Applied Geochemistry 54 (2015) 1–12

Contents lists available at ScienceDirect

Applied Geochemistry

journal homepage: www.elsevier .com/ locate/apgeochem

An improved cubic model for the mutual solubilities of CO2–CH4–H2S–brine systems to high temperature, pressure and salinity

http://dx.doi.org/10.1016/j.apgeochem.2014.12.0150883-2927/� 2014 Elsevier Ltd. All rights reserved.

⇑ Corresponding author.E-mail address: lijun2009s@gmail.com (J. Li).

Jun Li a,⇑, Lingli Wei b, Xiaochun Li a

a State Key Laboratory of Geomechanics and Geotechnical Engineering, Institute of Rock and Soil Mechanics, Chinese Academy of Sciences, Wuhan 430071, Chinab Shell China Innovation and R&D Centre, Beijing 100004, China

a r t i c l e i n f o

Article history:Available online 29 December 2014Editorial handling by M. Kersten

a b s t r a c t

The phase behavior of CO2–CH4–H2S–brine systems is of importance for geological storage of greenhousegases, sour gas disposal and enhanced oil recovery (EOR). In such projects, reservoir simulations play amajor role in assisting decision makings, while modeling the phase behavior of the relevant CO2–CH4–H2S–brine system is a key part of the simulation. There is a need for an equation of state (EOS) for suchsystem which is accurate, with wide application range (pressure, temperature and aqueous salinity),computationally efficient and easy for implementation in a reservoir simulator.

In this study, an improved cubic EOS model of the system CO2–CH4–H2S–brine is developed based onthe modifications of the binary interaction parameters in Peng–Robinson EOS, which is widely imple-mented in reservoir simulators. Thus the new model is suited for numerical implementation in reservoirsimulators.

The available experimental data of pure gas brine equilibrium and gas mixture solubility in water/brineare carefully reviewed and compared with the new model. From the comparison, the new model canaccurately reproduce (1) the CO2–brine mutual solubility data at temperature from 0 �C to 250 �C, pres-sure from 1 bar to 1000 bar and NaCl molality (mole number in 1 kg water, molal is used for short) from 0to 6 molal, (2) CH4–brine mutual solubility data at temperature from 0 �C to 250 �C, pressure from 1 barto 2000 bar and NaCl molality from 0 to 6 molal, (3) H2S–brine mutual solubility data at temperaturefrom 0 �C to 250 �C, pressure from 1 bar to 200 bar and NaCl molality from 0 to 6 molal, and (4) has goodaccuracy for gas mixture solubility in brine.

� 2014 Elsevier Ltd. All rights reserved.

1. Introduction

CO2 capture and sequestration (CCS) is thought to be an impor-tant way to face the global climate change (IPCC, 2005). Some ofthe aquifers especially under the oil layers of depleted oil reser-voirs are saturated with CH4 (Hovorka et al., 2006;Mukhopadhyay et al., 2012). The depleted gas reservoirs which stillcontain significant amount of hydrocarbons are also considered aspotential CO2 sequestration formations (van der Meer et al., 2005).With the increase of the global energy demands and the technol-ogy progress, oil reservoirs containing sour gas (mainly H2S andCO2) become more and more attractive for oil recovery. There-injection of the sour gas into the reservoirs or saline aquifersis an important way of dealing with the sour gas for HSE (health,safety and environment) reasons (Abou-Sayed et al., 2005; Bachuand Gunter, 2004).

The phase behaviors of CO2, H2S, CH4 and brine systems areessential to understand the migration and variation of the fluidsafter CO2 or sour gas injection, as well as the stability and safetyof the gas injection activities. The thermodynamic modeling workof hydrocarbons, CO2, CO, etc. started from 1980s (Li and Nghiem,1986; Harvey and Prausnitz, 1989; Gao et al., 1999; Zuo and Guo,1991). These models can only reproduce gas solubilities at lowsalinity, low temperatures or low pressures which are not applica-ble to reservoir conditions. To develop the gas solubility models,Duan and co-workers gave comprehensive reviews for the singlegas component solubility in pure water or brine measurementsof CO2, CH4 and H2S (Duan and Sun, 2003; Duan and Mao, 2006;Duan et al., 1992; Li and Duan, 2011; Mao et al., 2013). But theirwork does not cover about gas mixture solubility which is of morepractical importance in actual field applications. Ziabakhsh-Ganjiand Kooi (2012) and Zirrahi et al. (2012) are the most recent workon modeling the CO2, CH4, H2S and brine equilibrium. Their resultsare accurate from the comparison with the existing experimentaldata for both single component gas solubility and gas mixture sol-ubility. However, the applicable pressure (lower than 600 bar) and

2 J. Li et al. / Applied Geochemistry 54 (2015) 1–12

temperature (lower than 110 �C) exclude some applications ofpractical interest. Oldenburg et al. (2004) proposed a new EOSmodule for TOUGH2 (Pruess et al., 1999) with their thermody-namic model of CO2/N2–CH4–H2O system for the application ofgas injection in aquifers containing CH4. By the new TOUGH2 mod-ule, gas mixture solubility can be calculated in pure water. Thesalinity effect on gas solubility has not been considered in themodel yet. Battistelli et al. (2003) and Battistelli (2008) developedTMVOC (as a TOUGH2 family simulator) to model three phase,non-isothermal flow of mixtures of water, non-condensible gases,volatile organic components and dissolved solids in multidimen-sional heterogeneous porous media. The simulator was used withTOUGHReact (Xu et al., 2007) for the simulation of acid gas injec-tion (Zheng et al., 2010; Zhang et al., 2011). Further, the EOS

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0 20 40 60 80 100

CO2

solu

bilit

y in

brin

e (m

ole/

KgW

)

Pressure/bar

mNaCl = 6 molalExperimental data from Rumpf et al. (1994)

(a)

333.15 K

353.15 K

433.15 K

333.15 K353.15 K

433.15 K

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0 500 1000 1500 2000

CH4

solu

bilit

y in

NaC

l sol

u�on

s (m

olal

)

Pressure (bar)

mNaCl=0.055mole/KgWmNaCl=1.9mole/KgWmNaCl=5.8mole/KgW

Experimental data: Blount and Price (1982), 374K

(b)

0

0.01

0.02

0.03

0 20 40 60 80 100

H 2S

mol

e fr

ac�o

n in

aqu

eous

pha

se

Pressure (bar)

40 deg-C

60 deg-C

80 deg-C

120 deg-C

Experimental data: Xia et al. (2000)mNaCl = 4.01 molal

(c)

Fig. 1. Comparisons of the gas solubility in NaCl solutions calculated by the SWmodel (Søreide and Whitson, 1992) with the related experimental data. (a) CO2

solubility in NaCl solutions at different temperatures and pressures, with NaClmolality 6 molal; (b) CH4 solubility in NaCl solutions at different pressures and NaClmolalities; (c) H2S solubility in NaCl solutions at different temperatures andpressures, with NaCl molality 4.01 molal. Dots are experimental data and thedashed lines are calculated by the SW model.

TMGAS (Battistelli and Marcolini, 2009) (coupled into TOUGH2)was developed for brine and gas mixtures (CO2, H2S and hydrocar-bons) based on Søreide and Whitson (1992). The TMGAS model canaccurately reproduce the gas–brine equilibria in wide temperatureand pressure range, but the accuracy decreases for salt molalityhigher than 2 molal (from the comparisons with the experimentaldata). Recently, Bacon et al. (2014) coupled a revised TMGAS modelinto the STOMP-COMP simulator for the simulation of acid gasinjection.

To consider the complexity of the compounds with hydrogenbonding, Kontogeorgis et al. (1996) developed a ‘‘cubic plus associ-ation’’ (CPA model) equation of state based on the classic cubicEOS. Tan et al. (2013) used the CPA model for the SO2, CO2 andbrine equilibrium modeling. Sun and Dubessy (2010, 2012) andSun et al. (2014) developed an improved SAFT (Statistical Associat-ing Fluid Theory) model by introducing a Lennard-Jones (LJ) term(SAFT-LJ models). The models were used for accurately calculatingthe phase equilibrium of CO2–brine systems and water–hydrocar-bon systems. These models (CPA or SAFT-LJ) are accurate for stand-alone simulations but not suitable for EOS compositional reservoirsimulations as they are usually computational time consuming.

Søreide and Whitson (1992) developed their modified Peng–Robinson EOS (Peng and Robinson, 1976) model (SW model) forthe phase partitioning calculation of reservoir gas (hydrocarbons,H2S, N2 and CO2) and brine (with NaCl included) system. Theymade modifications for binary interaction parameters of aqueousand non-aqueous phases respectively. Shah et al. (2008) used theSW model to calculate water/H2S equilibrium and the resultsexcellently agreed with the related experimental data for theirmeasurements of water and acid gas interfacial tension. The SWmodel can predict the single component gas solubility in aqueousphase at low salinity with acceptable accuracy for most of thegases referred above, but the performance still has space forimprovements when the salinity increases (Mao et al., 2005;Duan and Mao, 2006). Fig. 1 shows the comparison between theSW model results and the related experimental data. From thecomparisons, the SW model shows obvious inaccuracies for pre-dicting gas solubilities in NaCl solutions. However, the SW modelprovides a good framework for phase behavior calculation of brineand the above gas mixture system with modifications of theparameters. As all the EOS compositional simulators use cubicEOS implementation due to its computational efficiency, the modelin this work is also based on the modifications of Peng–Robinsonmodel, and attempts to reproduce the available experimental dataof the system CO2–CH4–H2S–brine to high temperature, pressureand salinity.

