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CO2 SOLUBILITY IN WATER AND BRINE UNDER

RESERVOIR CONDITIONS
a b
ROBERT M. ENICK & SCOTT M. KLARA
a
Department of Chemical and Petroleum Engineering, OakRidge Associated University
Fellow University of Pittsburgh, 1249 Benedum Engineering Hall, Pittsburgh, PA, 15261
b
U.S. Department of Energy, Morgantown Energy Technology Center, P.O. Box 880,
Morgantown, WV, 26507-0880
Version of record first published: 24 Jun 2009.

To cite this article: ROBERT M. ENICK & SCOTT M. KLARA (1990): CO2 SOLUBILITY IN WATER AND BRINE UNDER RESERVOIR
CONDITIONS, Chemical Engineering Communications, 90:1, 23-33

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 Chem. Eng. Comm. 1990, Vol. 90, pp. 23-33
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CO 2 SOLUBILITY IN WATER AND BRINE

UNDER RESERVOIR CONDITIONS
ROBERT M. ENICK

OakRidge Associated University Fellow

University of Pittsburgh
1249 Benedum Engineering Hall
Downloaded by [LMU Muenchen] at 21:05 16 February 2013

Department of Chemical and Petroleum Engineering

Pittsburgh, PA 15261

and
SCOTT M. KLARA

Morgantown Energy Technology Center

U.S. Department of Energy
P.O. Box 880
Morgantown, WV 26507-0880

(Received November 7, 1988; in final form October 31, 1989)

The reference Henry's constant was determined from 110 solubility data found in the literature for the
CO 2/H20 system over a temperature range of 298 to 523 K and a pressure range of 3.40 to
72.41 MPa. Since the Krichevsky-llinskaya equation was used to model the system, a correlation for
the A parameter was also developed.
In addition to the Krichevsky-llinskaya equation, another two-parameter correlation for the
solubility of carbon dioxide in water was obtained by using the Krichevsky-Kasarnovsky equation.
The reference Henry's constant and partial molar volume of carbon dioxide at infinite dilution were
treated as adjustable parameters. The calculated values of the partial molar volume at infinite dilution
did not correspond to experimentally determined values found in the literature. Therefore, a third
correlation for the reference Henry's constant was obtained by using the Krichevsky-Kasarnovsky
equation in conjunction with the correct values of the partial molar volume. This one parameter
(Henry's constant) model did not fit the experimental data as well as the two-parameter models.
The decreased solubility of CO 2 in brine was accounted for empirically by a single factor correlated
to the weight percent of dissolved solids. A literature data set of 167 solubilities, with a temperature
range of 298 to 523 K and a pressure range of 3.0 to 85.0 MPa, was used to develop this correlation. A
wide scatter of data characterizes this correlation, which relates the CO 2 solubility in brine to the CO 2
solubility in water at the same temperature and pressure. The correlation is designed for applications
in which the determination of concentrations of individual ions is impractical and the implementation
of only one additional parameter is desirable, such as the use of compositional simulators to model
miscible displacement in the petroleum industry.
These correlations can be easily implemented into reservoir simulation calculations to account for
the effects of CO 2 solubility in brine. These effects are often ignored even though they can have
dramatic effects on the performance of the CO 2 enhanced oil recovery process. The correlations
presented in this paper for the Henry's constant and the effect of dissolved solids can adequately
account for these CO 2 solubility effects.
KEYWORDS Solubility Henry's constant Carbon dioxide Brine High-pressure.

