiments using
composite carbonate cores. This paper presents the results of these coreflooding experiments and the steps
followed to build representative ASP flooding simulation models as well as the workflow to calibrate these
models to the observed experimental data. Moreover, the paper highlights the challenges associated with
ASP coreflooding process and its modeling in the difficult environment of carbonate reservoirs. The paper
also presents the techniques followed to overcome some of these challenges.
The modeling of two corefloods are presented in this paper, the first is for high-pressure live oil ASP
coreflood, and the second is for low-pressure, surrogate oil ASP coreflood. The carbonate composite cores
were first flooded with seawater down to residual oil saturation, Sorw. The ASP coreflood started with pre-
flushing phase using softened seawater, followed by an ASP slug, and ended by injecting a number of pore
volumes of polymer solution for mobility control. The representative ASP flooding simulation models of
this paper captured the vital mechanisms involved in the ASP chemical EOR process, such as:

• Micro-emulsion phase behavior, surfactant solubility ratios and resulting IFT changes

• Saponification process by the reaction of naphthenic acids of the crude oil with the injected alkali

• Adsorption of surfactant and polymer on the carbonate rocks as a function of pH and time

• The geochemistry of aqueous and oleic phase reactions

• Updating reservoir capillary number, resulting from the changes to IFT and wettability

• Effect of changes in capillary number is reflected by different sets of interpolation Kr curves

• The rheological behavior of polymer solutions

2 SPE-195039-MS

• Optimum salinity and salinity gradient effect.

Assisted history matching software was employed in the calibration of the two corefloods following a
stepwise procedure by first matching the water flood results, then matching the surfactant production values,
and finally matching the remainder of the ASP flood results. This paper discusses the parameters that needed
to be tuned in order to attain a match of both waterflood and ASP flood results. The matched results included
the oil recovery, flow pressure differential, and the concentration of chemical effluents traced during the
experiments. The profile of ASP oil recovery in these carbonate composite cores is more gradual, and is
different from those observed in sandstone corefloods.

Chemical ASP Flooding

Approximately only one-third of the oil present in known reservoirs is economically recoverable with
established technologies of primary and secondary recovery techniques1. The level of the remaining oil
saturation, trapped in the reservoir due to the interplay between reservoir forces of viscous, gravity and
capillary forces2, is a function of the capillary number, the higher the capillary number, the lower the
remaining oil3. The target of EOR techniques is to decrease the remaining oil saturation by increasing the
capillary number2. This is possible by reducing the interfacial tension (IFT) between the injected fluid and
the reservoir resident oil. Increasing the viscosity of the displacing fluid mainly affects the macroscopic
(volumetric) sweep via more favorable mobility control and the effects of the increased viscosity on the
microscopic (displacement) sweep2 are less important.
Alkaline/Surfactant/Polymer (ASP) flooding, is one of the most commonly known chemical EOR
techniques. ASP is typically injected into reservoirs after waterflooding, in order to increase the oil recovery
by reducing IFT between the aqueous and oleic phases. The alkali is injected primarily as a sacrificial
chemical to prevent surfactant losses due to adsorption. A secondary objective of the alkali injection is
to react with the acid component in the oil to produce in-situ surfactant (soap). Synthetic surfactant is
also injected to increase the effectiveness of the process. The soap and synthetic surfactant lower the IFT
between the oleic and aqueous phases, improving the microscopic sweep efficiency4. The macroscopic
sweep efficiency, on the other hand, is improved by an internal polymer drive suitably adjusted to the oil
viscosity. The alkali/surfactant slug is typically followed by a polymer flood for mobility control2,5–6.

Types of Microemulsions
Solubility and interfacial activity of soaps is sensitive to salinity. Depending on the salinity of the aqueous
phase, one of three types of microemulsions may be formed, resulting in two or three phases in equilibrium7.

• Microemulsion Type II-, where oil is solubilized in water, is an under optimum salinity system.
Two phases co-exist: an excess of oil phase and a water-microemulsion phase containing brine,
surfactant and some solubilized oil.
• Microemulsion Type II+, where water is solubilized in oil, is an over-optimum salinity system.
Two phases co-exist: an excess of water phase and an oil-microemulsion phase containing oil,
surfactant and some solubilized water.
• Microemulsion Type III, where surfactant is the middle bi-continuous phase, is an optimum salinity
system. It consists of oil and water phases separated by a middle micro-emulsion phase where
ultralow IFTs can be observed4,7.

Performance of ASP Chemical Flooding

Numerous laboratory measurements are needed to quantify the behavior of an ASP formulation before a test
can be designed and implemented in the field to ensure a high chance of success8–9. A successful laboratory
SPE-195039-MS 3

approach to chemical flooding generally results in a chemical formulation having a desired microemulsion
phase behavior and giving good recovery of residual oil in cores10–12.
Chemical phase-behavior experiments for a particular field seek to identify a surfactant mixture type
and concentration, as well as the necessary alkali concentration and possibly a co-solvent to achieve low
interfacial tension values between the crude oil and the brine9. After finding the optimum phase behavior,
the ASP formulation is tested in coreflood experiments to prove its ability to liberate and mobilize remaining
oil. These experiments provide information about the adsorption characteristics of the chemical components
as well as the displacement stability of the (internal) polymer drive9.

