SPE 35164
A Compositional Model for C0 2 Floods Including C0 2 Solubility in Water
Yih-Bor Chang, Brian K. Coats and James S. Nolen, Western Atlas Software
Copyrlglat 1!1961 Soddy ol Petroletna Eaglaeerts
Tills paper was prepared for preseatatloa at tbe Permlaa Basla 011 & Gas Recovery Coofereace
lteld Ia Mldl.. d, Texas, 2729 MaNit 1996.
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Abstracts
This paper presents a three-dimensional, three-phase
compositional model for simulating C02 flooding including
C02 solubility in water. Both fully implicit and IMPES
formulations are included. In this model, C02 is allowed to
dissolve in the aqueous phase while all other components
except water exist in the oi~ and gas phases. Oil- and gas-
phase densities and fugacities are modeled by a cubic
equation of state. The aqueous phase properties are functions
of the amount of dissolved C02. C02 solubility is computed
using a C02 fugacity coefficient table that is converted
internally from input C02 solubility data as a function of
pressure at reservoir temperature. Correlations for computing
the solubility of C02 in water and other properties of C02
saturated water are presented. Results for simulation runs
with and without C0 2 solubility in water are shown for
comparison.
lntrod uction
Compositional models using a cubic equation of state are
usually used to simulate the enhanced recovery process of gas
injection. In most of the published models, for example
Coats 1 and Young and Stephenson2, all hydrocarbon
components exist in the oil ,and gas phases but are not
allowed to dissolve in the aqueous phase. Usually, this
assumption is adequate since the hydrocarbon solubility in
water is low over the range of temperature and pressure for
gas injection. Carbon dioxide, however, is an exception to
this assumption. The solubility of C0 2 in water is much
higher than that of hydrocarbon components and is a factor
that can not be neglected in the simulation process 3 This is
especially true when C02 is injected into a previously
189
Society of Petroleum Engineers
waterflooded reservoir or when C02 is injected with water for
mobility control 4 The objective of this paper is to model oil
recovery processes involving C0 2 injection while taking into
account the effects of C02 solubility in water.
The effects of the presence of an aqueous phase on the
phase behavior of CO:zfhydrocarbon systems have been
experimentally studied by Pollack et al. 5 It was found that
the presence of water reduces the amount of C02 available for
mixing with the hydrocarbons, and shifts the pressure-
composition diagram of CO:Jcrude oil system. The solubility
of C02 in water is a function of temperature, pressure and
water salinity3 A thorough study of C02 solubility data in
distilled water was presented by Dodds et al. 6 In general,
C02 solubility increases with pressure and decreases with
temperature. An increase in salinity of the reservoir water
decreases C02 solubility significantly. Li and Nghiem7 used
Henry's Law to estimate C02 solubility in distilled water and
used the scaled-particle theory to take into account the
presence of salt in the aqueous phase. Enick and Klara 8 also
used Henry's Law to predict C0 2 solubility in distilled water.
The decreased solubility of C02 in brine was accounted for
empirically by a single factor correlated to the weight percent
of dissolved solid. However, a wide scatter of data
characterizes their correlation.
A compositional model for simulating CO:z floods
including C0 2 solubility in water is presented. In this model,
hydrocarbons and C02 are allowed to exist in the oil and gas
phases while only C02 and water exist in the aqueous phase.
A cubic equation of state is used to model oil- and gas-phase
densities and fugacities. An input table of CO:z solubility in
water, water formation volume factor, water compressibility
and water viscosity is required for this model. These data,
which are obtained either experimentally or generated from
correlations, are entered as a function of pressure at reservoir
temperature. The C0 2 solubility in water is internally
converted into a fugacity coefficient table as a function of
pressure. The fugacity coefficients are then used to compute
the amount of C0 2 in water during simulation using the
equality of component chemical potential constraint. The
water formation volume factor, compressibility and viscosity
are then computed as a function of the amount of CO:z
dissolved in the water.
2 A COMPOSITIONAL MODEL FOR C0 2 FLOODS INCLUDING C0 2 SOLUBILITY IN WATER SPE35164

=aP[1-bsi~J::_.
A new empirical correlation is presented for the solubility
of C02 .in distilled water as a function of pressure and R cP )]
temperature. The calculated solubility in distilled water can sw 2 c P+ 1 '\

be further adjusted for the effects of salinity to obtain the if P < po {1)
solubility of C02 in NaCl brine. In addition, correlations for and
computing C02 saturated water formation volume factor, Rsw = R;w + m(P- po) if P ~ po (2)
compressibility and viscosity are also given. Finally,
simulation results compare reservoir performance with and
where
without C02 solubility in water.
(3)
General Description of the Model
The simulator described here is an isothem1al, three-
dimensional, compositional model. This model can simulate 4
water, oil and gas flow in reservoirs of heterogeneous b = ,Lb; 10_3; yi
permeability and porosity. The fluid flow is simulated using i-0
Darcy's law, incorporating viscous, gravity and capillary and 0<b<1 (4)
forces. Relative permeabilities and capillary pressures are
4
functions of saturations and optionally can be specified as a
function of interfacial tension. The model consists of mass C = 10-3 ~C; 10_3; Ti (5)
,.o
balances for water and nc hydrocarbon components and
associated constraint equations. Oil- and gas-phase densities
and fugacities are calculated from a cubic equation of state9
(6)
Component volume shift factors 10 can be optionally included
for volume translation. Both Lohrenz et a/. 11 and Pedersen et
a/. 12 correlations are available for calculating oil- and gas-
phase viscosities. Interfacial tension, if needed, is calculated
from the Macleod-Sugden correlation13 It is assumed that (7)
instantaneous equilibrium exists between oil, gas and water,
and that water and hydrocarbon components are mutually
m-a 1-b si { -
:Tt C po ) 1t
+-
C p
0

