SPE 123866

A New EOR Method

S. Hamid Behzadi and Brian F. Towler, SPE, University of Wyoming

Copyright 2009, Society of Petroleum Engineers

This paper was prepared for presentation at the 2009 SPE Annual Technical Conference and Exhibition held in New Orleans, Louisiana, USA, 4–7 October 2009.

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Abstract

A new method of enhanced oil recovery has been developed and applied to a sector simulation using
some of the data from the South Slattery Field, Minnelusa A reservoir. The new method, termed
ASPaM, combines features of CO2 miscible flooding with Alkaline-Surfactant-Polymer (ASP) flooding
to produce an enhanced WAG flood. A numerical pre-processor program had to be developed to
produce the required mixing zone properties of a CO2 front, which are input to the CMG simulator,
STARS. STARS is a chemical flood simulator, but cannot accomodate the solvent model. The pre-
processor calculates oil and solvent properties based on the Todd-Longstaff procedure. Sensitivity
analysis showed this new method can give a much better recovery in comparison to ASP or CO2 WAG
flooding for different depositional environments. ASPaM benefits from high micro and macro sweep
efficiencies plus miscible flooding, even for a small ASP slug size. The simulation results revealed the
recovery from this scheme is considerably better than ASP and CO2 flooding separately. It showed the
recovery can be improved and accelerated by the application of ASPaM, and its performance is a
function of the miscibility of the CO2-oil miscible zone and the reduction in IFT at the ASP-oil interface
at reservoir conditions. Moreover the water/gas ratio of ASPaM is totally different in scale compared to
a typical WAG scheme. A significant acceleration and improvement in recovery is achieved with a 10 %
pore volume ASP slug size. This work indicates CO2 flooding and sequestration can be stabilized and
enhanced if it combines even with a small ASP slug size. The results so far have been very encouraging.
Introduction
Carbon dioxide has been used for enhanced oil recovery (EOR) purposes since the 1950's (Izgec et al,
2005). Research on the use of CO2 for EOR continues with ever growing interest; however, research
concerning terrestrial sequestration of CO2 for environmental purposes is relatively recent (Jessen et al,
2001). The CO2 can make up multi-contact and first contact miscibility with oil at reasonable reservoir
pressures while other miscible gases may not reach this point for up to a couple of thousand psi more.
Although the microscopic sweep effciency of carbon dioxide flooding is good, its macroscopic sweep
effciency is relatively poor due to phase segregation and unfavorable mobility ratio. However, the WAG
gas injection scheme was originally proposed to tackle this shortcoming, mainly by using the water to
control the mobility of the displacement and to stabilize the front.
WAG injection has been applied with success in most field trials. The majority of the fields that have
been WAG flooded, are located in Canada and the U.S., but there are also some fields in the former
2 SPE 123866