Modeling of ASP Coreflooding

For better understanding of flow mechanisms during chemical ASP floods, the coreflooding experiments
need to be properly modeled, and calibrated by history matching the coreflooding experimental data. The
logical step, after the laboratory investigation and its modeling, is to upscale the laboratory results and
test the process on a pilot scale in the field. A cost effective implementation of the process requires the
generation of a pilot sector model to be utilized for the optimization of the cEOR ASP flood parameters in
the field. This sector model needs first to be history matched for the past field and pilot waterflood activities.
Second, the model should be history matched to the single well chemical tracer tests, SWCTT, and interwell
chemical tracer tests, IWCTT, conducted in the pilot wells. This model is then converted to a chemical
EOR model, once we merge the upscaled chemical ASP parameters deduced from the modeling and the
calibration of the ASP coreflooding experiments.
Key ASP Modelling Features. In addition to modeling the physics of multiphase flow in porous media,
proper ASP simulation models should consider some or all of the following mechanisms depending on
project requirements and availability of data,
1. In situ soap generation13:
Alkali agents are injected to increase pH and react with the acids in crude oil to generate soap
in-situ. Acid Number is used as a measure for the potential of the crude oil to form soap. The acid
number is a measurement of acidity that is determined by the amount of potassium hydroxide in
milligrams that is needed to neutralize the acids in one gram of oil. The generation of soap is modeled
by partitioning the acid in the crude oil to water according to the solubility governed by the partition
coefficient. The acid in water will then dissociate in the aqueous phase to produce soluble anionic
surfactant (A- -) referred to as soap.
2. Microemulsion phase behavior and IFT Reduction13–14:
The modeling approach of microemulsion phase behavior relies on approximating Type III
microemulsion with two pseudo phases; i.e. oil and water phases. This model was developed by Jong
et al. (2016)14 and is used in different EOR processes such as Low Tension Gas, and ASP flooding.
The merits of this approach are:
a. The Windsor Type III microemulsion phase behavior is handled by partitioning the
microemulsion phase between the oil and the water phases according to the principle of
controlling the IFT, and relies on the solubilization ratio curves. No separate microemulsion
phase is required.
b. The viscosity increase due to the microemulsion phase is modelled using a separate viscosity
calculation when the surfactant is partitioned in the oil phase.
c. The optimal salinity as well as IFT are modeled as functions of the in situ soap to injected
surfactant ratio. This accounts for the effect of salinity gradient on the phase behavior.
3. Interpolation of Relative Permeability Curves:
4 SPE-195039-MS

Capillary desaturation process is modeled by the interpolation of relative permeabilities as a

function of recurrently calculated capillary number. Three sets of relative permeability curves are
typically used, the first is for typical waterflooding, the third set is for miscible flooding (with Type
III microemulsion), and a middle set with more water wet curves and lower residual oil saturations.
4. Rheology of Polymer Solutions:
Proper Rheology model should consider the following aspects of polymer solutions:
a. Polymer viscosity as a function of polymer concentration.
b. Polymer viscosity as a function of the salinity.
c. Polymer viscosity as a function of shear rates.
d. Polymer disproportionate perm reduction (DPR) effect and Inaccessible Pore Volume (IPV), and
e. Reactions to simulate degradation of polymer solutions.
5. Adsorption of Polymer and surfactant on reservoir rocks:
Polymer and surfactant adsorption should be considered in any proper modeling of ASP process,
as it has technical and economic impact on the ASP flooding process.
6. Complete geochemistry model13

a. Aqueous phase reactions: These are fast reversible aqueous reactions that are modeled with the
instantaneous chemical equilibrium reactions.
b. Mineral dissolution and precipitation reactions: These are slow reactions, typically modeled as
rate dependent reactions.
c. Ion exchange equilibria: These reactions are equilibrium reactions that occur on the surface of
clays. The equilibria are described using selectivity coefficients that follow the Gaines-Thomas
convention

Application of ASP Flooding in Carbonate Reservoirs

Almost all the chemical EOR applications have been performed in sandstone reservoirs, except for a few
projects that were conducted in carbonate reservoirs15. One of the biggest challenges to the application of
ASP flooding in Carbonate reservoirs is reducing the surfactant retention to low enough values for the
process to be economical16. High surfactant retentions between 0.44 to 1.9 mg/g rock were reported in
different studies performed on carbonate rocks.

SAMA Carbonate Reservoir

The Sabriyah Mauddud (SAMA) is a giant carbonate oil reservoir. It covers over 200 square kilometers
in the northern region of Kuwait17. The field is an elongated, faulted anticline, with structural plunge of
several degrees to the north and south, with northwest-southeast trending faults. The Mauddud Formation
consists predominantly of highly heterogeneous limestone, primarily driven by depositional and diagenetic
processes. It has mixed wettability with tendency to be more extremely oil wet reservoir with porosity and
permeability ranging between 18 to 30% and 7 to 700 mD, respectively. Vertical to Horizontal Permeability
ratio is variable ranging between 0.01 to unity. Formation brine of SAMA reservoir is of very high salinity
reaching up to 235,000 ppm.