23
 24 ROBERT M. ENICK AND SCOTT M. KLARA
INTRODUCTION

Most carbon dioxide (CO z) miscible displacement phase behavior studies have
concentrated on the COz/hydrocarbon phase equilibria, even though brine exists
naturally in the reservoir, is injected during the waterflood, and is also introduced
into the formation along with COz in order to inhibit its tendency to "finger"
through the relatively viscous oil. The primary thermodynamic effect of the
aqueous phase has been assumed to be its solubilization of light gases, especially
COz, since water and liquid hydrocarbons are relatively immiscible at reservoir
conditions. Many investigators have proposed using Henry's law to model the gas
solubility in pure water and an equation of state to describe the hydrocarbon
phase equilibria. 1-6
Several empirical correlations for the Henry's constant or reference Henry's
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constant of COz in water have been published.v" but that of Li and Nghiern" is
more appropriate for reservoir conditions since it was based on high pressure
data. The partial molar volume of COz at infinite dilution in water, a parameter
in the Poynting correction used in the Henry's law analysis, is often estimated
using the correlation of Lyckman et al., 7 as reported in a simple correlation by
Heidemann and Prausnitz.z Li and Nghiem" have suggested a modification of the
Henry's constant to account for dissolved solids. Scaled particle theory (SPT) was
used to account for the decreased solubility of light gases. The molecular
diameter of the solute, a parameter that has a strong effect on SPT predictions,
was optimized to match the solubility of COz in brine.
Water solubility in the hydrocarbon phases, including the COrrich vapor or
liquid, is typically neglected since it is very small over the range of reservoir
conditions. However, this aspect can be incorporated into phase behavior
predictions."
Cubic equations of state have also been employed in an attempt to describe all
fluid phases with one modeI. 5 .8- IZ Recently, Panagiotopolous and Reid'? pre-
sented a mixing rule for highly polar asymmetric systems such as COz/HzO.
Enick, Holder, and Mohamed!" incorporated this mixing rule into a three/four-
phase flash algorithm 15 and subsequently Pollack et al., 16 demonstrated its ability
to predict the effect of an aqueous phase (water or brine) on COz/hydrocarbon
phase behavior. This same study, however, indicated that the results obtained by
neglecting water solubility in the hydrocarbon phases and modeling COz
solubility in brine using Henry's law and an empirical factor to account for a
decrease in solubility due to dissolved solids were very similar to those obtained
from the equation-of-state. Both modeled the experimentally observed shift in
the pressure-composition diagram of COz/crude oil systems. Since Henry's law
algorithm usually involves less computational time and trouble, it was considered
to be the preferable alternative.
The purpose of this study, therefore, was to accurately correlate carbon dioxide
solubility in water by regressing the Henry constant for the COz/HzO system
using all available literature data at reservoir conditions. The fugacity of COz was
calculated with the Peng-Robinson equation of state since that equation is
commonly used in compositional simulation. The effect of dissolved solids on the
 CO 2 SOLUBILITY IN WATER AND BRINE 25
solubility of CO 2 in the aqueous phase was also determined by evaluating
literature data at reservoir conditions. This effect was correlated to a single
parameter, the total dissolved solids (TDS) concentration, since it not only is a
commonly used parameter for brines, but also requires the use of only one
additional material balance in a compositional simulator.

CO 2 SOLUBILITY IN WATER

A large volume of data exists on the solubility of CO 2 in water.'7-36 Many

experimental studies have also been performed to determine the solubility of
water in C02.17.22-27,37,38 Panagiotopolous and Reid 13 have correlated mutual
solubility data in the 298 to 348 K range, using the Peng-Robinson equation of
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state and a two parameter mixing rule for highly polar asymmetric systems, Their
work was extended by Enick, Holder, and Mohamed'? to 383 K, Li and Nghiem"
used Henry's law and an equation of state to describe the aqueous and COz-rich
phases, respectively, over a 298 to 523 K temperature range and a 6,9 to 100 MPa
pressure range, Approximately 60 CO2 solubilities were used in their study, The
partial molar volume of CO 2 at infinite dilution in water was estimated using the
Lyckman et al. correlation? as presented by Heidemann and Prausnitz." The gas
and liquid phase compositions were regressed by optimizing the gas phase
interaction parameter and the Henry's constant.
In our study, 110 solubilities (consisting of all of the data from the aforemen-
tioned CO 2-solubility data base which fell within the temperature and pressure
range of interest) along 12 isotherms between 298 and 523 K were compiled over
a 3,40 to 72.41 MPa pressure range. The data from all sources were used
together, they were not treated separately, These data were used to find the value
of the reference Henry's constant," H~o" which best satisfied the following
expression at each temperature,
Since

teo, _ HO [Veo,(p - P"w)] - H (1)