~1t- -
C po
--
)]} (8)
insoluble. C02 is aUowed to exist in all three phases. There { [ 2 C' po + 1 2 C' po + 1 2 C ' P0 +1
is no precipitation or chemical reaction, and physical
dispersion is not modeled.
The compositional model includes both fully implicit and
Rsw is C0 2 solubility in scf of C0 2 per STB water, T is
temperature in degree Fahrenheit, P is pressure in psia, and
IMPES (implicit-pressure, explicit-saturation) fomiUiations.
the coefficients are
The fully implicit formulation is similar to the formulation by
Coats\ and the IMPES formulation is a modification of the
Young and Stephenson2 formulation. This model is capable i=O i=l i=2 i=3 i=4
of simulating reservoir perfonnance with locally refined ai 1.163 -16.630 111.073 -376.859 524.889
grids. Using the local grid refinement option, a grid can be bi 0.965 -0.272 0.0923 -0.1008 0.0998
specified to be fully implicit or IMPES, and a simulation Cj 1.280 -10.757 52.696 -222.395 462.672
model can have mixed implicit/IMPES grid types.
This correlation matches the solubility data of Wiebe14 for
Correlations for C02 Saturated Water Properties liquid and supercritical carbon dioxide in. water within 10
Correlations are developed for estimating properties of C0 2 scf/STB for temperatures between 54 and 212 degrees
saturated water for binary COzfwater systems as functions of Fahrenheit and pressures up to 10,000 psia. Figure 1 is a
temperature, pressure and salinity. The estimated properties comparison of the computed data and the measured data by
include C0 2 solubility in water (Rsw), water formation factor Wiebe 14 at 104, 122, 167 and 212 F.
(Bw), water compressibility (Cw) and. water viscosity (f!w). The calculated solubility in distilled water can be further
adjusted for the effects of salinity to obtain the solubility of
C0 2 Solubility in Water. The solubility of C0 2 in distilled C0 2 in brine.
water may be estimated as a function of temperature and
press~re with the following equations:

190
SPE 35164 A COMPOSITIONAL MODEL FOR C0 2 FLOODS INCLUDING C0 2 SOLUBILITY IN WATER 3

Reservoir Simulation Model

log( Rsb) = -0.028 S y-O.l 2 (9) This reservoir simulation model consists of 211c+5 equations
RSW for each grid block, where ne is number of hydrocarbon
components. The ne hydrocarbon components and :water
of brine in weight percent of solid, and T is temperature in mass balance equations are
degree where Rsb is C02 solubility in scf of C02 per STB
brine, S is salinity Fahrenheit. The measured data in NaCI
solutions from Malinin and Savelyeva 15, Malinin and D r
R.~ ~ [(ot>. ,; -(4> n; r]- A[T. :: S.x; (Ill' -y .w) l
Kurovskaya 16 and McRee17 were used to obtain this
correlation. Equation (9) also matches these C02 solubility
data in NaCI solution within 10 scf/STB. Figure 2 shows
-+ :: S,Y; (AP+M'.,. -y ,w)]
the computed data and measured data from Malinin and
Savelyeva 15, and Malinin and Kurovskaya 16 Figure 3 is a
-A[T"' krw we~ (M'- AP
lA-w Bw cwo
-y
w
AD)]b.r,c~ + q. = 0
1

comparison of the computed data and the experimental data i = 1,2, ... ,nc (12)
ofMcRee17

Water Formation Volume Factor. The formation volume Rwrb V,.

AI
[('s. )"'"'-('S.,)~]-A[T. krw ..2:._.(AP-AP_,-y.,AD)]+q., -o
B., B., 1-' .. B.,
factor of C02 saturated water (or brine) is calculated using
(13)

B = p w,sc + 0.02066 R sb where b i,c~ = 1 if component i is C02 otherwise b i,c~ = 0.