2. Theoretical background

Peng and Robinson (1976) developed a two parameter cubicequation of state with the following form:

P ¼ RTV � b

� aðTÞVðV þ bÞ þ bðV � bÞ ð1Þ

where P is pressure (in MPa), T is temperature (in K), R is gas con-stant and V is volume (cm3). a and b are parameters.a ¼ aðTcÞ � aðTr;xÞ. Tc is critical temperature. Tr is reduced temper-ature. x is acentric factor. In this work, for the a-term, we followthe SW model (Søreide and Whitson, 1992):

a1=2 ¼ 1þ 0:4530 1� Tr 1� 0:0103C1:1sw

� �h iþ 0:0034 T�3

r � 1� �

ð2Þ

where Csw is NaCl molality. Similar as the SW model, the binaryinteraction coefficients for the constant ‘‘a’’ in the mixing rule

J. Li et al. / Applied Geochemistry 54 (2015) 1–12 3

equation of the original Peng–Robinson model were determined foraqueous and non-aqueous phases respectively

aNA ¼X

i

Xj

yiyjðaiajÞ12 1� kNA

ij

� �ð3Þ

aAQ ¼X

i

Xj

xixjðaiajÞ12 1� kAQ

ij

� �ð4Þ

Here, NaCl is a pseudo-component which is completely dissociatedin water. xi is the mole fraction of component i in aqueous phase,and yi is the mole fraction of component j in non-aqueous phase.

The binary parameters kAQij and kNA

ij

� �for the aqueous and non-

aqueous phases are functions of temperature and dissolved salt(NaCl) molality in the aqueous phase.

With the above framework of modeling, the main objectives inthis work are to: (1) improve the single component gas solubilityaccuracy at high salinity condition for system of CO2–brine, CH4–brine and H2S–brine; (2) improve the gas mixture solubility accu-racy in aqueous phase; and (3) reproduce the H2O solubility accu-rately in non-aqueous phase. For the distribution of theexperimental data and the application significance in reservoirstudy, the objective temperature, pressure and NaCl molalityranges of the modeling work for CO2–brine and CH4–brine systemsare 0–250 �C, 1–1000 bar and 0–6 molal respectively. For H2S–brine system, as the experimental data pressure range is small,the objective temperature, pressure and NaCl molality range ofthe modeling work is 0–250 �C, 1–200 bar and 0–6 molalrespectively.

To improve the accuracy of the single gas component solubilityin water and brine, the binary interaction parameters kAQ

ij for CO2–H2O, CH4–H2O and H2S–H2O were refitted from the experimentaldata of single component gas solubility in water and brine. ForH2O and CO2, the binary interaction parameter is a function of tem-perature, pressure and NaCl molality in water with 10 parameters:

kAQH2O—CO2

¼ a1 þ a2Csw þ ða3 þ a4CswÞT

TCO2c

þ ða5 þ a6CswÞT

TCO2c

!2

þ a7 þ a8Csw þ ða9 þ a10CswÞT

TCO2c

!lnðPÞ ð5Þ

where T is temperature (K) and P is pressure (bar); Csw denotes theNaCl molality; TCO2

c denotes the critical temperature of CO2; a1 to a10

are constants that are shown in Table 1. Compared with the SWmodel, (1) only linear Csw term is used for the NaCl molality depen-

dence; (2) the term TT

CO2c

� �2

is added; and (3) the pressure depen-

dent term is added with lnðPÞ.

Table 1Regressed aqueous phase binary interaction parameters in Eq. (5) and (6) from thiswork.

Parameters H2O–CO2 H2O–CH4 H2O–H2S

a1 �5.6554E�1 �1.5500E+0 �4.2619E�1a2 8.1650E�2 1.3828E�1 2.45089E�2a3 5.4814E�1 1.0334E+0 6.73586E�1a4 �1.2555E�1 �1.1873E�1 �5.30943E�2a5 �1.0692E�1 �1.4884E�1 �2.16250E�1a6 5.4441E�2 3.0121E�2 3.46184E�2a7 4.9081E�3 – –a8 �1.3859E�3 – –a9 �8.4159E�4 – –a10 1.0764E�3 – –

For H2O–CH4 and H2O–H2S systems, the binary interactionparameter is a function of temperature and NaCl molality with 6constants:

kAQH2O�i ¼ a1 þ a2Csw þ ða3 þ a4CswÞ

T

Tic

þ ða5 þ a6CswÞT

Tic

!2

ð6Þ

Here, Tic is the critical temperature of CH4 or H2S. a1–a6 are the con-

stants as listed in Table 1. Compared with the SW model, only linear

Csw term is used for the NaCl molality dependence, and the TTi

c

� �2

term is added.The non-aqueous phase binary interaction parameters kNA

ij

� �are set identical with the SW model. See Table 2.

3. Calculation routine

When a system in equilibrium at given temperature and pres-sure, the necessary and sufficient condition is that the fugacitiesare equal for any component in all phases (when the same EOS isused for different phases):

f NAi ¼ f AQ

i ð7Þ

where f NAi denotes the fugacity of component i in non-aqueous

phase, and f AQi denotes the fugacity of component i in aqueous

phase. From Eq. (7),

/NAi yi ¼ /AQ

i xi ð8Þ

where /NAi and /AQ

i are the fugacity coefficients in non-aqueous andaqueous phases respectively. The fugacity coefficients can be calcu-lated from the modified cubic EOS, same with Eq. (19) in Peng andRobinson (1976). If the K value of component i is defined as Ki ¼ yi

xi,

we have

Ki ¼/AQ

i

/NAi

ð9Þ

The phase partitioning can be solved iteratively:(1) Provide the feed composition (zi) for the system. We need to

solve the mole fraction of each species (xi or yi) in differentphases under the given condition (T, P and NaCl molality).

(2) Initial estimation. Wilson approximation (Michelsen andMollerup, 2007) can be used for the initial K value estima-tion. Alternatively, we can also provide guessed gas solubil-ity with small values as the initial estimation, and Psat

H2O=P canused as the initial estimation of H2O mole fraction in thenon-aqueous phase.

(3) Solve the Rachford-Rice equation (Michelsen and Mollerup,2007) for non-aqueous phase mole fraction b.

Table 2Non-aq

H2O–H2O–H2O–CO2–CO2–CH4–

Xn

i¼1

ziðKi � 1Þ1þ ðKi � 1Þb ¼ 0 ð10Þ

Calculate xi and yi from

(4)

ueous phase binary interaction parameters.

kNA

CO2 0.1896CH4 0.485H2S 0:19031� 0:05965 � Tr ;H2SCH4 0H2S 0H2S 0

Table 3The deviation CO2 solubility calculated the model from the experimental data.

References mNaCla T (K) P (bar) Nb AADc (%)

Malinin and Savelyeva (1972) 0 298.15–348.15 47.92 11 3.21Malinin and Kurorskaya (1975) 0 298.15–423.15 47.92 6 2.48Todheide and Franck (1963) 0 323.15–623.15 200–3500 17 4.16Takenouchi and Kennedy (1964) 0 383.15–623.15 100–1500 41 4.98Takenouchi and Kennedy (1965) 0 423.15–623.15 100–1400 23 5.29Wiebe and Gaddy (1939) 0 323.15–373.15 25.33–709.28 29 2.93Wiebe and Gaddy (1940) 0 298.15–313.15 25.33–506.63 42 2.98Malinin (1959) 0 473.15–573.15 98.07–490.33 10 4.53Zawisza and Malesinska (1981) 0 323.15–473.15 1.54–53.89 33 3.94Müller et al. (1988) 0 373.15–473.15 3.25–81.1 49 4.68King et al. (1992) 0 288.15–298.15 60.8–202.7 27 2.82Ellis and Golding (1963) 0 450.15–538.15 25.25–101.01 10 4.23Nighswander et al. (1989) 0 352.85–471.25 20.4–102.1 33 9.40Prutton and Savage (1945) 0 374.15–393.15 23.3–654.56 26 7.14Drummond (1981) 0 303.85–537.75 39.1–143.87 43 5.65Anderson (2002) 0 274.15–288.15 0.76–21.79 54 9.43Bamberger et al. (2000) 0 323.2–353.1 40.5–141.1 29 1.38Gillesp and Wilson (1982) 0 288.75–366.45 6.9–202.7 24 5.55Stewart and Munjal (1970) 0 273.15–298.15 10.13–45.6 12 14.5Servio and Englezos (2001) 0 277.05–283.15 20–42 9 6.24Teng et al. (1997) 0 278–298 1–294.9 48 6.20Shagiakhmetov and Tarzimanov (1981) 0 323.15–373.15 100–800 9 3.52Oleinik (1986) 0 283.15–343.15 10–160 23 2.73Yang et al. (2000) 0 298.29–298.57 21.7–76.9 9 4.88Zel’vinskii (1937) 0 273.15–373.15 10.84–94.46 80 2.97Bartholomé and Friz (1956) 0 283.15–303.15 1.01–20.27 15 5.25Matous et al. (1969) 0 303.15–353.15 8.82–39.01 13 3.30Morrison and Billett (1952) 0 286.45–347.85 1.03–1.39 18 8.63Markham and Kobe (1941) 0 273.35–313.15 1.02–1.09 3 8.82Harned and Davis (1943) 0 273.15–323.15 1.02–1.14 14 4.79Briones et al. (1987) 0 323.15 68.2–177.8 7 4.00Dhima et al. (1999) 0 344.25 100–1000 7 4.47Zheng et al. (1997) 0 278.15–338.15 0.49–0.84 10 8.08Valtz et al. (2004) 0 278.22–318.23 4.65–70.63 47 5.99Kritschewsky et al. (1935) 0 293.15–303.15 4.86–29.38 10 7.15Rosenbauer et al. (2001) 0 294.15 100–600 3 3.25Dohrn et al. (1993) 0 323.15 101–301 3 10.45D’Souza et al. (1988) 0 323.15–348.15 101.33–152 4 6.50Sako et al. (1991) 0 348.3–421.4 101.8–174.5 6 10.49Kiepe et al. (2002) 0 313.2–393.17 0.9509–92.58 39 7.93Bando et al. (2003) 0 303.15–333.15 100–200 12 5.16Chapoy et al. (2004a,b) 0 274.14–351.31 1.9–93.33 27 6.55Li et al. (2004) 0 332.15 33.4–198.9 6 6.41Sabirzyanov et al. (2003) 0 298.15–423.15 100–800 17 10.05Ferrentino et al. (2010) 0 313 75–150 12 3.75Han et al. (2009) 0 313.2–343.2 43.3–183.4 28 2.37Valtz et al. (2004) 0 278.22–318.23 4.65–79.63 47 6.06Koschel et al. (2006) 0 323.1–373.1 20.6–194.7 8 3.43Liu et al. (2011) 0 308.15–328.15 20.8–159.9 31 2.54Ellis and Golding (1963) 0.5–2.0 449.15–603.15 35.76–207.54 21 3.70Drummond (1981) 1–6.51 293.65–673.15 34.48–392.78 290 6.36Takenouchi and Kennedy (1965) 1.09–4.16 423.15–673.15 100–1400 34 7.85Malinin and Savelyeva (1972) 0.36–4.46 298.15–348.15 47.92 13 3.93Malinin and Kurorskaya (1975) 1–5.92 298.15–423.15 47.92 27 5.45Nighswander et al. (1989) 0.1727 353.35–473.65 21.1–100.3 34 8.22Markham and Kobe (1941) 0.2–4 273.35–313.15 1.02–1.08 15 9.66Harned and Davis (1943) 0.2–3 273.15–323.15 1.02–1.14 55 7.21Onda et al. (1970) 0.51–3.21 298.15 1.045 8 6.73Yasunishi and Yoshida (1979) 0.46–5.73 288.15–308.15 1.0132 27 4.07Bando et al. (2003) 0.17–0.53 303.15–333.15 100–200 36 5.85Rumpf and Maurer (1993) 4.0–6.0 313.15–433.08 4.67–96.42 63 5.64Gu (1998) 0.5–2.0 303.15–323.15 17.73–58.96 60 4.00