USSR (Nelson et al, 1984). WAG injection has been employed since the 1960's. Both miscible and
immiscible injections have been used with many type of gas (Christensen et al, 2001). The terminology
of miscible WAG, here, means the gas/oil miscibility may be attained by multiple-contact.
However, the WAG mobility control is not feasible in high or medium viscosity oil; but it can be
upgraded by using polymer to raise the aqueous phase viscosity. Moreover the microscopic sweep
effciency of the water slug can be improved, if the interfacial tension (IFT) of the water/oil interface is
reduced. Alkaline-Surfactants are typical additives offering considerable IFT reduction and
consequently oil recovery improvement. The alkali converts naphthalic acids in the crude oil to soaps.
The combination of the soaps and a suitably chosen injected surfactant reduces the interfacial tension to
ultra low values, where residual oil can be mobilized and oil trapping prevented and it also reduces
surfactant adsorption (Liu et al, 2008). Soaps are usually too lipophilic to produce ultra low interfacial
tension at reservoir conditions. Effective, hydrophilic, injected surfactants can be injected in an alkaline-
surfactant process at salinities below their optimal salinities for oil recovery when used in the absence of
alkali (Nelson et al, 1984).
This is investigated in application to the South Slattery Field in Wyoming, which has been previously
studied by Sheppy (1986), Towler (1991) and Gao and Towler (2009). The South Slattery Field is a
small Minnelusa field in the Powder River Basin with about 12 MMSTB oil in place. Different chemical
flooding scenarios have been investigated in addition to the new methodology, ASP alternating with
miscible CO2 (ASPaM) to improve recovery. Simulation of a sector of the field was carried out using
STARS, the advanced chemical flood simulator from CMG. The historical water flood data has been
matched and a chemical flood model was investigated, which included accounting for chemical
adsorption, the residual resistance factor, surface tension as a function of the chemical concentration and
interpolation of relative permeability based on capillary number and solvent concentration.
Theoretically, the South Slattery Field contains all of the conditions that CO2 flooding needs; depth,
temperature, oil gravity, porosity, permeability, etc. A continues CO2 injection was used for comparison
in the simulation research. The existence of a density difference causes the CO2 to distribute unevenly.
The CO2 sweep effciency is low due to reservoir heterogeneity and unfavorable mobility ratio, which
controls the volumetric sweep effciency between the injected phase and displaced oil bank. Although,
the water-flooding performance can be improved by using ASP as a capillary-induced bypassing and the
reduction of viscous fingering. The CO2 flooding is a well recognized and tested enhanced oil recovery
method because the microscopic sweep effciency of CO2 flooding is very high. But its volumetric sweep
effciency is a cause for concern. The CO2 dissolves easily in oil and reduces the oil viscosity, swells the
oil and extracts the light components.
Simulation
The advanced process chemical flood simulator, STARS, was used to simulate the different chemical
scenarios. STARS has the ability to simulate all aspects of ASP flooding but it cannot handle the
miscible phase. No commercial simulator can accommodate both ASP and miscible flooding.
Consequently we calculated the oil and solvent properties separately using the Tod and Longstaff (1972)
method described below. The following features were applied to simulate the required fluid-fluid and
fluid-rock interactions:
• IFT reduction for up to two components.
• Modification of the relative permeability from reduction in capillary number.
• Water viscosity increased by adding polymer.
• Adsorption of chemical components.
• Residual resistance factor due to adsorption.
SPE 123866 3

• Alteration of oil relative permeability owing to miscible flooding.

• Oil density reduction due to swelling.
• Reduction of oil viscosity by dissolution of CO2 in oil.
• Alkaline consumption by carbonic acid.
A key feature in the modeling by STARS is, it interpolates between different sets of relative
permeability curves based on capillary number calculated by:
Nca = (v*µ) /σ ……………….. (1)
Where Nca is the capillary number v is the velocity of the fluid μ is viscosity σ is IFT between oleic and
aqueous phases.
The injection of chemicals which decrease the IFT, increase the capillary number, which translates into
a change in relative permeability and a reduction in the residual oil saturation. The stoichiometric
chemical reaction option in STARS enables us to model the consumption of injected chemicals and
resulting reaction products, which might restrict a fluid flow. This feature can also be use to model the
interaction of alkali with the rock, resulting in the loss of alkali; as well as reaction of the alkali with
naturally occurring acids in the oil to generate additional in-situ surfactant (Pandey et al, 2008).
Here, eight components have been used to properly model the complex IFT change, chemical
adsorption, miscible and dissolution phenomenons. The multiple alkaline consumption reactions such
as; formation brine, cation exchange, hydrogen ion exchange reaction with petroleum acids, silica
dissolution and kaolinite transformation are lumped to the adsorption of alkaline to the rock, except for
the reaction with the carbonic acid. This helps us to keep accuracy, reduces simulation time and
numerical failure. The liquid-gas k-value tables were not required for dead oil but are necessary for
dissolution of carbon dioxide in water. The Duan (Duan et al, 2005) model is used for the calculation of
the solubility of carbon dioxide in aqueous solutions containing Na+, K+, Ca2+ , Mg2+, Cl-1 and SO-4 in a
wide temperature, pressure and ionic strength range.
ln (mCO2 ) = ln(yCO2ФCO2P) - μ1(0)CO2 /RT + 0.07mSO4 -2λCO2-Na(mNa + mK + 2mCa + 2mMg)
-ζCO2-Na-Cl mCl (mNa + mK + mCa + mMg) ………………… (2)
where T is absolute temperature in Kelvin, P represents the total pressure of the system in bar, R is
universal gas constant, m means the molality of components dissolved in water, yCO2 is the mole fraction
of CO2 in the vapor phase, ФCO2 is the fugacity coeffcient of CO2, μ1(0)CO2 is the standard chemical
potential of CO2 in the liquid phase, λCO2-Na is the interaction parameter between CO2 and Na+, ζCO2-Na-Cl
is the interaction parameter between CO2 and Na+,Cl-. All parameters presented in equation 2 can be
calculated directly without any iteration, except the fugacity coeffcient of CO2, ФCO2 , which is
calculated from the fifth order virial EOS developed by Duan et al. (Duan et al, 1992), and a time-
consuming iterative procedure was needed to solve the EOS (Duan et al. 2005). He offered an equation
to calculate ФCO2 as a function of temperature and pressure.
ФCO2 = c1 + [c2 + c3T + c4/T + c5/ (T – 150)] P+ [c6 + c7T + c8/T] P2
+ [c9 + c10T + c11/T] ln (P) + [c12 + c13T]/P+c14/T+ c15T2…… (3)
where T is in Kelvin and P in bar. The parameters ci’s were fitted to ФCO2 calculated from the EOS of
Duan et al. (Duan et al, 1992) at the T-P range where CO2 solubility model is valid. They reproduce
ФCO2 over a wide T-P range with a single set of parameters as it was not feasible to employ only one set
of parameters. Thus, they divided the T-P range into six sections and fit a set of parameters for each
4 SPE 123866