(10)
w Pw,alm + 0.0058 Rsb
where Bw is water formation volume factor in rb/STB, Pw,sc is
water density at standard temperature and pressure in lb/cu ft,
and Pw,atm is water density at reservoir temperature and 14.7
psia in lb/cu ft. Both Pw,sc and Pw,atm can be calculated from,
for example Rowe and Chou 18, correlations. Equation (10) is
In Eq. (12), C02 is allowed to dissolve in the aqueous phase
while a]) other components except water exist in the oil and
gas phases. We also assume no C02 in the injected water and
the separator water does not have any dissolved C0 2
Summing Eq. (12) over all hydrocarbon components yields
the total hydrocarbon equation

:~ [(<!> n, t' -(<1> n.}"]- t.[ Tm :: ~. (AP-y .w)]

developed using the data of Parkinson and De Nevers 19 and
Sayegh and Najman20 R,.., =

Water Compressibility. For pressures less than 5000 psia,

the water compressibility factor of C02 saturated water is -!l.[T krg
J.t t {M + !l.P
g ~g
- yg w)]
l .
m ego
calculated using the correlation from Rowe and Chou 18 For
pressures greater than 5000 psia,
k w
-fl. Tm -~~ (!l.P- !l.Pcwo -y wtill) + q1 = 0
B
[ f..tw w
1 1
- + 7.033 (P- 5000) (11) (14)
Cw,SOOO
The total hydrocarbon equation is used in our model instead
where Cw,sooo is water compressibility at reservoir temperature of the mass balance equation for component llc
and 5000 psia from the Rowe and Chou 18 correlation in
psia- 1 The above correlation is derived from the water The fie+ 1 fugacity constraints (for a three phase block),
compressibility correlation by Osif 1 The effects of dissolved
C02 in water on water compressibility is assumed negligible Rt.i = JF.z,o - JF.z,g = 0 i = 1,2, ... ,nc (15)
when using the Rowe and Chou 18 and Osif21 correlations.
and
Water Viscosity. The effects of dissolved C02 in water on
water viscosity were found to be very small by Sayegh and (16)
Najman20 Water viscosity can be calculated from the Kestin
et al. 22 correlation, neglecting the effects of dissolved C0 2
where xis one of the hydrocarbon phases (o or g), express the
requirement that oil- and gas-phase fugacities must be equal
for each hydrocarbon component, and C0 2 fugacities in the

191
4 A COMPOSITIONAL MODEL FOR C02 FLOODS INCLUDING C02 SOLUBILITY IN WATER SPE35164

hydrocarbon phase and the aqueous phase must be equal. of these 2nc+5 unknowns. Then the variables y nc (or X nc )
The C02 equilibrium constraint applies if and only if C02,
and Znc are eliminated using the mole fraction constraints.
the water phase, and at least one hydrocarbon phase are all
present. A cubic equation of state is used to compute oil- and Figure 4 shows the ~.tructure of the Jacobian for the diagonal
gas-phase fugacities. C02 fugacity in the aqueous phase is term with three hydrocarbon components. We have assigned
calculated from a C02 fugacity coefficient table which is C02 to be component number one in this figure. In this
computed internally from input C02 solubility data. The figure, the symbols "x" and "*",respectively, denote new and
method for computing the C02 fugacity coefficient table is modified elements due to C0 2 solubility in water. The
discussed later. There are two mole fraction constraints and symbol "o" denotes elements that are not affected by
one water saturation constraint considering C02 solubility in water. Only five more elements
from the material balance equations are added to the Jacobian
compared with the Jacobian without including C02 solubility
and in water. These "extra" elements are the derivatives of C02,
total hydrocarbon and water material balance equations with
respective to Wc 02 and Sw. These elements can be easily
rnPES Formulation For the IMPES fonnulation, the eliminated, and then the resulting Jacobian becomes the same
variable Jli in equation {12} is expressed as fom1 as the one without including C02 solubility in water.
Thus, we can apply the same solution procedure as suggested
by Young and Stephenson 2.
i = 1,2, ... ,nc In their paper, Young and Stephenson2 also suggested a
procedure that can yield zero material balance errors. This is
because in their model porosity and water formation volume
and the variable Dt in equation (14} is
factor are function of pressure only. After solving for
pressure, the total hydrocarbon and water material balance
S w equation can be rearranged to solve for F and Sw exactly.
n, = F + w CDz
Bw This procedure, however, can not be applied directly to our
model. This is because the water formation volume factor,
where Bw, is a function of pressure and C0 2 content in water (wco ).
2

Secondly, the C02 component and total hydrocarbon material

balance equations include material in the hydrocarbon phase
as well as C02 in the aqueous phase. To achieve zero
z. = Lx. +Vy. material balance error, we need to solve for Wco after
i = 1,2, ... ,nc 2
' ' . ' obtaining pressure but before solving for other variables.
with Fortunately, the changes in Zj can be expressed as a function
of w co and then combined with the backward substitution
2

equation for W co to fonn a quadratic equation in tenns of

2
and L+V =1
W co
2
After solving for w co2 , we update Bw, and then solve
for all other variables using the procedure suggested by
The saturation equation is expressed in temlS ofF, L, V and Young and Stephenson.
Swas
Implicit Formulation For the implicit fonuulation, the