a NaCl molality of the experimental solution with unit molal.b Number of the experimental data in the range temperature from 0 �C to 250 �C and pressure from 1 bar to 1000 bar.c Average absolute deviations calculated by this model with temperature from 0 �C to 250 �C and pressure from 1 bar to 1000 bar.

4 J. Li et al. / Applied Geochemistry 54 (2015) 1–12

xi ¼zi

1þ ðKi � 1Þb ; yi ¼ziKi

1þ ðKi � 1Þb ð11Þ

Update /NAi and /AQ

i with xi and yi from the cubic EOS in the

(5)previous section, and K values from Eq. (9).

(6) Calculate esp ¼maxK�i �K�;old

i

K�;oldi

��������. If esp is smaller than 1.E�5,

stop, otherwise go to step (3).

4. Parameterization

The parameters that need to be determined are the binary inter-action parameters of the cubic EOS for aqueous phase. They arekAQ

H2O—CO2, kAQ

H2O—CH4, and kAQ

H2O—H2S, as functions of temperature, andNaCl molality from Eqs. (5) and (6). The parameters in Eqs. (5)and (6) can be evaluated in two steps: (1) evaluate the parameters

Table 4The deviation CH4 solubility calculated the model from the experimental data.

References mNaCla T (K) P (bar) Nb AADc (%)

Bunsen (1855) 0 279.35–298.75 1.01–1.03 5 7.52Winkler (1901) 0 273.42–353.15 1.01–1.47 9 11Wetlaufer et al. (1964) 0 278.2–318.2 1.01–1.10 3 5.11Morrison and Billett (1952) 0 285.1–348.4 1.01–1.39 12 3.41Claussen and polglase (1952) 0 274.8–312.8 1.01–1.07 6 7.54Lannung and Gjaldbaek (1960) 0 291.15–310.15 1.02–1.06 6 2.2Namiot (1961) 0 297.15–283.15 1.01 2 8.86Wen and Hung (1970) 0 278.15–308.15 1.01–1.06 4 5.07Ben-Naim et al. (1973) 0 278.15–298.15 1.01–1.03 5 6.52Ben-Naim and Yaacobi (1974) 0 283.15–303.15 1.01–1.04 5 4.79Moudgil et al. (1974) 0 298.15 1.03 1 3.6Yamamoto et al. (1976) 0 273.15–302.7 1.01–1.04 35 7.70Muccitelli and Wen (1980) 0 278.15–298.15 1.01–1.03 5 7.14Cosgrove and Walkley (1981) 0 278.15–318.15 1.01–1.10 9 3.13Rettich et al. (1981) 0 275.46–328.15 1.01–1.16 16 4.72Culberson and McKetta (1950) 0 298.15 36.2–667.4 11 9.81Culberson and Mcketta (1951) 0 298.2–444.3 23.5–689.1 71 1.93Duffy et al. (1961) 0 298.15–303.15 3.17–51.71 17 8.83O’Sullivan and Smith (1970) 0 324.65–398.15 101.3–616.1 18 4.25Amirijafari and Campbell (1972) 0 310.93–344.26 41.4–344.7 8 1.38Price (1979) 0 427–627 35.4–1972.6 37 9.98Blount and Price (1982) 0 373.37–374.15 150.01–1542.06 25 3.74Crovetto et al. (1982) 0 297.5–518.3 13.27–64.51 7 6.02Stoessell and Byrne (1982) 0 298.2 24.1–51.7 3 4.19Cramer (1984) 0 277.2–573.2 11–132 22 8.48Yarym-Agaev et al. (1985) 0 298.2–338.2 25–125 15 4.47Dhima et al. (1999) 0 344 200–1000 4 2.32Kiepe et al. (2003) 0 313.35–373.29 3.40–92.60 36 7.10Wang et al. (2003) 0 283.2–303.2 20–400.3 17 5.59Chapoy et al. (2004a,b) 0 275.11–313.11 9.73–179.98 16 4.85Wiesenburg and Guinasso, 1979 0 273.15–303.15 1 19 9.63Lekvam and Bishnoi (1997) 0 274.19–285.67 5.67–90.82 18 6.63Eucken and Hertzberg (1950) 0–2.77 273.15–293.15 1.02–1.04 7 8.21Mishnina et al. (1962) 0–6.24 277.15–363.15 1.02–1.17 50 12.99Yano et al. (1974) 0–1.55 298.15 1.04 4 4.71Namiot (1961) 0–1.54 323–623 295 10 5.57Stoessell and Byrne (1982) 0–4 298.15 24.1–51.7 25 10.60Blount and Price (1982) 0.05–5.88 373.93–513.15 74.58–1572.06 645 7.85Ben-Naim et al. (1973) 0.25–2.09 283.15–303.15 1.02–1.05 20 11.42

a NaCl molality of the experimental solution with unit molal.b Number of the experimental data in the range temperature from 0 �C to 250 �C and pressure from 1 bar to 1000 bar.c Average absolute deviations calculated by this model with temperature from 0 �C to 250 �C and pressure from 1 bar to 1000 bar.

Table 5The deviation H2S solubility calculated the model from the experimental data.

References mNaCla T (K) P (bar) Nb AADc

Barrett et al. (1988) 0–5 296.65–369.65 1.01 270 10.89Selleck et al. (1952) 0 310.93–444.26 6.89–86.18 34 3.32Lee and Mather (1977) 0 293.15–453.15 2.6–66.5 57 4.71Hendriks and Meijer (2009) 0 310.93–422.04 7–208 27 5.31Xia et al. (2000) 4.01–5.95 313.13–393.19 2.48–97 66 5.18Suleimenov and Krupp (1994) 0–2.54 294.45–594.15 2.6–138.61 26 12.4

a NaCl molality of the experimental solution with unit molal.b Number of the experimental data.c Average absolute deviations calculated by this model.

J. Li et al. / Applied Geochemistry 54 (2015) 1–12 5

in the NaCl molality independent terms from the experimentaldata of gas solubility in pure water, which are a1, a3, a5, a7 and a9

in Eq. (5), and a1, a3 and a5 in Eq. (6); (2) evaluate the parametersin the NaCl molality dependent terms from the experimental dataof gas solubility in NaCl solutions, with are a2, a4, a6, a8 and a10 inEq. (5), and a2, a4 and a6 in Eq. (6). The weight least square methodis used for parameterization. The optimized parameters are list inTable 2.

5. Model validation

The model performance is evaluated by comparing the modelresults with the related experimental data: (1) CO2/CH4/H2S solu-

bilities in pure water or NaCl solutions; (2) H2O solubility innon-aqueous phase (CO2/CH4/H2S – rich phase); and (3) gas mix-ture – water or brine equilibria.