section (Duan et al, 2005). Table 1 lists the parameters for equation 3. The dissolution of carbon dioxide
is simulated in an authors’ program which produces an adequate feed for STARS.

Table 1: Parameter of equation 3 (Duan et al, 2005)

T-P
Par a b c
1 2 3 4d 5e 6f
c1 1 -7.17E-01 -6.51E-02 5.03839 -16.0632 -1.57E-01
c2 4.76E-03 1.60E-04 -2.14E-04 -4.43E-03 -2.71E-03 4.46E-04
c3 -3.36E-06 -4.93E-07 -1.14E-06 0 0 -9.11E-07
c4 0 0 0 1.957273 1.41E-01 0
c5 -1.31794 0 0 0 0 0
c6 -3.84E-06 -2.79E-07 -1.16E-07 2.42E-06 8.11E-07 1.06E-07
c7 0 1.19E-09 1.20E-09 0 0 2.43E-10
c8 2.28E-03 0 0 -9.38E-04 -1.15E-04 0
c9 0 0 0 -1.5026 2.389567 3.59E-01
c10 0 0 0 3.03E-03 5.05E-04 6.33E-05
c11 0 0 0 -31.3773 -17.7635 -249.897
c12 -96.5395 -221.343 -12.8471 985.9223 0
c13 4.48E-01 0 0 0 0
c14 101.8108 71.82039 0 0 888.768
c15 5.38E-06 6.61E-06 -1.51E-05 -5.50E-07 -6.63E-07

a: 273 K < T < 573 K, P < P1 when T < 305 K, P1 equals to the saturation pressure of CO2; when 305 K < T < 405
K, P1 = 75+(T-305)* 1.25 when T > 405 K, P1 = 200 bar b: 273 K <T <340 K, P1 <P < 1000 bar c: 273 K<T
<340 K, P >1000 bar d: 340 K<T<435 K, P1 <P <1000 bar e: 340 K <T <435 K, P >1000 bar f: T >435 K, P

The ASP data published for Mangala Field (Pandey et al, 2008a; Pandey et al, 2008b) was used for this
simulation. The table 2 shows IFT data used to calculate capillary numbers in the simulation model,
which was measured in softened injection water as a function of alkali concentration using a spinning
drop tensiometer (Pandey et al, 2008b). In addition, the value of the adsorption of polymer, alkaline,
surfactant, accessible pore volume and residual resistance factor were considered in the simulations. The
relative permeability shifts from purely immiscible to miscible as the capillary number changes from
Log(Nca)=-6 to 0.5.
SPE 123866 5

Table 2: IFT measurement (Pandey et al, 2008).

Alkali IFT (dyne/cm)
Concentration Zero 0.1% Wt
Wt% Surfactant Surfactant
0 14.03 0.8847
0.1 0.1 0.01
0.25 0.015 0.0038
0.5 0.0087 0.0035
0.75 0.0057 0.0019
1 0.0033 0.0017
1.25 0.0034 0.0008
1.5 0.0061 0.0005
1.75 0.0063 0.0005
2 0.0074 0.0005