(~+~)+S
variable ni in equation (12} is expressed as
R s~ = F ~
-1= 0
0 ~g w
S w
n. = 'i: S x. + 'i: S y. + w COJ. b.
' ':lo o ' ':lg g ' Bw ,,cOJ_
The unknown variables are V, 'l:h i=1, .. ,1lc; Zj, i=1, .. ,nc; w C02
,
F, Sw, and P for a predominantly liquid cell (Vy iteration),
and the variable nt in equation (14} is
and L, Xi, i=1, .. ,1lc; Zj, i=1, .. ,nc; Wco2 , F, Sw, and P for a
predominantly vapor cell (Lx iteration). For a three phase S w
grid block, the 2nc+3 equations of fugacity constraints, mass n, -- 'i:
"::o
s
0 +':lg
'i: s g +---.;;...
W C02

balances and saturation constraint are first linearized in tenns Bw

192
SPE 35164 A COMPOSITIONAL MODEL FOR C02 FLOODS INCLUDING C02 SOLUBILITY IN WATER
The unknown variables are Yh i=1, .. ,1lc; Xi, i=1, .. ,1lc;
Sw, S 8 and P. In the case of a three phase grid block, the
21lc+ 2 equations of fugacity constraints and mass balances are
first linearized in tenns of these 21lc+5 unknowns. Then the
variables y n and Xn are eliminated using the mole fraction
c c
constraints, and the variable So is eliminated using the
saturation constraint. Figure 5 shows the structure of the
Jacobian for the diagonal term with three hydrocarbon
components. In the solution procedure, Gaussian elimination
is used_ to solve for the ne+ 1 unknowns of Yh i= 1, .. ,1lc-1; x1,
and W co in terms of the remaining ne+ 1 unknowns of Xi,
2
i=2, .. ,1lc-1; Sw, Sg and P. The remaining ne+1 unknowns are
called primary unknowns, while the ne+ 1 eliminated
unknowns are called secondary unknowns. The linearized
mass balance equations, after eliminating the secondary
unknowns using the constraint equations, form a set of ne+ 1
equations in terms of ne+ 1 primary unknowns. The linear
system is solved iteratively, and the solution vector is then
used to compute the secondary unknowns through back
substitution as described by Coats1
Phase Equilibrium Calculations During simulation, we
need to determine the number and type of phases in a grid
cell. A sequential approach is used in the model. For a cell
with hydrocarbons, C02 and water, a two-phase
hydrocarbon/water flash is first performed to compute the
amount of C02 in water and the composition of the
hydrocarbon phase. Equation (16) is the primary equation
and wco2 is the primary unknown for this flash calculation.
Next the computed hydrocarbon composition is tested by a
two-phase oil/gas flash calculation for the possibility of
splitting the single hydrocarbon phase into two phases. If
only one hydrocarbon phase can be found at the end of the
oil/gas flash calculation, then the p~ase equilibrium
calculation is complete. If the oil/gas flash calculation yields
two hydrocarbon phases, then we know that oil/gas/water
three-phase equilibria exist in this grid cell, and we perfonn a
three-phase flash to determine the compositions of the oil, gas
and aqueous phases.-
Aqueous Phase Properties In addition to the fluid flow
properties, equations (12) to (16) also require PVT properties
of oil, gas and aqueous phases. Oil- and gas-phase densities
and fugacities are computed using a cubic equation of state.
A method for calculating the aqueous phase properties during
simulation is discussed in this section.
As mentioned earlier, an input table of C02 saturated
water properties of binary CO~water system is needed in our
model. These data, either measured experimentally or
estimated from correlations, include C02 solubility in water,
water formation volume factor, water compressibility and
5
water viscosity. These data are entered as a function of
wco2' So, pressure at the reservoir temperature. The format and use of
this table are similar to the conventional black oil table except
now the solution gas is C02, the liquid phase is water instead
of oil, and the formation volume factor is for C02 saturated
water instead of gas saturated oil.
A table of C02 fugacity coefficient in the aqueous phase,
cp c~,w' is computed internally from the input C02 solubility
for a saturated binary CO~water system. The phase
equilibrium constraint for the C02 component in a binary
CO~water system is
-or
where we use the subscript w to denote the aqueous phase and
v for the C02 rich phase. y co is the mole fraction of C02 in
2
the C02 rich phase and 00 C02 is the mole fraction of C0 2 in
the aqueous phase which can be computed from the input
C02 solubility in water, Rsb At the conditions of typical C02
floods, the water vapor pressure is small relative to the total
pressure and C02 vapor pressure. If we assume that the water
mole fraction in the C02 rich phase is negligible, i.e.
=
y c~ 1, the fugacity coefficient of C02 in the aqueous phase
can be approximated as
where <P c~~ is the fugacity coefficient of pure C02 in the
vapor phase computed using an equation of state (EOS).
For a binary CO~water system, the computed fugacity
coefficient of C0 2 in the aqueous phase, 4> c~,w , is a function
of temperature and pressure but not composition since cp EOS
c~,v
is for pure C0 2 and oo c~ is for the binary CO-'water
V system ,
and both are a function of temperature and pressure onlY. at a
constant water salinity. For isothermal reservoir simulations,
<P c~,w is assumed to be a function of pressure only and is
used in Eq. (16) for computing C0 2 content in the aqueous
phase with an arbitrary hydrocarbon system.
After computing C0 2 content in the aqueous phase using
the phase equilibrium algorithm mentioned above, water
viscosity, saturated water formation volume factor, water
compressibility, and water saturation pressure can. be
calculated from the table of C02 saturated water properties of
CO~water system using linear interpolation. These aqueous
phase properties are assumed to be functions only of aqueous
193
6 A COMPOSITIONAL MODEL FOR C0 2 FLOODS INCLUDING C02 SOLUBILITY IN WATER SPE 35164

phase C0 2 content. The water formation volume factor at
block pressure P, Bw, is calculated from the saturated water
formation volume factor (B:aJ), water compressibility (Cw),
and water saturation pressure (P:aJ) as:
dissolved C0 2 , which is considered "lost", is not available for
mixing with oil.
Figures 8 and 9 are comparisons of oil recoveries. ~or
simulation runs with and without considering C02 solubility
in water. In these figures, the left axis is the cumulative oil
produced for runs including C02 solubility in water, and the