To evaluate the model accuracy, we compared the current avail-able experimental data points with our model results for the solu-bilities of CO2, CH4 and H2S. The average absolute deviations (AAD)of the model with experimental data of each reference were pro-vided for all the gases. Tables 3–5 show the data source, the rangeof temperature, pressure and NaCl molality, number of data pointsof each literature and the average absolute deviations correspond-ing to CO2, CH4 and H2S respectively. AAD is defined as:

AAD% ¼ 1Nexp

X jxcal � xexpjxexp

ð12Þ

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

0 200 400 600 800 1000

CO2

solu

bilit

y in

pur

e w

ater

(mol

al)

Pressure (bar)

Wiebe and Gaddy (1940), 313.15 K

Wiebe and Gaddy (1939), 373.15 K

Malinin(1959), 473.15 K

Wiebe and Gaddy (1940), 291.15 K

(a)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

0 200 400 600 800 1000 1200

CO2

solu

bilit

y in

brin

e (m

olal

)

Pressure (bar)

Takenouchi and Kennedy (1965)

This work

473.15K, mNaCl=1.09mole/KgW

423.15K, mNaCl=1.09mole/KgW

423.15K, mNaCl=4.28mole/KgW

(b)

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0 20 40 60 80 100

CO2

solu

bilit

y in

brin

e (m

olal

)

Pressure (bar)

Rumpf et al.(1994), 333.15K

Rumpf et al.(1994), 353.15K

Rumpf et al.(1994), 433.15K

mNaCl = 6 molal

(c)

1.0E-3

1.0E-2

1.0E-1

0 100 200 300 400 500 600 700 800

H 2O

mol

e fr

ac�o

n in

CO

2ric

h ph

ase

Pressure (bar)

Wiebe and Gaddy (1941)

348.15 K

323.15 K

298.15 K

(d)

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.45

0.50

0 200 400 600 800 1000 1200 1400

H 2O

mol

e fr

ac�o

n in

CO

2 ric

h ph

ase

Pressure (bar)

422.98 K

461.62 K

478.35 K

Experimental data: Tabasinejad et al. (2011)

(e)

Fig. 2. Comparisons of the mutual solubilities of CO2–H2O–NaCl system calculated by this model and the related experimental data. (a) CO2 solubility in pure water varyingwith pressure at different temperatures; (b) CO2 solubility in NaCl solutions varying with pressure at different temperatures and NaCl molality; (c) CO2 solubility in NaClsolutions varying with pressure at NaCl molality = 6 molal and different temperatures; (d) H2O solubility in CO2 – rich phase varying with pressure at different temperatures(lower temperatures); and (e) H2O solubility in CO2 – rich phase varying with pressure at different temperatures (higher temperatures). Dots are experimental data and linesare the model results.

6 J. Li et al. / Applied Geochemistry 54 (2015) 1–12

where xcal denotes the calculated gas solubility; xexp denotes theexperimental solubility; and Nexp is the number of data points.

5.1. CO2–brine mutual solubility

For the system CO2–H2O/brine, there are abundant experimen-tal data for CO2 solubility in water or brine. The AAD comparisonsof CO2 solubility in water or brine are shown in Table 3. The exper-imental TP range is from 0 �C to more than 350 �C, and 1–3500 bar.Only experimental data with T from 0 �C to 250 �C and P from 1 barto 1000 bar are chosen for comparison. From Table 3, most of theAAD values are lower than 10%, and generally around 5%.Fig. 2(a) shows the comparison between the calculated CO2 solu-bility in pure water and the experimental work from Wiebe andGaddy (1939, 1940), and Malinin (1959) varying pressure (1–1000 bar) at different temperatures. In Fig. 2(b) and (c), compari-sons are shown between the calculated CO2 solubility in NaClsolutions and the experimental data from Takenouchi and

Kennedy (1965), and Rumpf et al. (1994) at different temperaturesand pressures to high NaCl molality (6 molal). For H2O solubility inCO2 – rich phase, Wiebe and Gaddy (1941) carried out the experi-ments at 100 �C with pressure to 800 bar, and Tabasinejad et al.(2011) did measurements with temperature to more than 200 �Cand pressure to more than 1000 bar. Fig. 2(d) and (e) shows thecomparisons with the model calculations. From the comparisonsshown in Fig. 1, to high temperature (250 �C), high pressure(1000 bar), and high salinity (6 molal), the model can accuratelyreproduce the experimental data of CO2 solubility in water/brine,and H2O solubility in CO2-rich phase.

5.2. CH4–brine mutual solubility

Table 4 shows the AAD comparisons between CH4 solubility inpure water or brine calculated by this model and the experimentaldata from different references with temperature from 0 to 250 �C

0

0.1

0.2

0.3

0.4

0.5

0 200 400 600 800 1000

CH4

solu

bilit

y in

pur

e w

ater

(mol

al)

Pressure (bar)

298.2 K344.3 K377.6 K410.9 K444.3 K

Experimental data: Culberson and Mcke�a (1951)

(a)

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0 300 600 900 1200 1500

CH4

solu

bilit

y in

NaC

l sol

u�on

s (m

olal

)

Pressure (bar)

Blount and Price,1982

This work374 K, mNaCl=0.055 molal

374 K, mNaCl=1.9 molal

374 K, mNaCl=5.8 molal

(b)

1.0E-4

1.0E-3

1.0E-2

0 50 100 150 200 250 300 350

H 2O

mol

e fr

ac�o

n in

CH

4ric

h ph

ase

Pressure (bar)

288.11 K 293.11 K

298.11 K 303.11 K

308.11 K 313.12 K

318.12 K

Experimeantal data:Chapoy et al. (2004)

(c)

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0 200 400 600 800 1000

H 2O

mol

e fr

ac�o

n in

CH

4ric

h ph

ase

Pressure (bar)

423.2 K

473.2 K

523.2 KExperimental data:Sultanov et al. (1972)

(d)

Fig. 3. Comparisons between mutual solubilities in CH4–H2O–NaCl system calculated by this model and the related experimental data. (a) CH4 solubility in pure watervarying with pressure at different temperatures; (b) CH4 solubility in NaCl solutions varying with pressure at different temperatures and NaCl molalities; (c) H2O solubilitiesin CH4-rich phase varying with pressure at different temperatures (lower temperatures); and (d) H2O solubilities in CH4-rich phase varying with pressure at differenttemperature (higher temperatures). Lines are calculated from this model and dots are experimental data.

0.00

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0 50 100 150 200 250

H 2S

solu

bilit

y in

wat

er (m

ole

frac

�on)

Pressure (bar)

Selleck et al. (1952), 37.78 deg-C

Selleck et al. (1952), 70 deg-C

Selleck et al. (1952), 100 deg-C

Gillespie and Wilson (1980; 1982), 149 deg-C

(a)

0

0.01

0.02

0.03

0 20 40 60 80 100

H 2S

mol

e fr

ac�o

n in

aqu

eous

pha

se

Pressure (bar)

40 deg-C

60 deg-C

80 deg-C

120 deg-C

Experimental data: Xia et al. (2000)mNaCl = 4.01 molal

(b)

0

0.01

0.02

0.03

0 20 40 60 80 100

H 2S

mol

e fr

ac�o

n in

aqu

eous

pha

se

Pressure (bar)

40 deg-C

60 deg-C

80 deg-C

120 deg-CExperimental data: Xia et al. (2000)

mNaCl = 5.95 molal

(c)

1.0E-3

1.0E-2

1.0E-1

1.0E+0

0 50 100 150 200 250

H 2O

mol

e fr

ac�o

n in

H2S

rich

pha

se

Pressure (bar)

310.93 K

366.48 K

422.04 K

477.59 K

Experimental data: Gillespie and Wilson (1982)

(d)

Fig. 4. Comparisons between the mutual solubilities of H2S–H2O–NaCl systems calculated by this model and the experimental data. (a) H2S solubility in pure water varyingwith pressure at different temperatures; (b) H2S solubility in NaCl solutions varying with pressure at different temperatures and NaCl molality 4.01 molal; (c) H2S solubility inNaCl solutions varying with pressure at different temperatures and NaCl molality 5.95 molal; and (d) H2O solubility in H2S rich phase varying with pressure at differenttemperatures. Lines are this model results, and dots are experimental data.

J. Li et al. / Applied Geochemistry 54 (2015) 1–12 7

8 J. Li et al. / Applied Geochemistry 54 (2015) 1–12

and pressure from 1 bar to 1000 bar selected. From the table, mostof the AAD values are within 10%.

Fig. 3(a) shows the comparison of CH4 solubility in pure watercalculated by this model and the related experimental data(Culberson and Mcketta, 1951) varying with pressure from 1 barto 1000 bar at different temperatures. Fig. 3(b) shows the CH4 sol-ubility in NaCl solutions calculated by this model and the experi-mental data from Blount and Price (1982) with pressure to morethan 1000 bar and NaCl molality to nearly 6 molal. Fig. 3(c) and(d) shows the H2O solubility in CH4 rich phase with pressure to1000 bar at different temperatures (calculated results and theexperimental data). From the comparisons, the mutual solubilities(CH4 solubility in water/brine, H2O solubility in CH4 rich phase) canbe accurately reproduced by this model to high temperature, pres-sure and salinity.

5.3. H2S–brine mutual solubility

The available experimental data of H2S – brine mutualsolubilities are not as abundant as CO2/CH4 – brine systems. The

5.0E-3

9.0E-3

1.3E-2

1.7E-2

2.1E-2

2.5E-2

0.4 0.5 0.6 0.7 0.8 0.9

CO2

mol

e fr

ac�o

n in

aqu

eous

pha

se

nCO2/(nCO2+nCH4)

500 bar

300 bar

325 K325 K325 K325 K325 K325 K325 K

(a)

5.0E-4

1.0E-3

1.5E-3

2.0E-3

2.5E-3

3.0E-3

0.4 0.5 0.6 0.7 0.8 0.9

CH4

mol

e fr

ac�o

n in

aqu

eous

pha

se

nCO2/(nCO2+nCH4)

500 bar

300 bar

325 K325 K

(b)

Fig. 5. CO2 + CH4 gas mixture solubilities calculated by this model (lines) and the exper325 K with pressure from 300 bar to 500 bar; (b) CH4 mole fraction in aqueous phase at 3at 376 K with pressure from 100 bar to 500 bar; and (d) CH4 mole fraction in aqueous phafeed composition, and nCH4 denotes CH4 mole fraction in feed composition.