- eo,exp RT - co"
Yeo"w
then
In ( -t eo,
-) = In H*eo,+-- P = I n HOeo,+--
veo, () °)
veo, ( P-Pw, (2)
Yeo,.w RT RT
where
In H*
co,
= In H O
co,
_ veo,P"w
RT (2a)

Equation 2 is known as the Krichevsky-Kasarnovsky equation.Y''"

Carbon dioxide fugacities were obtained using the Peng-Robinson equation of
state, and vapor-phase (C0 2-rich phase) compositions were obtained from
literature values. For conditions at which no experimental vapor-phase composi-
tions were available, values were calculated using the Peng-Robinson equation of
state and the asymmetric mixing rule. An interaction parameter of 0.2 was used
 26 ROBERT M. ENICK AND SCOTT M. KLARA
in the fugacity calculation.v'" with slightly smaller values being employed above
373 K (Table 1, Reference 6). Li and Nghiem'' used the Peng-Robinson equation
of state with the conventional mixing rule for this phase only. Pollack et al., 16
used the two-parameter mixing rule of Panagiotopolous and Reid,13 in which one
of the parameters primarily characterizes the aqueous phase while the other
characterizes the CO 2-rich phase. This CO 2-rich phase parameter is really
equivalent to that of Li and Nghiem. The Lyckman et al., 7 correlation was used to
determine veo, since it agrees well with experimentally determined values of this
parameter.Y"? The correlation for the reference Henry's constant, Eq. (3),
H~o, = -4704.17 + 26.57845T - 0.0376298T 2 + 9.63891· lO- 6 T 3 (3)
agrees well with the results of Li and Nghiem" over the entire temperature range.
In our second analysis, the data were regressed by optimizing both H~o, and
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veo,. For many systems, the intercept of the plot of the left hand side of Eq. (2)
against pressure is the reference Henry's constant, and the slope is veo/RT. The
values of the Henry's constant and veo, obtained from this analysis, and all other
methods used in this study, are plotted in Figures 1 and 2. Empirical correlations
for each of these parameters are given below.
H~o, = -5032.99 + 30.74113T - 0.052667T 2 + 2.630218· lO- 5 T 3 • (4)
veo, = 1799.36 -17.8218T + O. 0659297T 2
- 1.05786· lO- 4T3 + 6.200275· lO- sT 4 (5)
Neither of these two expressions, but especially that for veo" should be
extrapolated beyond the 298 to 523 K range. The CO 2 solubilities obtained using
Eqs. (4) and (5) correlated with the data slightly better than solubilities obtained

600 , - - - - - - - - - - - - - - - - - - - ,

500

ro
n, 400
6
•
:r:
300
- - Eqn, 7. K-I

200
- - Eqn, 4, K·K rvC'o, Adjusted)
- - - Eqn, 3, K·K ('V;o, from Ref. 7)
- - - - Li and Nghiem 6
100 .L-_-'---_--'---_---'-_--"_._~_ _'____ __'___ ___'
~ ~ ~ ~ ~ 4~ ~ m ~

Temperature (K)

FIGURE I Correlations for the Henry constant of the COz/HzO system,

 CO 2 SOLUBILITY IN WATER AND BRINE 27
50 . - - - - - - - - - - - - - - - - - - - - - ,

45

40

35

30

7
- - Lyckman,et,al.
- - Based on the K-K Equation
with Vc~ treated as an
adjustable parameter
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10 L-_-'-_--'---_---'-_--l_ _L-_..L-_---'--_----l
~ 2~ ~ ~ ~ ~ ~ 5~ ~

Temperature (K)
FIGURE 2 Correlations for the partial molar volume of carbon dioxide at infinite dilution in water.