B Bsal [l+Cw (P-Psal)]

right axis is the difference in cumulative oil produced
_l__=_l w between runs ignoring and runs including C02 solubility in
w w
water. Figure 8 shows the results of case A runs. The major
impact of C0 2 solubility in water is delaying oil recovery, and
Simulation Results
the effect is more pronounced for run A-1 than run A-2.
The objective of these simulation runs is to investigate the
Recall that run A-1 is for simulating IM C0 2 injection
effects of C02 solubility in water on oil recovery. For each
conditions, and Run A-2 is for MCM conditions. At the end
case, we made a pair of simulations, one includes C02
of year eight, the runs with C0 2 solubility produced about 180
solubility in water and one ignores C02 solubility. The
MSTB oil less than the runs without C02 solubility. The oil
reservoir and fluid properties are from Killough and
recoveries for case B are shown in Figure 9. Recall that the
Kossack23 . The same three dimensional 7 by 7 by 3 grid is
reservoir is waterflooded before WAG cycles for case B. Now
also used in our study. Two wells, one for injection and one
C0 2 solubility not qnly delays the oil recovery but also
for production, were located in opposite comers of the grid.
reduces the final oil recovery. The effect is more pronounced
The injection well is located in the grid block (i,j)=(1,1) with
for run B-2 (MCM conditions) than for run B-1 (IM
all three layers perforated. The production well is in the grid
conditions). At the end of year nine, the runs with C02
block (i,j) = (7,7) with only the third layer perforated !he o~!
solubility produced about 200 MSTB less oil than the runs
is characterized by a six-component Peng-Robinson
with no C02 solubility. This is about 5% of post-waterflood
equation of state description. We changed the inject~~ gas
oil recovery at year nine.
from a mixture of C1, C2 and C6 to C02. The solubility of
Although a simple reservoir model was used in the above
C02 in water is calculated using equations (1) to (9), and
simulation, similar effects of C02 solubility in water on oil
water formation volume factor is from equation (10) at 160 oF
production are also found in one of our field simulation. This
and 10 wt% salinity. For the purpose of comparison, constant
is a model of about 5,000 gridblocks with six layers. The
values of water compressibility and viscosity, 3.3x10"5 psi" 1
reservoir had about 50 years of primary production and
and 0.7 cp respectively, are used for all runs.
waterflooding, and is planned for C0 2 flooding for almost 30
Two WAG injection cases were designed in our study.
years of WAG cycles. The C02 flood is fo1lowed by another
Both cases start with two years of oil production at a
15 years of chase water injection. Our simulation results
maximum rate of 2000 STB/D with no injection. For case A,
show that about 10 to 15% of total injected C02 dissolved in
a three-month WAG cycle begins at the end of year two. The
water or about 11 to 15% of the C0 2 in the reservoir
WAG cycles last for 12 years, and are followed by a six-year
chase water period. For case B, waterflood begins at the end
dissol~ed in water during the WAG cycles. A maximum of
15% post-waterflood oil production, or 8% of total oil
of the second year and continues for 4 years. The waterflood
production are delayed when C0 2 solubility is simulated. The
is followed by 8 years of three-month WAG cycles which are
simulation results presented here, however, should not be
followed by 6 years of chase water. Case A mimics secondary
generalized to all reservoirs without considering other facto~.
C02 flooding while case B mimics tertiary C02 flooding.
The effect of C02 solubility in water on C02 flood Oil
Two runs were made for each case, the first one simulated an
recovery will probably depend on reservoir heterogeneity,
immiscible (IM) C0 2 flood, and the second simulated a
rock and fluid properties, and injection/production history of
multiple contact miscible (MCM) C0 2 flood. Table 1
the reservoir.
summaries run conditions.
Figure 6 shows the ratio of total C0 2 dissolved in water
Conclusions
to cumulative C0 2 injected. For a11 runs, this ratio reaches its
A three-dimensional, three-phase compositional model is
peak value near the end of the first year of WAG cycles, and
presented for simulating C0 2 floods including C02 solubility
then gradually declines until the end of the WAG cycles. The
in water. Oil- and gas-phase densities and fugacities are
maximum ratios are about 7% and 12% for Case A and B
modeled by a cubic equation of state. C0 2 solubility in water
respectively. Figure 7 shows the ratio of total C02 dissolved
is computed using a C0 2 fugacity coefficient table which is
in water to the total amount of C02 in the reservoir. The
internally converted from input C0 2 in water solubility data
latter is calculated as the difference between cumulative C02
as a function of pressure at the reservoir temperature.
injected and produced. About 8 to 13% of the C02 in the
Correlations for estimating C0 2 solubility in water and
reservoir dissolved in water during WAG cycles. The
NaCl brine, water formation volume factor of C02 saturated