Table 6The results of CO2 + H2S gas mixture solubility in brine, measured by Bachu and Bennion

Contacting gascomposition (mole%)

Gas water ratio Solution gas composition(mole%)

Solution

CO2 H2S CO2 H2S

100 0 16.9 100 0 1.85690 10 19.1 74.41 25.59 1.74970 30 24.5 56.58 43.42 1.68750 50 30.6 36.39 63.61 1.59330 70 34.8 22.85 77.15 1.53710 90 40.5 9.09 90.91 1.481

0 100 44.3 0 100 1.451

experiment pressure is to about 200 bar, and temperature is tolower than 200 �C. Table 5 shows the AAD comparisons betweenH2S solubility in pure water or brine calculated by this modeland the experimental data from different references. From thecomparisons, most of the AAD values are around 5%.

Fig. 4(a) shows comparisons between calculated H2S solubilityin pure water at pressure from 1 bar to 250 bar, and temperaturefrom 38 �C to 149 �C and the experimental data (Selleck et al.,1952; Gillesp and Wilson, 1980, 1982). Fig. 4(b) and (c) showsthe comparisons between the calculated H2S solubility in NaClsolutions at pressures to 100 bar, temperature to 120 �C and NaClmolality 4 molal and �6 molal (Xia et al., 2000). Fig. 4(d) showsthe calculated H2O solubility in H2S rich phase with pressure tomore than 200 bar and temperature to 200 �C and the relatedexperimental data (Gillesp and Wilson, 1982). From the compari-sons, the model can accurately reproduce the experimental dataof mutual solubility for H2S–H2O–NaCl system with pressure toabout 200 bar, temperature 200 �C and NaCl salinity about 6 molal.More experiment studies are needed to validate the model perfor-mance of the system.

0.0E+0

5.0E-3

1.0E-2

1.5E-2

2.0E-2

2.5E-2

0.4 0.5 0.6 0.7 0.8 0.9

CO2

mol

e fr

ac�o

n in

aqu

eous

pha

se

nCO2/(nCO2+nCH4)

500 bar

400 bar

300 bar

200 bar

100 bar

376 K376 K376 K(c)

0.0E+0

5.0E-4

1.0E-3

1.5E-3

2.0E-3

2.5E-3

3.0E-3

0.4 0.5 0.6 0.7 0.8 0.9

CH4

mol

e fr

ac�o

n in

aqu

eous

pha

se

nCO2/(nCO2+nCH4)

500 bar

400 bar

300 bar

200 bar

100 bar

376 K376 K (d)

imental data of Qin et al. (2008) (dots). (a) CO2 mole fractions in aqueous phase at25 K with pressure from 300 bar to 500 bar; (c) CO2 mole fractions in aqueous phasese at 376 K with pressure from 100 bar to 500 bar. nCO2 denotes CO2 mole fraction in

(2009), and calculated by this work.

gas density (g/l) Solution gas molality(experiment, molal)

Solution gas molality(calculation)

CO2 H2S CO2 H2S

0.7442 0 0.748 00.6262 0.2154 0.692 0.1750.6151 0.4721 0.577 0.4940.4915 0.8591 0.450 0.8000.3513 1.1861 0.300 1.1200.1628 1.6283 0.114 1.4790 1.9695 0 1.776

J. Li et al. / Applied Geochemistry 54 (2015) 1–12 9

5.4. Gas mixture solubility

To validate the model reliability, we also compare the modelresults with gas mixture – water/brine experiments. Qin et al.(2008) reported 21 experimental data points for CO2–CH4–H2Oequilibria at 376 K and 325 K, and at pressure from 100 bar to500 bar with different fluid compositions. We compared the calcu-lated results with the experimental data (Fig. 5). From Fig. 5, theexperimental can be reasonably reproduced. At 325 K, CO2 solubil-ities are slightly lower estimated, and CH4 solubilities are slightlyover estimated (with AAD � 10% or lower). At 376 K, the modelhas even much better performance compared with the experimen-tal data.

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

0 20 40 60 80 100

Mol

ality

of d

isso

lved

gas

in b

rine

(mol

al)

H2S mole percentage (%)

CO2-Bachu and Bennion, 2009H2S-Bachu and Bennion, 2009CO2-This modelH2S-This model

Fig. 6. CO2 + H2S gas mixture molality varying with H2S mole fraction in vapor gas.Dots are converted results from experimental raw data (Bachu and Bennion, 2009)and the solid lines are calculated by this model.

0.0E+00

2.0E-03

4.0E-03

6.0E-03

8.0E-03

1.0E-02

1.2E-02

1.4E-02

1.6E-02

1.8E-02

0 50 100 150 200

CO2

mol

e fr

ac�o

n in

aqu

eous

pha

se

Pressure (bar)

38 C, this model 38 C, Huang et al., 1985107 C, this model 107 C, Huang et al., 1985177 C, this model 177 C, Huang et al., 1985

(a)

0.0E+00

2.0E-04

4.0E-04

6.0E-04

8.0E-04

1.0E-03

1.2E-03

0 50 100 150 20

CH4

mol

e fr

ac�o

n in

aqu

eous

pha

se

Pressure (bar)

38 C, this model

38 C, Huang et al., 1985

107 C, this model

107 C, Huang et al., 1985

177 C, this model

177, Huang et al., 1985

(b)

Fig. 7. Comparison between this model results and measured data from Huang et al. (198CO2, 15% CH4, 5% H2S.

For CO2 + H2S gas mixture solubility in brine, the only experi-mental work that could be found so far is Bachu and Bennion(2009). The water sample was from Keg River Formation in WestCanadian Sedimentary Basin with salinity 118,950 ppm (10�6 massfraction). The equilibrium temperature and pressure were asaccording to the reservoir condition, which were 61 �C and135 bar. Fig. 6 shows the comparison between the convertedexperimental results and the calculated results of gas mixturemolality by both this model. From the comparison, we can find thatthe experimental results agree well with the calculations (SeeTable 6).

Huang et al. (1985) measured the phase equilibria for H2O–CO2–CH4–H2S system, with the feed composition (mole fraction)50% H2O, 30% CO2, 15% CH4, and 5% H2S. Fig. 7 shows the compar-ison between the experimental results and the calculated resultsby this model. From the comparison, most of the measurementscan be well predicted by this model except H2S solubility in waterat 38 �C and H2O solubility in gas phase at 177 �C. The AAD is about7%.

From the comparisons, the model has reliable performance ongas mixture – water/brine equilibria. However, the existing exper-imental data of multi-component systems are still limited accord-ing to the authors’ knowledge, and more experimental work isneeded to be more conclusive.

6. Conclusions

In this paper, we established a phase partitioning model for thesystem CO2–CH4–H2S–brine for a wide range of temperature, pres-sure and salinity, based on the revisions of Peng–Robinson EOS.From the comparison with the existing experimental data, thenew model can accurately reproduce the mutual solubilities:

0

0.0E+00

1.0E-03

2.0E-03

3.0E-03

4.0E-03

5.0E-03

6.0E-03

7.0E-03

0 50 100 150 200

H 2S

mol

e fr

ac�o

n in

aqu

eous

pha

se

Pressure (bar)

38 C, this model 38 C, Huang et al., 1985

107 C, this model 107 C, Huang et al., 1985

177 C, this model 177 C, Huang et al., 1985

(c)

0.0E+00

2.0E-02

4.0E-02

6.0E-02

8.0E-02

1.0E-01

1.2E-01

1.4E-01

0 50 100 150 200

H 2O

mol

e fr

ac�o

n in

non

-aqu

eous

pha

se

Pressure (bar)

38 C, this model

38 C, Huang et al., 1985

107 C, this model

177 C, Huang et al., 1985

177 C, this model

177 C, Huang et al., 1985

(d)

5) for H2O–CO2–CH4–H2S equilibria. Feed composition (mole fraction): 50% H2O, 30%

10 J. Li et al. / Applied Geochemistry 54 (2015) 1–12

� CO2 solubility in the aqueous phase and H2O in CO2-richphase at temperatures from 0 to 250 �C, pressures from 1to 1000 bar, and NaCl molality from 0 to 6 molal.

� CH4 solubility in aqueous phase and H2O solubility in CH4-rich phase at temperatures from 0 to 250 �C, pressures from1 to 1000 bar and NaCl molality from 0 to 6 molal.

� H2S solubility in the aqueous phase and H2O in H2S-richphase at temperature 0–250 �C, pressures from 1 to200 bar and NaCl molality from 0 to 6 molal.

� Gas mixture solubility in water or brine.

For CO2–brine and CH4–brine, the model is sufficient for reser-voir applications. However, due to the limitation of experimentpressure for H2S–brine system, we still cannot claim the modelbehavior to higher pressure, and it is not sufficient to some reser-voir applications. More experimental work should be carried out tocalibrate the modeling. Also, we still need more systematicallyexperimental work for gas mixture – brine systems to supportthe modeling.

Acknowledgements

This work is sponsored by Shell. Dr. Jeroen Snippe is thanked formany useful suggestions. Drs. Rui Sun and Shide Mao are thankedfor their literature searches for available experimental data. Theauthors Jun Li and Xiaochun Li acknowledge the support of Inter-national Science & Technology Cooperation Program of China(2013DFB60140).

References

Abou-Sayed, A.S., Summers, C., Zaki, K., 2005. An assessment of economical andenvironmental drivers of sour gas management by injection. In: The SPEInternational Improved Oil Recovery Conference in Asia Pacific, Kuala Lumpur,Malaysia.

Amirijafari, B., Campbell, J.M., 1972. Solubility of gaseous hydrocarbon mixtures inwater. Soc. Petrol. Eng. J. 12 (01), 21–27.

Anderson, G.K., 2002. Solubility of carbon dioxide in water under incipient clathrateformation conditions. J. Chem. Eng. Data 47, 219–222.

Bachu, S., Bennion, D.B., 2009. Chromatographic partitioning of impuritiescontained into a CO2 stream injected into a deep saline aquifer: Part 1. Effectsof gas composition and in situ conditions. Int. J. Greenhouse Gas Control 3, 458–467.