Development and Performance of SAMA Reservoir:

Generally, SAMA reservoir is still underdeveloped with lower oil recoveries. Since its discovery in 1956,
until very recently there has not been any significant production from SAMA when weighed against its
estimated in-place volumes18. Oil production started in January 1958 and continued under primary recovery
until year 200017. Because of a water injection pilot, that was initiated in year 1997 and ran through year
SPE-195039-MS 5

1999, inverted 9-spot waterflood patterns were implemented in 200117–18. A significant amount of oil is
estimated to remain in SAMA mainly due to the high degree of heterogeneity and the adverse mobility
ratio for waterflood18. To improve waterflood performance, a hybrid injection scheme was considered, in
which central and mid-flank areas were developed by inverted 9-spot patterns while horizontal wells were
planned in the periphery with injectors in lower layers and producers in upper layers for a gravity stable
displacement. While this hybrid-development plan was estimated to improve the waterflood performance,
remaining oil in SAMA was still predicted to be high19.
A Single Well Chemical Tracer Test, SWCTT, conducted in SAMA in 2011 to estimate residual oil
saturation to water, Sorw, found it to be around 0.3118. It is clear that the SAMA reservoir would require
the application of an EOR technique to maximize its overall oil recovery. A modeling study19, conducted
using a sector model, provided technical analysis of the viability of several EOR methods such as miscible
CO2, WAG, and chemical EOR processes. The surfactant-polymer EOR process showed very promising
oil recovery capability.
A closely spaced 5-spot pilot with four injectors and one central producer has been prepared in SAMA.
The injection schedule for the pilot has been prepared considering that the pilot pore volume would be
flooded at the rate of about one pore volume per year, The pilot is in waterflooding phase now. The plan
is to complete the modeling process well ahead of time to optimize the chemical ASP process for the field
applications.

Laboratory Testing - SAMA ASP Flooding Project

A suite of laboratory tests have been conducted to identify surfactants and polymers suitable for the
chemical EOR process for SAMA reservoir, and to quantify the behavior of the ASP flooding prospects. The
laboratory tests included microemulsion phase behavior tests, aqueous stability tests, selection of polymer
and rheology tests, and coreflood experiments. Two sets of SAMA laboratory tests were performed using
surrogate oil as a proxy live oil and with true live oil. Surrogate oil was obtained by diluting the dead oil
with 23.2% toluene to create an oil with the same Equivalent Alkane Carbon Number (EACN).
Core plugs were drilled from SAMA preserved whole cores and saturated with crude oil to preserve its
native state. These core plugs consists mostly of calcite and contains some iron bearing minerals such as
iron dolomite and pyrite16.

Microemulsion Phase Behavior with Hybrid Alkali

Hybrid-alkali has major advantages for ASP flooding in carbonate reservoirs without anhydrite. Hybrid-
alkalis, combining sodium hydroxide, NaOH, and sodium carbonates, Na2CO3, uses sodium carbonate as
a sacrificial agent to protect against calcite dissolution and in-situ mixing with hard brine during transport.
When hybrid-alkali solutions encounter divalent cations, carbonate complexes precipitate preventing shifts
in optimal salinity and maintaining pH greater than 12.516. Increasing pH with hybrid alkali to about 12.6,
contributed to higher oil recovery and low surfactant retention in carbonate rocks.
By measuring phase behavior, Alkaline-Surfactant formulations were examined to determine the
optimum salinity, interfacial tension, and viscosity during and after equilibration of the fluids. After allowing
the microemulsion to reach equilibrium, solubilization ratios are measured from phase volumes. The IFT and
optimum salinity are estimated by the emulsion test and from the phase behavior plot of the solubilization
ratios at equilibrium16.
A high-pressure live-oil phase behavior experiment was performed using a reconstituted live oil. Identical
low-pressure surrogate-oil phase behavior scans were completed, as well, to assess the effect of oil on the
microemulsion phase behavior. The surfactant-alkaline-polymer formulation, that showed the lowest IFT,
fastest equilibration time, and lowest microemulsion viscosities, constitutes of 1.5 wt% surfactant (0.65 wt
6 SPE-195039-MS

% C24-45PO-30EO-COO-, 0.45 wt% C15-18 IOS, 0.40 wt% C19-23 IOS,), 3500 Polymer (AN 125 SH), and
4% wt% Alkali (0.5 wt% NaOH, and 3.5 wt% Na2CO3). 0.5 wt% of Phenol-4EO was used as a solvent.
The C24 hydrophobe is more compatible with SAMA crude than other hydrophobes and forms a
smooth Type I, Type III, Type II phase transition as salinity increases. This formulation is a more
hydrophilic surfactant blend making it a more robust formulation operationally. The added hydrophilicity
also compliments the salinity gradient by balancing the incremental hydrophobic, organic soap generated
at pH 12.5.
Figure 1 presents the oil and water solubilization ratios for SAMA live oil. Figure 2 presents the oil and
water solubilization ratios for SAMA surrogate oil. The optimal salinity for the live oil is about 88,000 ppm
TDS, determined by the emulsion test. Type I microemulsions were observed at salinities below 80,000
ppm TDS and Type II microemulsions were observed above 95,000 ppm TDS. In other words, the lowest
IFT was observed between 80,000 and 95,000 ppm TDS. Qualitatively, the IFT with live crude was ultra-
low at optimal salinity, had low microemulsion viscosity and equilibrated rapidly after mixing.