using Eq. (3) and the Lyckman et al., 7 correlation since two parameters were
adjusted to match the data rather than one.
Parkinson and Deblevers'" first noted that partial molar volumes obtained in
this manner for the CO 2/H20 system did not correspond to experimental values
even though linear plots of Eq. (2) with high correlation coefficients were
obtained. This is clearly evident in our results by the decrease in veo, at high
temperatures, Figure 2. This trend is contrary to experimentally determined
values of VeO,,41.42 which are well represented by the Lyckman et al., 7 correlation
over this temperature range. Gibbs and Van Ness? explained that it was possible
to correlate solubilities for the CO 2/H20 system in this manner, but the partial
molar volumes at infinite dilution could bear no similarity to actual values. They
showed that the Krichevsky-Ilinskaya equation," Eq. (6), is more appropriate
for this system. Unlike the Krichevsky-Kasarnovsky equation, it accounts for the
change in the activity coefficient of the solute as a function of composition."

teo,
In ( - ) veo, ( ) _ I H* A( 2
- - RT P - n eO'+RT YH,O.w-
1) (6)
Yeo,.w
The A parameter is determined from the slope of linear plots of the left-hand side
of Eq. (6) against (Y~,o. w - 1).
The correlations obtained for the two parameters, H~o, and A, obtained by
performing a least-squares analysis of Eq. (6), are given below. They are also
illustrated in Figures 1 and 3, respectively.
H~o, = 5076.29+ 31.9877T - 0.057691 T 2 + 3.18012· 1O-5T3 (7)
A = -2.08184 . 106 + 2.13034 . 104T - 79.8190T 2 + 0.129991 T 3
- 7.76471 . 1O-5T4 (8)
The correlation for H~o, is, as expected, nearly identical to that obtained by
 28 ROBERT M. ENICK AND SCOTT M. KLARA
4000 , - - - - - - - - - - - - - - - - - - - - ,
Correlated, Eqn. 8
Data
3000

Q)
"0 2000
:;:

-o
~
«
"iii
1000
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·1000 L-_-'-_--'-_---'-_----'_ _-'---_--'--_---'--_----.J

~ 2~ 300 3~ ~ 4~ ~ ~ ~

Temperature IK)
FIGURE 3 Correlation for A in the Krichevsky-Ilinskaya equation.

using the Krichevsky-Kasarnovsky equation and by treating the partial molar

volume of carbon dioxide at infinite dilution as an adjustable parameter,
Eq. (5).41
The pressure range associated with all three correlations neglects low-pressure
data «3.4 MPa) since they are not relevant to the modeling of reservoir
conditions. Slightly different values for the fitted parameters will be obtained for
low-pressure data. 6 •43

EFFECT' OF DISSOLVED SOLIDS ON CO 2 SOLUBILITY

Dissolved solids in the aqueous phase are known to decrease the solubility of light
gases such as CO 2 , Li and Nghiem" suggest that the scaled particle theory
(SPT)'5-49 can be used to determine the Henry's constant for these systems.
Literature values so-s4 for three parameters used in the SPT (a, (1', and E) can be
obtained for each ion present in the brine. In order to match experimental
solubility data, the a parameter of the solute is optimized.
In this work, the reduction of CO 2 solubility due to dissolved solids was
correlated to CO 2 solubility in pure water, as suggested by Klins. ss A data set of
167 solubilities27- 36 was obtained, for a temperature range of 298 to 523 K and a
presure range of 3.0 to 85.0 MPa, for aqueous solutions containing sodium
chloride, calcium chloride, and unspecified brines. No trends other than total
dissolved solids (TDS), such as temperature and pressure, were distinct enough to
correlate from this large set of data. All ions were found to decrease solubility
to a comparable extent when the TDS concentration was measured on a weight,
not molar, basis. This greatly simplifies computations for compositional simula-
tions of CO 2 displacement since all ions can be simply lumped together on a
 CO 2 SOLUBILITY IN WATER AND BRINE 29