Bachu, S., Gunter, W.D., 2004. Acid-gas injection in the Alberta Basin, Canada: a CO2-storage experience. Geological Storage of Carbon Dioxide, vol. 233. GeologicalSociety, London, Special Publications.

Bacon, D.H., Ramanathan, R., Schaef, H.T., McGrail, B.P., 2014. Simulating geologicco-sequestration of carbon dioxide and hydrogen sulfide in a basalt formation.Int. J. Greenhouse Gas Control 21, 165–176.

Bamberger, A., Sieder, G., Maurer, G., 2000. High-pressure (vapor plus liquid)equilibrium in binary mixtures of (carbon dioxide plus water or acetic acid) attemperatures from 313 to 353 K. J. Supercrit. Fluids 17, 97–100.

Bando, S., Takemura, F., Nishio, M., Hihara, E., Akai, M., 2003. Solubility of CO2 inaqueous solutions of NaCl at (30 to 60) �C and (10 to 20) MPa. J. Chem. Eng. Data48 (3), 576–579.

Barrett, T.J., Anderson, G.M., Lugowski, J., 1988. The solubility of hydrogen sulphidein 0–5 m NaCl solutions at 25–95 �C and one atmosphere. Geochim.Cosmochim. Acta 52 (4), 807–811.

Bartholomé, E., Friz, H., 1956. Solubility of CO2 in water. Chem. Ing. Tech. 28, 706–708.

Battistelli, A., 2008. Modeling multiphase organic spills in coastal sites with TMVOCV. 2.0. Vadose Zone J. 7, 316.

Battistelli, A., Marcolini, M., 2009. TMGAS: a new TOUGH2 EOS module for thenumerical simulation of gas mixtures injection in geological structures. Int. J.Greenhouse Gas Control 3, 481–493.

Battistelli, A., Oldenburg, C.M., Moridis, G.J., Pruess, K., 2003. Modeling gas reservoirprocess with TMVOC V. 2.0. Proceedings, TOUGH Symposium. LawrenceBerkeley National Laboratory, Berkeley, CA.

Ben-Naim, A., Yaacobi, M., 1974. Effects of solutes on the strength of hydrophobicinteraction and its temperature dependence. J. Phys. Chem. 78 (2), 170–175.

Ben-Naim, A., Wilf, J., Yaacobi, M., 1973. Hydrophobic interaction in light and heavywater. J. Phys. Chem. 77, 95–102.

Blount, C.W., Price, L.C., 1982. Solubility of Methane in Water under NaturalConditions: A Laboratory Study. DOE Contract No. DE-A508-78ET12145. FinalReport.

Briones, J.A., Mullins, J.C., Thies, M.C., Kim, B.U., 1987. Ternary phase equilibria foracetic acid–water mixtures with supercritical carbon dioxide. Fluid PhaseEquilib. 36, 235–246.

Bunsen, R.W., 1855. In: Clever, H.L., Young, C.L. (Eds.), Solubility Data Series (1987),Methane, vol. 27–28. Pergamon Press, Oxford.

Chapoy, A., Mohammadi, A.H., Chareton, A., Tohidi, B., Richon, D., 2004a.Measurement and modeling of gas solubility and literature review of theproperties for the carbon dioxide�water system. Ind. Eng. Chem. Res. 43 (7),1794–1802.

Chapoy, A., Mohammadi, A.H., Richon, D., Tohidi, B., 2004b. Gas solubilitymeasurement and modeling for methane–water and methane–ethane–n-butane–water systems at low temperature conditions. Fluid Phase Equilib.220 (1), 111–119.

Claussen, W.F., Polglase, M.F., 1952. Solubilities and structures in aqueous aliphatichydrocarbon solutions. J. Am. Chem. Soc. 7 (19), 4817–4819.

Cosgrove, B.A., Walkley, J., 1981. Solubilities of gases in H2O and 2H2O. J.Chromatogr. 21, 161–167.

Cramer, S.D., 1984. Solubility of methane in brines from 0 to 300.degree.C. Ind. Eng.Chem. Process Des. Dev. 23 (3), 533–538.

Crovetto, R., Fernandez-Prini, R., Japas, M.L., 1982. Contribution of the cavity-formation or hard-sphere term to the solubility of simple gases in water. J. Phys.Chem. 86 (21), 4094–4095.

Culberson, O.L., McKetta Jr., J.J., 1950. Phase equilibria in hydrocarbon–watersystems II – the solubility of ethane in water at pressures to 10,000 psi. J. Petrol.Technol. 2 (11), 319–322.

Culberson, O.L., Mcketta, J.J., 1951. Phase equilibria in hydrocarbon–water systems.3. The solubility of methane in water at pressures to 10000 psia. Trans. Am. Inst.Min. Met. Eng. 192, 223–226.

Dhima, A., de Hemptinne, J.-C., Jose, J., 1999. Solubility of hydrocarbons and CO2

mixtures in water under high pressure. Ind. Eng. Chem. Res. 38 (8), 3144–3161.

Dohrn, R., Bünz, A.P., Devlieghere, F., Thelen, D., 1993. Experimental measurementsof phase equilibria for ternary and quaternary systems of glucose, water, CO2

and ethanol with a novel apparatus. Fluid Phase Equilib. 83, 149–158.Drummond, S.E., 1981. Boiling and Mixing of Hydrothermal Fluids: Chemical Effects

on Mineral Precipitation. Pennsylvania State University.D’Souza, R., Patrick, J.R., Teja, A.S., 1988. High pressure phase equilibria in the

carbon dioxide–n-hexadecane and carbon dioxide–water systems. Can. J. Chem.Eng. 66 (2), 319–323.

Duan, Z., Mao, S., 2006. A thermodynamic model for calculating methane solubility,density and gas phase composition of methane-bearing aqueous fluids from273 to 523 K and from 1 to 2000 bar. Geochim. Cosmochim. Acta 70 (13), 3369–3386.

Duan, Z., Sun, R., 2003. An improved model calculating CO2 solubility in pure waterand aqueous NaCl solutions from 273 to 533 K and from 0 to 2000 bar. Chem.Geol. 193 (3–4), 253–271.

Duan, Z., Moller, N., Weare, J.H., 1992. An equation of state for the CH4–CO2–H2Osystem: I. Pure systems for 0 to 1000 �C and 0 to 8000 bar. Geochim.Cosmochim. Acta 56, 2605–2617.

Duffy, J.R., Smith, N.O., Nagy, B., 1961. Solubility of natural gases in aqueous saltsolutions—I: liquidus surfaces in the system CH4–H2O–NaCl2–CaCl2 at roomtemperatures and at pressures below 1000 psia. Geochim. Cosmochim. Acta 24(1–2), 23–31.

Ellis, A.J., Golding, R.M., 1963. The solubility of carbon dioxide above 100 �C in waterand in sodium chloride solutions. Am. J. Sci. 261, 47–60.

Eucken, A., Hertzberg, G., 1950. Aussalzeffekt und ionenhydratation. Z. Phys. Chem.195, 1–23.

Ferrentino, G., Barletta, D., Donsi, F., Ferrari, G., Poletto, M., 2010. Experimentalmeasurements and thermodynamic modeling of CO2 solubility at high pressurein model apple juices. Ind. Eng. Chem. Res. 49 (6), 2992–3000.

Gao, G.-H., Tan, Z.-Q., Yu, Y.-X., 1999. Calculation of high-pressure solubility of gasin aqueous electrolyte solution based on non-primitive mean sphericalapproximation and perturbation theory. Fluid Phase Equilib. 165, 169–182.

Gillesp, P.C., Wilson, G.M., 1980. GPA Research Rep., Rep. No. RR-41: 1-34.Gillesp, P.C., Wilson, G.M., 1982. GPA Research Rep., Rep. No. RR-48: 1-73.Gu, F., 1998. Solubility of carbon dioxide in aqueous sodium chloride solution under

high pressure. J. Chem. Eng. Chin. Univ. 12 (2), 118–123.Han, J.M., Shin, H.Y., Min, B.-M., Han, K.-H., Cho, A., 2009. Measurement and

correlation of high pressure phase behavior of carbon dioxide–water system. J.Ind. Eng. Chem. 15 (2), 212–216.

Harned, H.S., Davis, R., 1943. The ionization constant of carbonic acid in water andthe solubility of carbon dioxide in water and aqueous salt solutions from 0 to50�. J. Am. Chem. Soc. 65 (10), 2030–2037.

Harvey, A.H., Prausnitz, J.M., 1989. Thermodynamics of high-pressure aqueoussystems containing gases and salts. AIChE J. 3 (4), 635–644.

Hendriks, E., Meijer, H., 2009. Solubility of Carbon Dioxide and Hydrocarbon Sulfidein Brines. Shell Internal Report. GS.09.50441.

Hovorka, S.D. et al., 2006. Measuring permanence of CO2 storage in salineformations: the Frio experiment. Environ. Geosci. 13 (2), 105–121.

Huang, S.S., Leu, A.D., Ng, H.I., Robinson, D.B., 1985. The phase behaviour of twomixtures of methane, carbon dioxide, hydrogensulfide, and water. Fluid PhaseEquilib. 19, 21–32.

IPCC, 2005. Special report on carbon dioxide capture and storage. CambridgeUniversity Press, Cambridge, United Kingdom, New York, NY, USA.

Kiepe, J., Horstmann, S., Fischer, K., Gmehling, J., 2002. Experimental determinationand prediction of gas solubility data for CO2 + H2O mixtures containing NaCl or

J. Li et al. / Applied Geochemistry 54 (2015) 1–12 11

KCl at temperatures between 313 and 393 K and pressures up to 10 MPa. Ind.Eng. Chem. Res. 41 (17), 4393–4398.