Figure 1—Microemulsion Phase Behavior Using Live Oil

Figure 2—Microemulsion Phase Behavior Using Surrogate Oil

The optimal salinity for the surrogate oil is about 70,000 ppm TDS, determined by emulsion test. Type I
microemulsions formed at salinities below 60,000 ppm TDS and Type II microemulsions formed at salinities
above 80,000 ppm TDS. That is, the lowest IFT was observed between 60,000 and 80,000 ppm TDS. The
solubilization ratio at optimal salinity is about 12 cc/cc.
The solubilization ratio at the optimal salinity with live oil is about eight cc/cc, which is approximately
30% less than the solubilization ratio using the surrogate oil. The lower solubilization ratio is due to less
SPE-195039-MS 7

generated soap at high-pressure sapphire cells than in low-pressure phase behavior pipettes. This is because
mixing is more efficient in the low-pressure pipettes than in the high-pressure sapphire cells due to the lack
of headspace in the sapphire cells. The solubilization ratios are expected to increase and the optimal salinity
decrease as hydrophobic soaps are generated over time.

SAMA ASP Corefloods

Corefloods were performed at reservoir temperature, 78 °C. The cores were initially saturated and flooded
with brine, and then sequentially with oil, and waterflood brine before the ASP flood was conducted as a
tertiary flood supplemented by a polymer drive stage. All fluids including crude oil were filtered through
a 0.45 |im nitrocellulose filter before injection. Since cellulose, filters decompose at high pH, ASP slugs
and polymer drives were filtered prior to adding sodium hydroxide and then mixed with a filtered solution
of sodium hydroxide.
Large number of corefloods were needed to achieve satisfactory performance in the very difficult
SAMA carbonate cores. The majority of corefloods were designed to minimize surfactant retention. Other
corefloods were performed to evaluate the chemical process type, injection strategy, sacrificial agents, and
novel chelating agents.
Reservoir corefloods achieved low residual oil saturations (Sorc = 0 to 0.06) when NaOH was used and
had very favorable pH propagation, indicating low alkali consumption. Using only Na2CO3 resulted in a
higher residual oil saturation (Sorc = 0.1) as well as higher surfactant retention. These results show that
high pH is required to produce sufficiently negative surface charge in limestones, which is the key to reduce
the adsorption of anionic surfactants.

High-Pressure Live-Oil Coreflood

The objective of the high-pressure coreflood was to test the performance of the ASP formulation in a SAMA
composite core with live oil. The plugs of the composite core were extracted from a SAMA preserved
whole core. The composite core was left in its native state at preserved saturations and was not cleaned with
solvent prior to the high-pressure coreflood to avoid altering its wettability, which was assumed to be oil-
wet. The live oil used for the high-pressure coreflood was the same live oil used in the high-pressure live-
oil phase behavior experiment.
The average porosity and permeability of the composite core are about 21% and 8.0 mD respectively.
The pore volume and saturations (Soi, Sorw, Sorc) were unknown until the pore volume was measured with
a salinity tracer at the end of the chemical flood and subsequent solvent cleaning. Once the pore volume
was measured, the remaining oil to water flood is simply the total pore volume minus the aqueous pore
volume after water flood, measured via salinity tracer. Initial oil is the remaining oil after water flood plus
the oil recovered from the water flood. For this high-pressure coreflood case, the initial oil has considerable
uncertainty because the oil recovered from the water flood was severely emulsified by 2400 psi pressure
drop and evolution of solution gas across the high pressure Back Pressure Regulator, BPR.
Table 1 presents the injection sequence for this live-oil, high-pressure, and high-pH ASP coreflood.
It starts with a waterflood, followed by preflush, and ASP slug and ends with polymer drive. After
the waterflood, all injected solutions contained alkalis of 0.5% NaOH and Na2CO3 at variable weight
percentages. The preflush was injected above optimum salinity with 4.0 wt% Na2CO3, the ASP slug was
injected at optimal salinity with 3.5 wt% Na2CO3, and the polymer drive was injected below optimum
salinity, with 0.25 wt% Na2CO3 to create a favorable salinity gradient. The polymer drive was diluted
to 30,000 ppm TDS to ensure surfactant transitioned into type I microemulsion even at dilute surfactant
concentrations. All solutions containing polymer were pre-sheared for 5 seconds before injection. Further,
they were co-injected with the co-solvent (phenol-4EO) to improve injectivity.
8 SPE-195039-MS

Table 1—Injection Sequence of the High-Pressure Live-Oil Coreflood, Indicating Incremental and
Cumulative Pore Volume Injected, the Injection Rates and Time Needed to Complete Each Flooding Stage

The oil recovery from the high-pressure, high-pH ASP flood resulted in a final residual oil saturation of
0.05 and 90.5% recovery of the remaining oil after waterflood. Figure 3 presents cumulative oil recovery
as a percent of remaining oil saturation to water flood, residual oil saturation to chemical flood and oil cut
on the left y-axis. Surfactant concentration data in the effluent are plotted against the right y-axis.

Figure 3—High-Pressure, High-pH ASP Flood: Oil Recovery, Oil Cut, Residual Oil Saturation, and Surfactant
Concentration vs. Pore Volume Injected. 0.41 PV Preflush, 0.47 PV ASP, and 6.85 PV of Polymer Drive.