The miscible displacement was modeled in a separate program which produces the mixing zone data for
application in STARS and compares the result of this adapted STARS model with a miscible simulator
to make sure the required accuracy is achieved. This software, written by the first author, is a solvent
simulator, and converts mixing zone properties to a series of reactions and components, which can be
used in STARS easily. The Todd and Longstaff (1972) miscible model was used to calculate the four
component version of miscible displacement, which has already been proved for linear and radial
displacement.
The following equations show how the miscible zone properties were calculated. The relative
permeabilities of the miscible oil and gas might be determined as follows (Todd and Longstaff, 1972):
Kro = (So /Sn) * Krn …………………….. (4)
Krg = (Sg/Sn) * Krn …………………….... (5)
Where Krn is the imbibition relative permeability of the non-wetting phase and Sn is the non-wetting
phase saturation. Equations 6 and 7 describe the effect of partial mixing of effective viscosities in terms
of an empirical model suggested by K.S. Lee and E.L. Claridge of the Shell development company:
μoe = μ1-ωo - μωm ……………………………(6)
μge = μ1-ωg - μωm ….……………………….. (7)
Where ω is the mixing parameter and μm is the mixture viscosity which is determined by ¼ power
fluidity-mixing rule.
(μm )1/4 = ( Sg/Sn ) * (μg)1/4 + ( So/Sn)* (μo)1/4 (8)
In addition the effective density can be calculated by:
ρoe = ρo( So/Sn)oe + (ρg)[1 - ( So /Sn)oe] ……. (9)
ρge = ρo( So/Sn)ge + (ρg)[1 - ( So /Sn)ge] ……(10)
6 SPE 123866

( So/Sn)oe=[(μo/μg)1/4- (μo/μoe)1/4]/[ (μo/μg)1/4 -1]……….(11)

( So/Sn)ge=[(μo/μg)1/4- (μo/μge)1/4]/[ (μo/μg)1/4 -1]……….(12)

Results
Our sector model has 20*20*3 grids with 10ft equal dimensions and
the injector and producer are diagonally located in the model. The 30 ft
thickness should be good enough to see the effect of phase segregation
where the oil API is 32. Moreover the viscosity instability in the
water/oil front is a detriment to the displacement as the viscosity ratio
is 30 and for the gas/liquid is much more than this. The first part of the
simulation was to make sure the adapted STARS input can simulate
the miscible displacement properly. The full sector model has been
used where all three main multiphase flow forces; gravity force,
viscosity force and capillary force are magnified to make sure it can
handle complex systems. To validate this method the simple solvent
approach used in STARS is compared with CMG’s compositional Figure 1: Comparison of Cum. and
daily production of adapted STARS and
simulator IMEX. Figure 1 shows the cumulative and daily production IMEX.
of the adapted STARS and IMEX models. The STARS results are
consistent with the IMEX simulator results.
One of the interesting features of ASPaM is that ASP and CO2 have a positive coupling effect on each
others displacement, especially the injectivity. Patel et al. (1987) observed that carbon dioxide injectivity
improves in more water wet systems. Therefore the wettability alteration by the ASP slug enhances the
injectivity of the CO2 injection. However this positive effect
has not yet been formulated and can not be implemented in this
simulation. The carbon dioxide also has a positive effect on
ASP flooding. Because the carbon dioxide slug, injected in
front of ASP, can reduce the oil viscosity significantly and
consequently improve the areal sweep effciency of ASP
flooding as well as its injectivity which is a genuine concern at
the field scale. However, even in our simulation experiment,
the injectivity in the linear pattern was raised 14 times, due to
some of the effects listed above. Figure 2 shows the water
breakthrough can be postponed by more than 8% pore volume
(PV) water injection by the use of a 4 % PV CO2 slug at the
front of ASP, which simply implies a piston like displacement.
In addition the injectivity of the ASP increased up to 55% for a
11% CO2 slug. Therefore we can say the combination of these
Figure 2: positive coupling effect of
two mechanisms might have a positive coupling effect on the CO2 and ASP.
displacement of both.
Numerous simulations have been done to compare different EOR mechanisms; WAG, CO2, ASP, WF
(water flooding) and PASP (pure ASP flooding, no chase water) flooding against ASPaM for different
depositional environments. The sequence in ASPaM is 10% ASP chased by water, preceded by a 10%
CO2 slug size and finally followed by continuous CO2 injection. While in the WAG that 10% ASP slug
is substituted by water. The first depositional system is an isotropic and homogenous reservoir. The
SPE 123866 7

recovery of ASPaM is definitely more than the other schemes especially if time is considered as shown
in figure 3a-b. Moreover ASPaM displays less water cut, shown in figure 3c. Although PASP, which
stands for pure ASP injection, shows better recovery but it is not economically feasible as the production
life is too long for the same recovery and cost of injection materials is very high. The effect of the water
slug size is shown in figure 3d; no significant influence of water slug size has been observed.

a b c d
Figure 3: a,b) comparison of ASPaM with the other methods c) water cut of different EOR schems d) water slug size effect on recovery.