194
SPE 35164 A COMPOSITIONAL MODEL FOR C02 FLOODS INCLUDING C0 2SOLUBILITY IN WATER 7

water, water compressibility, and water viscosity are cp = Porosity, fraction

presented. The C0 2 solubility in water can be estimated with <P co.z,v= Fugacity coefficient of C0 2 rich phase
the correlations within 10 scf/STB for most C0 2 flood
<P co.z,w= Fugacity coefficient of C02 in water
conditions.
Using a simple three-dimensional model, simulation yg = Gas specific gravity
results show that about 10% of C02 injected is dissolved in Yo = Oil specific gravity
water and unavailable for mixing with oil. This may be Yw = Water specific gravity
considered "lost" to the aqueous phase. The solubility effects 1-lg = Gas viscosity, cp
are more pronounced for tertiary C02 floods than secondary 1-lo = Oil viscosity, cp
C02 floods. As much as 5% of post-waterflood oil production 1-1w = Water viscosity, cp
can be delayed from our simulation results. Pw = Water density, lb/cu ft
w co.z = mole fraction of C0 2 in water
Nomenclature i;g = Gas molar density, lb-mole/cu ft
Bw = Water formation volume factor, rb/STB i;o = Oil molar density, lb-mole/cu ft
Cw = Water compressibility, 1/psi
D = Depth, ft Subscripts and Superscripts
F = Overall hydrocarbon phase molar density, lb- g = Gas phase
mole/cu ft = Component index
fi.g = Fugacity of component i in the gas phase n = Time step index
~.o = Fugacity of component i in the oil phase o = Oil phase
krg = Gas relative permeability w = Aqueous phase
kro = Oil relative permeability
krw = Water relative permeability Acknowledgments
L = oil mole fraction in hydrocarbon phase The authors wish to thank Western Atlas Software for
ni = total molar density of component i pennission to publish this paper.
nt = total molar density of all hydrocarbon
components References
p = Pressure, psia 1. Coats, K.H.: "An Equation of State Compositional Model,"
Pcgo = Oil/gas capiJiary pressure, psia SPEJ (Oct. 1980) 363-376.
Pcwo = Oil/water capiiiary pressure, psia 2. Young, L.C. and Stephenson, R.E.: "A Generalized
qi = Hydrocarbon component well rate for Compositional Approach for Reservoir Simulation," SPEJ
component i, lb-mole/D (1983) 23, No.5, 727-742.
qt = Total hydrocarbon weii rate, lb-mole/D 3. Klins, M.A.: Carbon Dioxide Flooding Basic Mechanisms and
qw = Water well rate, STB/D Project Design, International Human Resources Development
Corporation, Boston, MA, 1984.
Rsw = Solubility of C02 in distiiied water, scf/STB
4. Enick, R.M. and Klara, S.M.: "Effects of C02 Solubility in
Rsb = Solubility of C0 2 in NaCl brine, scf/STB Brine on the Compositional Simulation of C02 Floods," SPERE
s = Salinity of NaCl brine, weight percent (May 1992) 253-258.
Sg = Gas saturation, fraction 5. Pollack, N.R., Enick, R.M., Mangone, D.J., and Morsi, B.l.:
So = Oil saturation, fraction "Effect of an Aqueous Phase on CO:{fetradecane and
Sw = Water saturation, fraction COJlMaljamar-Crude-Oil Systems," SPERE (May 1988) 533-
T = Temperature, oF 541.
Tm Transmissibility 6. Dodds, W.S., Stutzman, L.F. and Sollami, BJ.: "Carbon
Dioxide Solubility in Water," Ind. & Eng. Chem. (1956) 1, No.
t = Time, day 1, 92-95.
Vm = Gridblock bulk volume, bbl
7. Li, Y.-K. and Nghiem, L.X.:" Phase Equilibria of Oil, Gas and
v = Gas mole fraction in hydrocarbon phase Water/Brine Mixtures from a Cubic Equation of State and
wco2 = Solubility of C02 in water, lb-mole/STB Henry's Law," Cdn. J. Chem. Eng. (June 1986) 486-496.
Xi = Mole fraction of component i in the oil phase 8 Enick, R.M. and Klara, S.M.: "C02 Solubility in Water and
Yi = Mole fraction of component i in the gas phase Brine Under Reservoir Conditions," Chem. Eng. Comm. (1990)
Zj = Overall mole fraction of component i in the 90,23-33.
hydrocarbon phases 9. Coats, K.H.: "Simulation of Gas Condensate Reservoir
Performance," SPE 10512, presented at the Sixth SPE
Symposium on Reservoir Simulation of the Sodety of
Greek symbols
Petroleum Engineers of AIME held in New Orleans, LA, Jan.
fl. = Difference operator 31-Feb. 3, 1982.