Kiepe, J., Horstmann, S., Fischer, K., Gmehling, J., 2003. Experimental determinationand prediction of gas solubility data for methane + water solutions containingdifferent monovalent electrolytes. Ind. Eng. Chem. Res. 42 (21), 5392–5398.

King, M.B., Mubarak, A., Kim, J.D., Bott, T.R., 1992. The mutual solubilities of waterwith supercritical and liquid carbon dioxide. J. Supercrit. Fluids 5, 296–302.

Kontogeorgis, G.M., Voutsas, E., Yakoumis, I., Tassios, D.P., 1996. An equation ofstate for associating fluids. Ind. Eng. Chem. Res. 35, 4310–4318.

Koschel, D., Coxam, J.-Y., Rodier, L., Majer, V., 2006. Enthalpy and solubility data ofCO2 in water and NaCl(aq) at conditions of interest for geological sequestration.Fluid Phase Equilib. 247 (1–2), 107–120.

Kritschewsky, I.R., Shaworonkoff, N.M., Aepelbaum, V.A., 1935. Combined solubilityof gases in liquids under pressure: I. Solubility of carbon dioxide in water fromits mixtures with hydrogen of 20 and 30 �C and total pressure of 30 kg/cm2. Z.Phys. Chem. A 175, 232–238.

Lannung, A., Gjaldbaek, J.C., 1960. The solubility of methane in hydrocarbons,alcohols, water and other solvents. Acta Chem. Scand. 14 (5), 1124–1128.

Lee, J.I., Mather, A.E., 1977. Solubility of hydrogen sulfide in water. Ber. Bunsenges.Phys. Chem. 81, 1021–1023.

Lekvam, K., Bishnoi, P.R., 1997. Dissolution of methane in water at lowtemperatures and intermediate pressures. Fluid Phase Equilib. 131 (1–2),297–309.

Li, J., Duan, Z., 2011. A thermodynamic model for the prediction of phase equilibriaand speciation in the H2O–CO2–NaCl–CaCO3–CaSO4 system from 0 to 250 �C, 1to 1000 bar with NaCl concentrations up to halite saturation. Geochim.Cosmochim. Acta 75 (19), 4351–4376.

Li, Y.-K., Nghiem, L.X., 1986. Phase equilibria of oil, gas and water/brine mixturesfrom a cubic equation of state and Henry’s law. Can. J. Chem. Eng. 64 (3), 486–496.

Li, Z., Dong, M., Li, S., Dai, L., 2004. Densities and solubilities for binary systems ofcarbon dioxide + water and carbon dioxide + brine at 59 �C and pressures to29 MPa. J. Chem. Eng. Data 49 (4), 1026–1031.

Liu, Y., Hou, M., Yang, G., Han, B., 2011. Solubility of CO2 in aqueous solutions ofNaCl, KCl, CaCl2 and their mixed salts at different temperatures and pressures. J.Supercrit. Fluids 56 (2), 125–129.

Malinin, S.D., 1959. The system water–carbon dioxide at high temperatures andpressures. Geokhimiya 3, 292–306.

Malinin, S.D., Kurorskaya, N.A., 1975. Investigation of CO2 solubility in a solution ofchlorides at elevated temperatures and pressures of CO2. Geokhimiya 4, 547–551.

Malinin, S.D., Savelyeva, N.I., 1972. The solubility of CO2 in NaCl and CaCl2 solutionsat 25, 50, and 75 �C under elevated CO2 pressures. Geokhimiya 6, 643–653.

Mao, S., Zhang, Z., Hu, J., Sun, R., Duan, Z., 2005. An accurate model for calculatingC2H6 solubility in pure water and aqueous NaCl solutions. Fluid Phase Equilib.238 (1), 77–86.

Mao, S., Zhang, D., Li, Y., Liu, N., 2013. An improved model for calculating CO2

solubility in aqueous NaCl solutions and the application to CO2–H2O–NaCl fluidinclusions. Chem. Geol. 347, 43–58.

Markham, A.E., Kobe, K.A., 1941. The solubility of carbon dioxide and nitrous oxidein aqueous salt solutions. J. Am. Chem. Soc. 63 (2), 449–454.

Matous, J., Sobr, J., Novak, J.P., Pick, J., 1969. Solubility of carbon dioxide in water atpressures up to 40 atm. Collect. Czechoslov. Chem. Commun. 34, 3982–3985.

Michelsen, M., Mollerup, J., 2007. Thermodynamic Models: Fundamentals &Computational Aspects, second ed. TIE-LINE Publications, Denmark.

Mishnina, T.A., Avdeeva, O.I., Bozhovskaya, T.K., 1962. The solubility of methane inNaCl aqueous solutions. Inf. Sb. Vses. Nauchn-Issled. Geol. Inst. 56, 137–145.

Morrison, T.J., Billett, F., 1952. 730. The salting-out of non-electrolytes. Part II. Theeffect of variation in non-electrolyte. J. Chem. Soc. (0), 3819–3822 (Resumed).

Moudgil, B.M., Somasundaran, P., Lin, L.J., 1974. Automated constant pressurereactor for measuring solubilities of gases in aqueous solutions. Rev. Sci.Instrum. 45 (3), 406–409.

Muccitelli, J., Wen, W.-Y., 1980. Solubility of methane in aqueous solutions oftriethylenediamine. J. Solution Chem. 9 (2), 141–161.

Mukhopadhyay, S., Birkholzer, J.T., Nicot, J.-P., Hosseini, S.A., 2012. A modelcomparison initiative for a CO2 injection field test: an introduction to Sim-SEQ. Environ. Earth Sci. 67, 601–611.

Müller, G., Bender, E., Maurer, G., 1988. Das Dampf-Flussigkeitsgleichgewicht desternaren Systems Ammoniak-Kohlendioxid-Wasser bei holen Wassergehaltenim Bereich zwischen 373 und 473 Kelvin. Ber. Bunsenges. Phys. Chem. 92, 148–160.

Namiot, A.Y., 1961. In: Clever, H.L., Young, C.L. (Eds.), Solubility Data Series (1987),Methane, 27–28. Pergamon Press, Oxford.

Nighswander, J.A., Kalogerakis, N., Mehrotra, A.K., 1989. Solubilities of carbondioxide in water and 1 wt% NaCl solution at pressures up to 10 MPa andtemperatures from 80 to 200 �C. J. Chem. Eng. Data 34, 355–360.

Oldenburg, C.M., Moridis, G.J., Spycher, N., Pruess, K., 2004. EOS7C Version 1.0:TOUGH2 Module for Carbon Dioxide or Nitrogen in Natural Gas (Methane)Reservoirs. LBNL-56589.

Oleinik, P.M., 1986. Method of Evaluating Gases in Liquids and VolumetricProperties of Solutions under Pressure. Neft. Promst., Ser. ‘‘Neftepromysl. Delo’’.

Onda, K., Sada, E., Kobayashi, T., Kito, S., Ito, K., 1970. Salting-out parameters of gassolubility in aqueous salt solutions. J. Chem. Eng. Jpn. 3, 18–24.

O’Sullivan, T.D., Smith, N.O., 1970. Solubility and partial molar volume of nitrogenand methane in water and in aqueous sodium chloride from 50 to 125.deg. and100 to 600 atm. J. Phys. Chem. 74 (7), 1460–1466.

Peng, D.-Y., Robinson, D.B., 1976. A new two constant of equation. Ind. Eng. Chem.Fundam. 15 (1), 59–64.

Price, L.C., 1979. Aqueous solubility of methane at elevated pressures andtemperatures. AAPG Bull. 63 (9), 1527–1533.

Pruess, K., Oldenburg, C., Moridis, G., 1999. TOUGH2 User’s Guide, Version 2. EarthSciences Division, Lawrence Berkeley National Laboratory, University ofCalifornia, Berkeley, CA.

Prutton, C.F., Savage, R.L., 1945. The solubility of carbon dioxide in calcium chloride-water solutions at 75, 100, 120 �C and high pressures. J. Am. Chem. Soc. 67,1550–1554.

Qin, J., Rosenbauer, R.J., Duan, Z., 2008. Experimental measurements of vapor–liquidequilibria of the H2O + CO2 + CH4 ternary system. J. Chem. Eng. Data 53, 1246–1249.

Rettich, T.R., Handa, Y.P., Battino, R., Wilhelm, E., 1981. Solubility of gases in liquids.13. High-precision determination of Henry’s constants for methane and ethanein liquid water at 275 to 328 K. J. Phys. Chem. 85 (22), 3230–3237.

Rosenbauer, R.J., Bischoff, J.L., Koksalan, T., 2001. An experimental approach to CO2

sequestration in saline aquifers: application to Paradox Valley, CO. EOS Trans.Am. Geophys. Union 47, Fall Meet. Suppl. (Abstract V32B-0974).

Rumpf, B., Maurer, G., 1993. An experimental and theoretical investigations on thesolubility of carbon dioxide in aqueous solutions of strong electrolytes. Ber.Bunsenges. Phys. Chem. 97, 85–97.

Rumpf, B., Nicolaisen, H., Ocal, C., Maurer, G., 1994. Solubility of carbon dioxide inaqueous solutions of sodium chloride: experimental results and correlation. J.Solution Chem. 23 (3), 431–448.

Sabirzyanov, A.N., Shagiakhmetov, R.A., Gabitov, F.R., Tarzimanov, A.A., Gumerov,F.M., 2003. Water solubility of carbon dioxide under supercritical andsubcritical conditions. Theor. Found. Chem. Eng. 37 (1), 51–53.

Sako, T. et al., 1991. Phase-equilibrium study of extraction and concentration offurfural produced in reactor using supercritical carbon-dioxide. J. Chem. Eng.Jpn. 24, 449–454.

Selleck, F.T., Carmichael, L.T., Sage, B.H., 1952. Phase behavior in the hydrogensulfide–water system. Ind. Eng. Chem. 44, 2219.