..
.s
.,
.,
·iii
III
:E .7

'"
·iU
;;:
t;; .s c
n;
;;:
i!!
::l
Q.
.s
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.
B
>
o
'0
:; .,
Q;
a:
~ Sea
Water Brine CaCI2 NaCI T(K)
:c::l
(;
.3
2" :ll'
sn 297
+
0
o
'" 298
323
.2 3<,
3cp\MPllj<SS
323

98'
eaa
.1
'"
saa

°0 10 15 ~ 25 ~
TDS,Weight %
FIGURE 4 CO 2 solubility in brine relative to pure H 20.

weight basis. Computational time requirements for reservoir simulation calcula-

tions are only marginally affected by the introduction of an additional parameter,
TDS, and its corresponding material balance equation. The "tracking" of brine
by incorporating additional material balances for each ion used in conjunction
with SPT to determine solubilities may not be a practical approach to this
modeling problem, even though it is more accurate. The final correlation
obtained from this study, shown in Figure 4, is
Weo,.b = weo,. w' (1.0 - 4.893414· 1O-2(TDS)
+ 0.1302838· 1O-2(TDS)2- 0.1871199· 1O-'(TDS)3). (9)

CONCLUSIONS

The major conclusions of this study are summarized below.

I. The reference Henry's constant for the CO 2/water system and the partial
molar volume of CO 2 at infinite dilution in water have been correlated from a
 30 ROBERT M. ENICK AND SCOTT M. KLARA
very large data base of literature data over the temperature and pressure ranges
associated with miscible displacement processes. Empirical temperature-
dependent expressions have been determined for (a) Ht02 and A for the
Krichevsky-Ilinskaya equation, (b) Ht0 2 and V~02 for the Krichevsky-
Kasarnovsky equation, and (c) Ht02 for the Krichevsky-Kasarnovsky equation
using the Lyckman, et al., 7 correlation for V~02'
2. Carbon dioxide solubilities in water are best matched in a thermodynami-
cally consistent manner when the Krichevsky-Ilinskaya equation is used. The
temperature-dependent A parameter exhibits a wide scatter about a polynomial
fit of its values at various temperatures, however. The Krichevsky-Kasarnovsky
equation gives equally accurate solubilities when the partial molar volume is
treated as an adjustable parameter, but the values of this parameter are
inconsistent with actual values. When the correct values for the partial molar
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volume are used, the accuracy of the predicted CO 2 solubilities decreases since
only one adjustable parameter, Ht0 2, appears in the equation.
3. An empirical correlation for the decreased solubility of CO 2 in an aqueous
phase containing dissolved solids is presented. One hundred sixty-seven literature
data points were used to develop this correlation. CO 2 solubility in brine relative
to that in water at the same temperature and pressure is correlated with the total
dissolved solids concentration. Although the correlation is easy to use in reservoir
simulation since all ions are lumped together, it is characterized by a wide scatter
of data and is less accurate than techniques which account for the combined
effects of individual ions.

NOMENCLATURE

A parameter in the Krichevsky-IIi:tskaya equation, Joules/mole.

{; fugacity of CO 2 , MPa
H e02 Henry's law constant of CO 2 , MPa
Ht0 2 reference Henry's law constant of CO 2 , MPa
H e02 Henry's law constant of CO 2 at a given pressure P"... MPa
M molecular weight
p pressure, MPa
p".. pressure where H?is evaluated, vapor pressure of water, MPa
P absolute pressure, MPa
R universal gas constant, 8.314 MPa cm3/mole K
T temperature, K
TDS total dissolved solids concentration (weight percent) excluding dis-
solved gases.
v molar volume, crrr'Zrnole
molar volume of CO 2 at infinite dilution, cm 3/mole
 CO 2 SOLUBILITY IN WATER AND BRINE 31
w solubility, weight fraction
Yco,.w mole fraction of CO 2 in the aqueous phase

Subscripts
b brine
w water

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