Mass of surfactant retained is 0.17 mg surfactant/mg rock with surfactant breaking through at 1.2 PV
injected. Some oil production (oil cut > 0) resulted from the high pH preflush phase. After producing the
oil bank (relatively higher oil cut values), a long tail of oil cuts was observed indicating the oil-wetness of
the SAMA composite core.

Low-Pressure Surrogate-Oil Coreflood

This coreflood is the closest to the performance of the one-spot pilot (SWCTT, Single Well Chemical Tracer
Test) conducted in one of the wells in SAMA in terms of residual oil saturation measurement and pore
volume injected. In terms of oil recovery as a function of PV injected, this coreflood looks much better
than the previous one as the oil recovery is obtained after ~4 PV of injection whereas the previous one
obtained after ~7 PV.
The objectives of the low pressure oil recovery reservoir coreflood was to evaluate the effectiveness of
different chemical formulations in reservoir rock and optimize the recovery process for the mineralogy,
SPE-195039-MS 9

pore structure, and wetting state of the SAMA rock. The average porosity and permeability of the cleaned
composite core in this low-pressure high-pH coreflood is about 22% and 60 mD respectively.
The injection scheme of the low-pressure, surrogate-oil coreflood is the same as that of the high-pressure,
live-oil coreflood, as reflected in Table 2. The injection salinities were modified, however, to better suit
the low-pressure surrogate-oil phase behavior. Further, the weight percent of Na2CO3 in the ASP slug was
modified to be 2.5 wt% instead of 3.5 wt%. Moreover, the preflush in this coreflood was performed at a
frontal velocity of about 1 ft/day, while that of the high-pressure flood was performed at an injection rate
of about 0.40 ft/day. On the other hand, the ASP slug and the polymer were performed at frontal velocities
of about 1.00 ft/day, while that of the high-pressure coreflood was performed at 1.77 ft/day.

Table 2—Injection Sequence of the Low-Pressure Surrogate-Oil Coreflood, Indicating Incremental and
Cumulative Pore Volume Injected, the Injection Rates and Time Needed to Complete Each Flooding Stage

Figure 4 presents the performance of this coreflood. The oil recovery from this high-pH ASP flood was
relatively high, with a final residual oil saturation of 5.4% and 91% OOIP oil recovery. Increased oil cuts
during the preflush stage indicates a shift in wettability and rock surface charge and/or formation of organic
soaps found naturally in the oil. Surfactant retention was measured to be 0.51 mg surfactant/mg rock. The
actual retention seemed to be much lower, but difficulty in processing surfactant in effluent samples made
it difficult to confirm that.

Figure 4—Low-Pressure, High-pH ASP Flood: Oil Recovery, Oil Cut, Residual Oil Saturation, and Surfactant
Concentration vs. Pore Volume Injected. 0.90 PV Preflush, 0.39 PV ASP, and 3.15 PV of Polymer Drive.
10 SPE-195039-MS

Note the production of the oil bank in this coreflood started right after injecting about 0.1 PV of the ASP
slug. The additional effect of alkali, in the preflush, generating soaps, may have mobilized some oil ahead
of the injection of the ASP slug. The propagation of the pH front was good, breaking through at around 0.3
PV injected, with a fluids of greater than 12 pH breaking through at about 0.8 PV injected.
The pressure drop across the composite core started to build up at the start of the preflush stage. Half
way through this stage the pressure differential started to drop until the start of the ASP slug stage at which
time, the pressure differential start to increase gradually again due to the injection of the higher viscosity
ASP slug. This behavior continued during the polymer drive with a little jump in pressure differential at the
start of the polymer drive stage, due to its higher viscosity compared to the ASP slug. The preflush pressure
increase is likely due to the formation of emulsions in the core due to the presence of alkali. Indeed, this
pressure differential could have contributed to the early production of the oil bank.
Viscosity of effluent samples were measured at 3.5 pore volumes injected. The viscosity ratio was found
to be about 1.4. A viscosity ratio greater than 1.0 indicates the polymer solutions did not degrade during the
flood, but continued to hydrolyze as the fluids propagated, which increases their viscosity.

Modeling and Calibration of ASP Corefloods

Both the high-pressure and the low-pressure ASP corefloods resulted in good incremental oil production
and gave the operator the confidence that ASP flooding holds a good potential for enhancing the oil recovery
from SAMA reservoir. To be able to advance to a field pilot level, the laboratory coreflood experiments were
modeled and calibrated. A state of the art, Equation-of-State, Compositional Simulator, CMG-GEMTM, was
utilized for this purpose. In addition to modeling the physics of multiphase flow in porous media, CMG-
GEMTM can efficiently model several additional mechanisms needed for modeling ASP processes.