195
8 A COMPOSITIONAL MODEL FOR C02 FLOODS INCLUDING C02 SOLUBILITY IN WATER SPE35164

10. Jhaveri, B.S. and Youngreen, G.K.: "Three-Parameter

Modification of the Peng-Robinson Equation of State to
Improve Volumetric Predictions," SPERE (Aug. 1988) 1033-
1040.
11. Lohrenz, J., Bray, B.G. and Clark, C.R.: "Calculating
Viscosities of Reservoir Fluids from their Compositions," SPEJ
(Oct.1964) 1171-1176.
12. Pedersen, K.S., Fredenslund, A. and Christensen, P.L.:
"Viscosity of Crude Oils," Chem. Eng. Sci. (1984) 39, 1011-
1016.
13. Reid, R.C., Prausnitz, J .M. and Poling, B.E.: The Properties of
Gases and Liquids, Fourth Edition, McGraw.. Hill, Inc., NY
(1987).
14. Wiebe, R.: "The Binary System Carbon Dioxide-Water Under
Pressure," Chem. Rev. (1941) 29,475-481.
15. Malinin, S.D. and Savelyeva, N.J.: "The Solubility of C02 in
NaCL and CaCL2 Solutions at 25, 50 and 75 Under Elevated
C02 Pressures," Geochemistry International (1972) 410-418.
16. Malinin, S.D. and Kurovskaya, N.A.: "Solubility of C02 in
Chloride Solutions at Elevated Temperatures and C02
Pressures," Geochemistry International (1975) 199-201.
17. McRee, B.C.: "C~: How It Works, Where It Works," Pet. Eng.
(Nov. 1977) 52-63.
18. Rowe, A.M. and Chou, J .C.: "Pressure-Volume-Temperature-
Concentration Relation of Aqueous NaCl Solutions," J. Chem.
and Eng. Data (1970) 15, No. 1, 61-66.
19. Parkinson, W.J. and De Nevers, N.: "Partial Molal Volume of
Carbon Dioxide in Water Solutions," I & EC Fund. (Nov.
1969) 8, No.4, 709-713.
20. Sayegh, S.G. and Najman, J.: "Phase Behavior Measurements
of C02-S02-Brine Mixtures," Cdn J. Chem. Eng. (April 1987)
65, 314-320.
21. Osif, T.L.: "The Effects of Salt, Gas, Temperature, and
Pressure on the Compressibility of Water," SPERE (Feb. 1988)
175-181.
22. Kestin, J., Khalifa, H.E., Abe, Y., Grimes, C.E., Sookiazian, H.
and Wakeham, W.A.: "Effect of Pressure on the Viscosity of
Aqueous NaCl Solutions in the Temperature Range 20-150
C," J. Chem. and Eng. Data (1978) 23, No.4, 328-336.
23. Killough, J.E. and Kossack, C.A.: "Fifth Comparative Solution
Project: Evaluation of Miscible Flood Simulators," SPE 16000,
presented at the Ninth SPE Symposium on Reservoir
Simulation held in San Antonio, TX, Feb. 1-4, 1987.
24. Peng, D.-Y. and Robinson, D.B.: "A New Two-Constant
Equation of State," Ind. Eng. Chem. Fund., (1976) 15, No. 1,
59-64.

196
SPE 35164 A COMPOSITIONAL MODEL FOR C02 FLOODS INCLUDING C02 SOLUBILITY IN WATER 9

T a bl e 1 : S ummary o f stmu
. ]atton
. runs
initial production waterflood WAG chase water
(years) (years) (years) (years)
runs A-1, A-2 1 to 2 3 to 14 15 to 20
runs B-1, B-2 1 to 2 3 to 6 6 to 14 15 to 20

max. inj. Ow max. inj. QA max. Pbh (psia) min. Pbh (psia)
(STB/D) (sefiD) injector producer
runA-1 7,500 15,000 4,500 500
runA-2 10,000 20,000 4,500 1,500
run B-1 7,500 15,000 4,500 500
run B-2 10,000 20,000 4,500 1,500

~ ~..___..___~----------~------------~------------r---------~------------,

200

~
:1:
~ 150
~
0
0
104 F (data)
- - 1 0 4 F (calc)
u c
.!. 100 122 F (data)
!: - - - 122 F (calc)
M
a:
50
167 F (data)
167 F (calc)
l:J. 212 F (data}
.... ~ ...... r 212F(calc)

0 2000 4000 6000 8000 10000 12000

Pressure (psia)

Figure 1: Comparison of measured 14 and caJcu]ated C0 2 solubilities in distilled water.

197
10 A COMPOSITIONAL MODEL FOR C02 FLOODS INCLUDING C0 2 SOLUBILITY IN WATER SPE35164

120

1-
1- 122 F (data)
100 -.--122 F (calc) 1--

~
A 167 F (data)
- - -167 F (calc)
0 80
~
212 F (data) -
~
N
::1: 212 F (calc)
e;! ~ .......
~ EiO
~ .....
...... -' .
~

....... _ "-
... ....
~ ~

~
0
0
u .... ......
_ I'~--- ~
..!!.
.a
Ill
a:
40
1- .... .L.-.
' ' - ......... . --
1--A.

- ...... A-----
..~
.............
.
20
0
0 5 10 15 20 25 30
Salinity (wt%)

Figure 2: Comparison ofmeasured 1516 and calculated C0 2 solubilities in NaCI brine at 695.5 psia.