Servio, P., Englezos, P., 2001. Effect of temperature and pressure on the solubility ofcarbon dioxide in water in the presence of gas hydrate. Fluid Phase Equilib. 190,127–134.

Shagiakhmetov, R.A., Tarzimanov, A.A., 1981. Measurements of CO2 Solubility inWater up to 60 MPa. Deposited Document SPSTL 200khp-D81-1982.

Shah, V., Broseta, D., Mouronval, G., Montel, F., 2008. Water/acid gas interfacialtensions and their impact on acid gas geological storage. Int. J. Greenhouse GasControl 2, 594–604.

Søreide, I., Whitson, C.H., 1992. Peng–Robinson predictions for hydrocarbons, CO2,N2 and H2S with pure water and NaCl brine. Fluid Phase Equilib. 77, 217–240.

Stewart, P.B., Munjal, P., 1970. Solubility of carbon dioxide in pure water, syntheticseawater, and synthetic seawater concentrates at 5 to 25 �C and 10 to 45 atmpressure. J. Chem. Eng. Data 15, 67–71.

Stoessell, R.K., Byrne, P.A., 1982. Salting-out of methane in single-salt solutions at25 �C and below 800 psia. Geochim. Cosmochim. Acta 46 (8), 1327–1332.

Suleimenov, O.M., Krupp, R.E., 1994. Solubility of hydrogen sulfide in pure waterand in NaCl solutions, from 20 to 320 �C and at saturation pressures. Geochim.Cosmochim. Acta 58 (11), 2433–2444.

Sun, R., Dubessy, J., 2010. Prediction of vapor–liquid equilibrium and PVTxproperties of geological fluid system with SAFT-LJ EOS including multi-polarcontribution. Part I. Application to H2O–CO2 system. Geochim. Cosmochim. Acta74, 1982–1998.

Sun, R., Dubessy, J., 2012. Prediction of vapor–liquid equilibrium and PVTxproperties of geological fluid system with SAFT-LJ EOS including multi-polarcontribution. Part II. Application to H2O–NaCl and CO2–H2O–NaCl System.Geochim. Cosmochim. Acta 88, 130–145.

Sun, R., Lai, S., Dubessy, J., 2014. Calculation of vapor–liquid equilibrium and PVTxproperties of geological fluid system with SAFT-LJ EOS including multi-polarcontribution. Part III. Extension to water–light hydrocarbons systems. Geochim.Cosmochim. Acta 125, 504–518.

Tabasinejad, F., Moore, R., Mehta, S.A., Van Fraassen, K.C., Barzin, Y., 2011. Watersolubility in supercritical methane, nitrogen, and carbon dioxide: measurementand modeling from 422 to 483 K and pressures from 3.6 to 134 MPa. Ind. Eng.Chem. Res. 50, 4029–4041.

Takenouchi, S., Kennedy, G.C., 1964. The binary system H2O–CO2 at hightemperatures and pressures. Am. J. Sci. 262, 1055–1074.

Takenouchi, S., Kennedy, G.C., 1965. The solubility of carbon dioxide in NaClsolutions at high temperatures and pressures. Am. J. Sci. 263, 445–454.

Tan, S.P., Yao, Y., Piri, M., 2013. Modeling the solubility of SO2 + CO2 mixtures inbrine at elevated pressures and temperatures. Ind. Eng. Chem. Res. 52, 10864–10872.

Teng, H., Yamasaki, A., Chun, M.-K., Lee, H., 1997. Solubility of liquid CO2 in water attemperatures from 278 K to 293 K and pressures from 6.44 MPa to 29.49 MPa,and densities of the corresponding aqueous solutions. J. Chem. Thermodyn. 29,1301–1310.

Todheide, K., Franck, E.U., 1963. Das Zwei phasengebiet und diekritische Kurve imSystem Kohlendioxid-Wasser bis zu Drucken von 3500 bar. Z. Phys. Chem. 37,387–401.

Valtz, A., Chapoy, A., Coquelet, C., Paricaud, P., Richon, D., 2004. Vapour–liquidequilibria in the carbon dioxide–water system, measurement and modellingfrom 278.2 to 318.2 K. Fluid Phase Equilib. 226, 333–344.

van der Meer, L., Hartman, J., Geel, C., Kreft, E.E., 2005. Re-injecting CO2 into anoffshore gas reservoir at a depth of nearly 4000 metres subsea. In: Proceedings

12 J. Li et al. / Applied Geochemistry 54 (2015) 1–12

of the 7th International Conference on Greenhouse Gas Control Technologies.Elsevier, London, UK, pp. 521–530.

Wang, L.-K., Chen, G.-J., Han, G.-H., Guo, X.-Q., Guo, T.-M., 2003. Experimental studyon the solubility of natural gas components in water with or without hydrateinhibitor. Fluid Phase Equilib. 207 (1–2), 143–154.

Wen, W.-Y., Hung, J.H., 1970. Thermodynamics of hydrocarbon gases in aqueoustetraalkyl ammonium salt solutions. J. Phys. Chem. 74 (1), 170–180.

Wetlaufer, D.B., Malik, S.K., Stoller, L., Coffin, R.L., 1964. Nonpolar groupparticipation in denaturation of proteins by urea + guanidinium salts. Modelcompound studies. J. Am. Chem. Soc. 86, 508–514.

Wiebe, R., Gaddy, V.L., 1939. The solubility in water of carbon dioxide at 50j, 75j,and 100 jC at pressures to 700 atm. J. Am. Chem. Soc. 61, 315–318.

Wiebe, R., Gaddy, V.L., 1940. The solubility of carbon dioxide in water at varioustemperatures from 12 to 40 �C and at pressures to 500 atm. J. Am. Chem. Soc.62, 815–817.

Wiebe, R., Gaddy, V.L., 1941. Vapor phase composition of carbon dioxide–watermixtures at various temperatures and at pressures to 700 atmospheres. J. Am.Chem. Soc. 63, 475–477.

Wiesenburg, D.A., Guinasso, N.L., 1979. Equilibrium solubilities of methane, carbonmonoxide, and hydrogen in water and sea water. J. Chem. Eng. Data 24 (4), 356–360.

Winkler, L.W., 1901. Solubility of gas in water. Ber. Dtsch. Chem. Ges. 34, 1408–1422.

Xia, J., Kamps, A.P.-S., Rumpf, B., Maurer, G., 2000. Solubility of hydrogen sulfide inaqueous solutions of the single salts sodium sulfate, ammonium sulfate, sodiumchloride, and ammonium chloride at temperatures from 313 to 393 K and totalpressures up to 10 MPa. Ind. Eng. Chem. Res. 39, 1064–1073.

Xu, T.F., Apps, J.A., Pruess, K., 2007. Numerical modeling of injection and mineraltrapping of CO2 with H2S and SO2 in a sandstone formation. Chem. Geol. 242,319–346.

Yamamoto, S., Alcauskas, J.B., Crozier, T.E., 1976. Solubility of methane in distilledwater and seawater. J. Chem. Eng. Data 21 (1), 78–80.

Yang, S.O., Yang, I.M., Kim, Y.S., Lee, C.S., 2000. Measurement and prediction ofphase equilibria for water + CO2 in hydrate forming conditions. Fluid PhaseEquilib. 175, 75–89.

Yano, T., Suetaka, T., Umehara, T., Horiuchi, A., 1974. In: Clever, H.L., Young, C.L.(Eds.), Solubility Data Series (1987), Methane. Pergamon Press, Oxford.

Yarym-Agaev, N.L., Sinyavskaya, R.P., Koliushko, I.L., Levinton, L.Y., 1985. Phase-equilibria in the water methane and methanol methane binary-systems underhigh-pressures. J. Appl. Chem. USSR 58 (1), 154–157.

Yasunishi, A., Yoshida, F., 1979. Solubility of carbon dioxide in aqueous electrolytesolutions. J. Chem. Eng. Data 24 (1), 11–14.

Zawisza, A., Malesinska, B., 1981. Solubility of carbon dioxide in liquid water and ofwater in gaseous carbon dioxide in the range 0.2–5 MPa and at temperatures upto 473 K. J. Chem. Eng. Data 26 (4), 388–391.

Zel’vinskii, Y.D., 1937. Measurements of carbon dioxide solubility in water. Zhurn.Khim. Prom. 14, 1250–1257.

Zhang, W., Xu, T.F., Li, Y.L., 2011. Modeling of fate and transport of coinjection of H2Swith CO2 in deep saline formations. J. Geophys. Res.-Solid Earth 116 (B02202),02201–02213.

Zheng, D.Q., Guo, T.M., Knapp, H., 1997. Experimental and modeling studies on thesolubility of CO2, CHC1F2, CHF3, C2H2F4 and C2H4F2 in water and aqueous NaClsolutions under low pressures. Fluid Phase Equilib. 129 (1–2), 197–209.

Zheng, L., Spycher, N., Birkholzer, J., Xu, T., Apps, J., 2010. Modeling Studies on theTransport of Benzene and H2S in CO2–Water Systems. LBNL-4339E.

Ziabakhsh-Ganji, Z., Kooi, H., 2012. An equation of state for thermodynamicequilibrium of gas mixtures and brines to allow simulation of the effects ofimpurities in subsurface CO2 storage. Int. J. Greenhouse Gas Control 11s, s21–s34.

Zirrahi, M., Azin, R., Hassanzadeh, H., Moshfeghian, M., 2012. Mutual solubility ofCH4, CO2, H2S, and their mixtures in brine under subsurface disposal conditions.Fluid Phase Equilib. 324, 80–93.

Zuo, Y.-X., Guo, T.-M., 1991. Extension of the Patel-Teja equation of state to theprediction of the solubility of natural gas in formation water. Chem. Eng. Sci. 46(12), 3251–3258.