Description of ASP Flooding Models

The corefloods were modeled as a 1-D vertical configuration model consistent with the laboratory setup.
The composite core (~1 ft long) was subdivided into about 100 grid blocks for the high-pressure coreflood,
and 120 grid blocks for the low-pressure coreflood. In both models, two smaller grid blocks were added at
the two ends of the core to represent the injection and production ends of the coreflood. A single porosity
of ~21% was assigned for the all grid of the first coreflood, and ~ 22% for the grid blocks of the second
coreflood. Different permeability was assigned to each of the four sections of the composite cores of the
two corefloods. A five component, EOS was used for the live oil in the modeling process. One set of
relative permeability curves was used for all four sections of each of the composite cores. Data needed for
the modeling of ASP corefloods included microemulsion and saponification data, surfactant and polymer
adsorption data, polymer solutions rheology data, and relative permeability interpolation data.
Three components were utilized to account for salinity in these corefloods. These were Sodium ion,
Na+, Soda Ash, NaOH, and Sodium Carbonate ion, NaCO3-. Considering only four aqueous reactions in
the modeling of both corefloods, resulted in the addition of eight aqueous components to the model. The
aqueous reactions used are as follows:
1. 'H+' + 'OH-' = 'H2O'
2. 'H+' + 'CO3––' = 'HCO3-'
3. 'H+' + 'NaCO3-' = 'HCO3-' + 'Na+'
4. 'HAo' = 'H+' + 'Aw-'
Other components included in these models include polymer, surfactants, in addition to the oil acid
component. Ion exchange was not activated, as it was judged as not important for these ASP floods.
Microemulsion phase behavior was input in terms of solubilization ratios versus salinity versus synthetic
surfactant concentration. Solubility ratios were converted to IFT versus salinity, as indicated above. An input
SPE-195039-MS 11

of the slope of the activity map (ie. delta salinity/delta So) prepared in the laboratory enabled the calculation
of the solubility ratio (and IFT) behavior at different oil saturations (ie. different WOR's) from the input
solubility ratio table. Therefore, a separate input of solubility ratio vs. salinity at different oil- water-ratios
was not required for the consideration of microemulsion phase behavior as a function of oil saturation. Live
oil solubilization ratios were used for the high-pressure coreflood, while that of the surrogate oil were used
for the low-pressure coreflood.
Polymer adsorption was not measured, and therefore an estimate was used for this parameter and was
considered as one of the history matching parameters. Surfactant adsorption was measured in the lab, but
with certain degree of uncertainty, and was therefore used as a history matching parameter but with smaller
range of variation. The high pH coreflood resulted in lower surfactant retention and therefore an option to
change the adsorption as a function of pH was used, and the parameters to define this variation were used
as history matching parameters. The surfactant adsorption as a function of pH is definitely important for
sector pilot model or full field models, as more pH variation is expected.
The surfactant adsorption as a function of time is a phenomenon that is frequently ignored in simulation
as the adsorption reaches equilibrium levels within a few hours or days in the laboratory. This time to reach
equilibrium is definitely short for field scale simulation cases and can be ignored. However, for laboratory
scale corefloods, this time is not short and if this phenomenon is ignored, it can lead to incorrect adsorption
levels being used to match the corefloods, which would cause incorrect values to be used in field scale
simulations. Therefore, a time dependent adsorption option was used as another history matching parameter.
The rate dependent adsorption equation is as follows:

Where
= moles of adsorbed component i per bulk volume at time n+1
= moles of adsorbed component i per bulk volume at equilibrium (from the tabular data)
 ki = adsorption rate constant in (1/s) - keyword ADSRATE
Polymer rheology was input in terms of viscosity data as a function of polymer concentration, salinity,
and shear rate. Two different tables were utilized, one for the polymer in the ASP blend, and the other
for the polymer in the polymer drive stage. The compositions of the injected fluids, in terms of all of the
components of the model, were considered for the waterflood, preflush, ASP slug and polymer drive stages.
Based on pore volumes injected for each stage and rate of injection, injection time was back- calculated
considering the pore volume of the composite core.

Calibration of ASP Corefloods

After carefully designing the base model for each coreflood, model calibration was undertaken. The
calibration process was performed in three phases, calibration of the waterflood phase, calibration of the
ASP flooding phase matching only surfactant production, and calibration of ASP flooding phase matching
all other parameters except surfactant production. The CMG-CMOST-AITM optimization software was
utilized for the assisted history matching (calibration) process.
The waterflood phase continued until about 99% watercut and stable pressure differential across the
core. Calibration of waterflood phase, involved history matching the experimentally measured data of
cumulative oil produced, the residual (remaining) oil saturation, and measured pressure differential data. The
most uncertain parameters in the waterflood phase were the water/oil relative permeability curves, as other
parameters were measured in the lab. The residual oil saturation to water, Sorw, oil relative permeability
at connate water saturation, Krocw, water relative permeability at residual oil saturation to water, Krwro,
12 SPE-195039-MS

in addition to the shapes of the oil and water relative permeability curves were considered as the tuning
parameters for the history matching process.
The second calibration phase that required the matching of only the surfactant production, required
adjustment of the surfactant adsorption data, including adsorption as a function of pH and time. Once this
match was obtained, these parameters could be fixed as the remaining matching parameters have a very
small effect on the surfactant production.
The calibration of the ASP Flood phase involved history matching of the experimental measured data of
cumulative oil produced, the molality of any of the measured effluents such as surfactant, polymer and/or
NaCO3--, and the pressure differential across the core. The tuning parameters used for the calibration of the
model during the ASP flooding phase included:

• The saturation and relative permeability endpoints of the second set of the interpolation Kr curves,

• The value of the capillary number at which the second Kr set is invoked,

• The polymer adsorption data,

• The soap/surfactant ratio value for the microemulsion optimum salinity,

• The microemulsion viscosity, and

• The viscosity of the polymer solution if not measured in the laboratory.