-
0
11

13)
~~/
~
H
- -- r---

~100
m
1-
~ m
/
. . . .. ........
N
0
0 ED
0
~ 4) I
I
I
'~ ~
,... ., ~,Ill .. # ~
.... . .. . .. . .

,. ~-

10 VJtOio(data)
1---
~ ~

"" --10wt01o(calq ,...__

..c
Cl)
a: 3) /:' 25 VJtOio(data)
1---

0
~~ . . .
- - - - 25 VJtOio(calq
I I

Figure 3: Comparison of measured 17 and calculated C0 2 solubilities in NaCJ brine at 100 F.

198
SPE35164 A COMPOSITIONAL MODEL FOR C02 FLOODS INCLUDING C02 SOLUBILITY IN WATER 11

0 0 0 0 0 0 oyl Rft
0 0 0 0 0 0 oy2 Rf2
0 0 0 0 0 0 ov Rf3
X X X X X owe~ RCOz.
X 0 0 X * . ozl Rm~
0 0 0 oz2 Rmb2
X 0 X * oF Rm~
X 0 * osw Rmb,..
0 0 0 0 0 0 0 0 p RsaJ

Figure 4: Structure of diagonal Jacobian of the IMPES formulation for~ components. The symbol "o" represents elements without
C02 solubility in water, "x" is for elements due to C02 solubility in water only, and "*" represents elements for which the C02
solubility term has been added to the hydrocarbon flow terms.

0 0 0 0 0 oyl Rft l
0 0 0 0 0 oy2 Rf2 I
0 0 0 0 0 oxl Rf3
X X X X OWCOz. RCOz.
0 0 0 X 0 0 * * osg Rm~
0 0 0 0 0 0' 0 ox2 Rmb2
0 0 0 X 0 0 * * osw Rmb I

X 0 0 oP Rmb,..

FigureS: Structure of diagonal Jacobian of the implicit formulation for 3 components. The symbol "o" represents elements without
C02 solubility in water, "x" is for elements due to C02 solubility in water only, and "*" represents elements for which the C02
solubility term has been added to the hydrocarbon flow terms.

199
12 A COMPOSITIONAL MODEL FOR C02 FLOODS INCLUDING C02 SOLUBILITY IN WATER SPE35164

12 --n.nA1 h

-----nnA2 ....: ', .......

~

- n.nB1
II

~10 ;." . ..,

:E' i
....
',, ~ .... -- ---
N 8 --- 1\1182 ~ ' ' .... ... .r
0
u '~ .,..'"., --- .... " .. ......, , .. ........... __
E6 r~ ~.......... .... _r-.... __. ... . .
...
,
,
, ., ....
::I ,............_
u
-.:
-
cu
ca 4 I
I

1
---- r--- ._
............. _/
I
~ I
.5 I
N 2 '
f
0
u
0
I I I
I
I

. . .
0 2 4 6 8 10 12 14 16 18
Years

Figure 6: Ratio of total C02 dissolved in water to cumulative C02 injected.

35 , ....

".,..,, , ..
--nnA1 ,I ' ,)

- - -nnA2
~.~ '1 7
nnB1
--nnB2 ~ v
~
~

'I
/I'
. . - -:;-- ~
_...
J':.~

.E r ~ r-:I--
i
---
N 5

I
I
0
C.)
_. ... .. I.
0
0 2 4 6 8 12 14 16 18

Figure 7: Ratio of total C02 dissolved in water to total C0 2 in reservoir.

200
SPE 35164 A COMPOSITIONAL MODEL FOR C02 FLOODS INCLUDING C02 SOLUBILITY IN WATER 13

--nnA-1
- - -nnA-2
-- nnA-1 .. .. ..... -.
,.,"" --"-
'~

~
- . - n.nA-2 . ..
, "
~

..,, ..... ..
'<of"""'
~ ~ m
8N ....
(/)

... ,
,....._
~
f--"'"
/~-r
., .............. ~ ... '
v""
.....
...,.., ~ ~ !.
. ~ '
,
Y\'
'
~~
8.... -d0
~
.
~~~
I, ~
~

..... -/'' v/

~ ' 0
0
e
7""'
/
,. //
v v '
' ' r-, . . . " ... / ' '\'.-.
'
' 8
"i
:::s
0
.5

l ' ~
c

0
v
0 2 4 6 8 10 12 14 16 18 20
8
~

~
Years
Figure 8: Cumulative oil produced and difference in cumulative oil produced between runs ignoring and including C02 solubility in
water for case A.

8'It
--n.nB-1
---nnB-2
..... ~- .. - -- -- ~
nn B-1 ,,. ,"" m
- -nnB-2

i: 1/
'
'.
I ... /! ,.."""'
.. ,~\
..... ~ -- 4
/

..--- .;...-'
,,_
~ 8N ....
(/)

!.
8.... -d0
/;'' v .
.. . , ... ... ~
// / ' .. 4 0
0
'....../ e
.......... ~
:::s
0
8 .5
r,...,
l
"i
..... ~
c
8

0 v
0 2 4 6 8 10 12 14 16 18 20
~

~
Years

Figure 9: Cumulative oil produced and difference in cumulative oil produced between runs ignoring and including C02 solubility in
water for case B.

201