The alkaline consumption by carbonic acid is an important issue

but, since ASP and CO2 are being injected alternatively, they
don't mix entirely and consequently the alkaline consumption is
not significant. However the simulation of alkaline consumption
and gas/liquid mass transfer is expensive. Nevertheless this
complex system is simulated for a 2-D model, a diagonal of the
sector model. Figure 4 reveals no considerable change in
ultimate recovery may happen if the alkaline consumption were
to be considered.
The recovery of ASPaM was investigated in three heterogenous
systems: coarsening upward, fining upward and random-
heterogeneity. The absolute permeability ratio of the overlaying
stratas in the coarsening upward system is 1/2/3 while in fining Figure 4: Effect of alkaline consumption by
upward it is 3/2/1. ASPaM in both fining upward and coarsening carbonic acid on recovery of ASPaM.
upward shows better recovery than ASP and CO2 flooding alone
while WAG almost has the same performance with ASPaM in the fining upward deposition. However
the recovery of both is much more than the homogenous system, figure 5. The difference between the
WAG and ASPaM performance increases in coarsening upward in comparison with a perfectly
homogenous system and it is attributed to better micro sweep effciency of the bottom layer in ASPaM,
while in WAG, the miscible zone, CO2 front, is redirected to the upper layers, figure 6, thus the bottom
layer displacement is immiscible. In the fining upward deposition, the miscible zone of CO2 is redirected
to bottom layers and improves the recovery of WAG. Therefore the difference between them reduces.
8 SPE 123866

Figure 5: Recovery of different EOR schemes in fining Figure 6: Recovery of different EOR schemes in coarsing
upward dipositional system. upward dipositional system.

The random heterogeneity is more complicated as the average permeability is changing with respect the
path chosen by the fluid. Two facies were chosen for this random system, where the low permeability
facies has 7% of the high permeability facies permeability with the same porosity. The stochastic
program was written to calculate the average permeability for any arbitrary pass, in addition to the
average permeability in the diagonal surface between the injector and producer, which are given in table
3. The other method to characterize heterogeneity is the Lohrenz coefficient. But the Lohrenz
coefficient may not be the proper method here as it is does not consider location and pathway through
the facies. Therefore the authors employed the described methodology, which is based on flow direction,
and represents better effect of permeability heterogeneneity on fluid flow.
Table 3: Normalized permeability for 2 Random Systems.

Pass Case-1a Case-2

Arbitrary Passb 0.37 0.45

Diagonal Pass 0.29 0.52

a:Normalized with respect to Homogenous system. b:Averaged for any arbitrary pass.

The results for ASPaM were unexpected; the recovery of ASPaM increased in these random-wise
heterogeneities while the recovery of WAG reduced. Maps of the solvent saturation in the random
system, reveals its saturation in the deeper layers increases, which improves the recovery. At the same
time the saturation of the trapped oil decreases due to multiphase flow and heterogeneity. The saturation
of the trapped oil in the WAG process in heterogenous systems is increased, due to the fact that it
interferes with the positive effect of miscible displacement by CO2. In fact heterogeneity has two effects;
it increases the saturation of trapped oil due to local trapping of the oil phase, which is a negative effect
of heterogeneity. In addition it may have a positive effect by redirecting the solvent zone to the non-
swept area.
SPE 123866 9

Based on this vision it was expected that CO2

flooding would give better results since less oil
would be trapped by water. Figure 7 shows the
recovery of ASPaM, WAG and CO2 for the
homogenous and two randomly heterogeneous
systems. The recovery by CO2 flooding, in the
heterogenous cases, shows a sudden rise after 4 PV
injection and overtakes the ASPaM after 9 PV for
Case-2, and for Case-1 it happens after another 3
PV of injection (12 PV).
Conclusions
In this study we introduced a new EOR scheme and
compared it against some other EOR schemes. This
EOR scheme which is a combination of the two
favorable commercial schemes,ASP and CO2
flooding, shows a significant improvement in
incremental recovery. In addition it has less
injectivity problem as the well has less water cut. Figure 7: Comparison of ASPaM, WAG and CO2 performance
in randomly heterogenousand hemogenous systems.
Furthermore, heterogeneity did not affect recovery
significantly and even may have a positive effect on recovery especially for a fining upward deposition
and a randomly heterogenous system.

Acknowledgement
Support for this work by the Enhanced Oil Recovery Institute of the University of Wyoming, under the
direction of Dr Jim Steidtmann, is gratefully acknowledged.

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