Calibration of High-Pressure Live-Oil Coreflood

The calibration of the high-pressure, live-oil ASP coreflood is presented in Figure 5. Indicated on this figure,
the four injection stages of the coreflood, waterflood, preflush, ASP slug, and polymer drive stages (Refer
to Table 1 for more details).

Figure 5—Measured vs Simulated of Oil Average Saturation, Pressure Differential across Section 4 of
the Composite Core, and the Molality of Surfactant Effluent for the High-Pressure, Live-Oil coreflood
SPE-195039-MS 13

As was mentioned previously, the match of the surfactant production was done separately before
matching the remaining parameters. This excellent match, shown in Figure 5, was obtained using an
adsorption rate constant (using the keyword of ADSRATE) of 4.25e-4 sec-1. The surfactant production
curve without using the keyword ADSRATE is also shown in Figure 5. Without this option, the surfactant
adsorption coefficient must be increased by 49% to obtain a surfactant production match, but as can be seen
the profile of this match is delayed. This is an example of how a match without the use of an adsorption
rate constant would lead to over estimates of surfactant adsorption.
The experimental data exhibited a slow oil recovery during the polymer drive stage. This is represented
by the long tail of the reduction in average oil saturation curve and required injecting relatively large number
of pore volumes of polymer solutions to complete the experiment. This signifies the oil wetness of the
carbonate rock, where oil is residing in the relatively smaller pores, while the polymer solution (water phase)
is flowing in the relatively larger pores. The model missed matching the breakthrough of the oil bank, but
was able to follow the slow recovery of the oil bank accurately.
The pressure differential across the composite core was matched accurately, during the waterflooding
phase. Its match during the ASP slug phase, however, was not that good. The experiment experienced an
unusual increase in pressure, for which the reasons were not very clear. The unusual pressure behavior was
seen mostly in sections 1 to 3 of the composite core, but to much less extent in the last section, section 4,
of the composite core. The model was able to get a fair match of the pressure differential across section
4, as shown in Figure 5.
The tertiary recovery process at optimum salinity or at under optimum salinity depends mostly on the
second set of the interpolation Kr curves and any interpolated curves with the first Kr set (waterflood set)
or the third Kr set (set of the microemulsion phase at optimum salinity). Figure 6 presents the shape and
the end-points of the second set of Kr curves (the interpolation Kr curves) that resulted from the coreflood
history matching process. The revision of the Kro curve at the lower oil saturation range as indicated in the
red circle in Figure 6, reflecting the oil wetness tendency of the composite core, allowed for continuous oil
production at lower oil cuts even after several pore volumes of polymer injection. The revision of the Kro
curve gave a better match of the average oil-saturation values (oil recovery value), as can be seen in Figure 5.

Figure 6—Water/Oil Kr Curves of the High Pressure Coreflood History Match

14 SPE-195039-MS

Calibration of Low-Pressure, Surrogate-Oil Coreflood

The calibration of the low-pressure surrogate-oil coreflood was also obtained in a stepwise fashion with
the same three steps that were used for the high-pressure, live-oil coreflood match. After calibrating the
waterflood phase, the calibration continued with the match of the surfactant production that required
adjustment of the surfactant adsorption data as a function of pH and time. However, for this coreflood
some iterations were required between matching only surfactant production, and matching all parameters
together, in order to obtain the best match. It was found that the match of the surfactant production was also
sensitive to the micro-emulsion (ME) viscosity parameters. As shown in Figure 7, two surfactant production
curves were shown with and without ME viscosity. It is clear that a better match of surfactant production
was achieved by considering the ME viscosity parameters, along with the surfactant adsorption parameters.

Figure 7—Measured vs Simulated Surfactant Production of the Low Pressure Coreflood

The effect of the keyword, ADSRATE, specifying the adsorption rate constant, on the matching of the
surfactant production is also shown in Figure 7. The surfactant production was delayed without the use of the
keyword. As the surfactant adsorption for this coreflood is much higher than for the high pressure coreflood,
the delay of surfactant production was found to be also much longer without the use of ADSRATE. This is
another example of how the use of ADSRATE will enable a much better calibration of surfactant adsorption.
Figure 8 illustrates the performance of the best-matched case that resulted from the assisted history
match. The four injection stages, including the waterflood, preflush, ASP slug, and polymer drive stages,
are indicated on these figures (refer to Table 2 for more details). This history match was obtained by tuning:

• The saturation and relative permeability endpoints of the second set of interpolation Kr curves,

• The threshold value of the capillary number at which this second set of Kr curves is invoked,

• The adsorption level of polymer solution,

• The viscosity of the water and oil micro-emulsions, and

• The soap ratio with optimum salinity gradient.

SPE-195039-MS 15

Figure 8—Measured vs simulated percent oil recovery of the residual oil to waterflood &
Pressure Differential across the Composite Core for the Low-Pressure, Surrogate-Oil coreflood

To prevent gas formation in the coreflood during the modeling process, the backpressure of the flood
was set to a pressure higher than the bubble point pressure of the surrogate oil. The measured data were
manipulated to match the inlet pressure of the coreflood. Close inspection of the experimental measured
data, as well as the capability of the model to match these data, exposed two challenging issues that need
more attention and clarifications:

• Normally waterflood stage is ended only after the pressure differential stabilizes and the WOR
reaches to about 99%. Further, the preflush stage is performed to precondition the salinity of the
formation water before the injection of the ASP slug, and it is not expected to produce any oil.
Injection of preflush fluid resulted in some oil production, as can be seen in Figure 8.
• The injection pressure exhibited normal behavior as the pressure decreased at the start of the
preflush stage because the preflush injection rate is half the rate of the previous waterflood stage.
Starting at the onset of the pre-flush stage, however, the injection pressure exhibited unusual
behavior as it began to increase to a peak at ~2.3 PV, then decreased. The injection pressure began
to increase again once the ASP injection stage began, which is the expected normal behavior.
The preflush water was injected above optimum salinity with 0.5 wt% NaOH and 4.0 wt% Na2CO3.
The incremental oil produced from this pre-flush stage indicates that the alkali is creating soap and IFT
reduction is occurring. The pronounced increase of pressure during the preflush stage indicates that a
micro-emulsion is created from this soap and this micro-emulsion (ME) phase has a significantly increased
viscosity. As shown in Figure 8, the effects of the ME viscosity has a significant effect on both the pressure
and oil recovery curves as the curves without ME viscosity do not show a pressure increase or oil recovery
increase until much later than observed in the coreflood. However, even with this ME viscosity option in
the simulator, the model still does not predict a pressure increase early enough in the pre-flush stage, as
measured in the lab.
16 SPE-195039-MS

The current model setup with the input of the solubilization ratio tables will not predict IFT reduction
and the formation of the micro-emulsion phase unless surfactant is present. The current model does have
the options to predict IFT reduction and ME phase, due to the presence of alkali with no surfactant present.
Due to this issue, the model predicted increase of pressure is later than observed in the lab. As a workaround
for this match, a small amount of surfactant was included in the composition of the injected preflush fluid
which allowed some increase of pressure due to the ME phase, but still somewhat late. This small amount
of surfactant also caused an increase of the oil production rate during the preflush stage that is slightly early
compared to the lab-measured data.
Figure 8 also shows the additional prediction without ADSRATE. Interestingly, this curve resembles the
curve without ME viscosity because the high surfactant adsorption causes the surfactant to be not available
for the formation of the ME phase, and therefore the ME viscosity does not increase and the pressure also
does not increase until much later than observed in the coreflood.
Figure 9 shows the three sets of water oil relative permeability curves used in the model. As can be seen
in this figure as the capillary number increases, the Krw curves increase until achieving the straight-line
miscible curves shown as set #3. In addition, the Kro curves show a similar increase with a reduction of
residual oil saturation with increasing capillary number (increasing set number).

Figure 9—Water/Oil Kr Curves of the Low Pressure Coreflood History Match

Summary and Conclusions

• The challenges associated with ASP flooding in carbonate reservoirs are summarized in this paper,
which presents two corefloods in carbonate composite cores of the SAMA reservoir; high-pressure,
live-oil coreflood, and low-pressure, surrogate-oil coreflood.
• The paper presented the key mechanisms that need to be considered for accurate modeling of the
ASP flooding process.
• Accurate modeling of the ASP flooding process requires an extensive amount of experimental data.
The more collected data, the more confidence we have in the chemical parameters produced by
history matching.
SPE-195039-MS 17

• The study was able to achieve good history matches for the experimental data of both the high-
pressure live oil, and the low-pressure surrogate oil corefloods.
• The history matches of both differential pressure and oil recovery depended to a high degree on
the increased viscosity due to micro-emulsions.
• The history matches of surfactant production depended on the pH as well as the adsorption rate as
a function of time. Without using adsorption rate as a function of time, the surfactant adsorption
coefficients obtained from a coreflood history match may not be representative.

Acknowledgments
The authors of this paper would like to thank Kuwait Oil Company and Computer Modeling Group for
granting permission to publish this paper. This authors would also like to acknowledge Ultimate EOR for
performing the coreflood experiments.

Nomenclature
ASP = Alkaline-Surfactant-Polymer
BPR = Back Pressure Regulator
DPR = Disproportionate Permeability Reduction
EACN = Equivalent Alkaline Carbon Number
EOR = Enhanced Oil Recovery
IFT = Interfacial Tension
IPV = Inaccessible Pore Volume
Kr = Relative Permeability Curves
Kro = Oil Relative Permeability Curve
Krocw = Oil Relative Permeability at Connate Water Saturation
Krw = Water Relative Permeability Curve
Krwro = Water Relative Permeability at Residual Oil Saturation to water
ME = MicroEmulsion
Nc = Capillary Number
pH = fluid acidity
ppm = Parts per Million
PV = Pore Volume
R= Solubilization Ratio
Ro = Oil Solubility
Rw = Water Solubility
Soi = Initial Oil Saturation
Sorw = Residual oil Saturation to Water
Sorc = Residual Oil Saturation to Chemicals
SWCTT = Single Well Chemical Tracer Test
TDS = Total Dissolved Solid
Wt% = Weight Percent
WAG = Water Alternating Gas
WOR = Water Oil Ratio

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