Version of Record: https://www.sciencedirect.

com/science/article/pii/S0011916421000436
Manuscript_c54b99875b0dbd11bfc7a115df55203b

1 A simple model for the prediction of mutual solubility in

2 CO2-Brine system at geological conditions
3 Xiaohui Sun, Zhiyuan Wang, Hangyu Li, Haikang He, Baojiang Sun*

4 School of Petroleum Engineering, China University of Petroleum (East China), 66 Changjiang West Road,

5 Huangdao, Qingdao, 266580, China

6 *Corresponding Author

7 E-mail address: sunbj1128@126.com (B. Sun)

8 Abstract

9 Reliable and accurate prediction of phase-partitioning behaviors in CO2-Brine system

10 over a wide range of temperature, pressure and ionic composition (T–P–msalts) is of

11 fundamental and practical importance to many geological-, energy-, and

12 environmental-related technical applications. In this work, a simple model for the prediction

13 of mutual solubility in the systems of CO2+H2O and CO2+Brine containing Na+, K+, Ca2+,

14 Mg2+, Cl-, and SO42- is proposed, which can cover the typical geological conditions (0–250 °C,

15 0–200 MPa). Validation of the model calculations against updated experimental data available

16 indicates that the simulation errors for CO2 solubility in pure water and brine are 6.899% and

17 8.08%, respectively, whereas the simulation error for water content in the CO2 rich phase is

18 9.67%. Compared to conventional complicated models, the proposed model is capable of

19 simultaneously predicting CO2 solubility in aqueous phase and water content in CO2 rich

20 phase, and obtains a comparable accuracy over a large T–P–msalts scale. The simulation results

21 demonstrate that the developed model can reproduce the abrupt variations in phase

22 compositions during the phase transition of the CO2 rich phase, and describe the influence of

23 different ions on CO2 solubility. More importantly, the model is explicit,

24 derivative-continuous and does not require iterative algorithms for its use, which means that it

25 is computationally efficient and reliable to be incorporated into a large-scale multiphase flow

26 simulator in geological processes.

27 Key words: carbon dioxide; mutual solubility; phase partitioning; brine; geological
1
© 2021 published by Elsevier. This manuscript is made available under the Elsevier user license
https://www.elsevier.com/open-access/userlicense/1.0/
 1 1. Introduction

2 Carbon dioxide (CO2), created by the burning of fossil fuels, is an important greenhouse

3 gas. Recently, more and more researches have been carried out to demonstrate the safe

4 long-term storage approaches of CO2 including geological storage and deep sea disposal [1-9],

5 and potential applications of CO2 in energy-related fields including CO2 enhanced oil

6 recovery (EOR) [10] and CO2 enhanced geothermal system (EGS) [11, 12]. Furthermore, CO2

7 is widely used in seawater desalination, wastewater treatment and supercritical fluid

8 extraction [13-19]. In these geological-, energy-, and environmental-related technical

9 applications, CO2 and water are the most commonly encountered fluid system [10, 17, 20].

10 Therefore, accurate determination of mutual solubility over a wide temperature, pressure and

11 ionic composition is of fundamental and practical importance, since it closely relates to

12 evaluating flow and heat transfer properties of fluid mixture [5, 9, 18, 21], analyzing the

13 reactivity between reservoir rocks and fluids [1, 11], estimating the capacity of CO2 storage

14 and displacing oil [8, 9, 17, 18], and designing separation equipment in chemical industries

15 [22].

16 While flowing in the subsurface wellbore and porous rocks, CO2 can gradually dissolve

17 into the aqueous phase. CO2 trapping in water, mainly controlled by temperature, pressure,

18 and dissolved salts, is the main mechanism of CO2 long-term safe sequestration and accounts

19 for 90% of the total storage capacity in saline aquifers [5, 18, 21]. Another important CO2

20 trapping mechanism is transformation to geologically stable carbonate minerals [9, 18, 23, 24],

21 when the dissolved CO2 forms carbonic acid and reacts with the ions and minerals. However,

22 CO2 dissolution can also generate a substantially adverse effect in petroleum and geothermal

23 systems. Because the reactivity of dissolved CO2 with minerals and ions can produce a solid

24 precipitate, block the pores and throats in rocks, and alter the formation porosity and

25 permeability [25]. Preliminary simulation results revealed that this chemical reaction could

26 lead to a 27% decrease of heat exploitation efficiency in geothermal system. Furthermore,

2
 1 Enick and Klara [26], and Chang et al. [27] found that CO2 dissolution in formation water can

2 significantly reduce the ultimate recovery in CO2 EOR process.

3 Compared to those of CO2 solubility in aqueous phase, the properties of water content in

4 CO2 rich phase have been largely ignored [1, 28, 29], but is also of comparable importance.

5 According to the principles of vapor-liquid equilibrium, water will evaporate into the CO2

6 rich phase accompanied by CO2 dissolving into water until the state of Gibbs energy

7 minimization and fugacity equality is reached. Therefore, the transport process of different

8 fluids during phase partitioning is interrelated. On the one hand, CO2 can extract water from

9 rocks and increase the salinity in the irreducible water, leading to a decrease of CO2 solubility

10 and release of dissolved gas. Furthermore, salting out induced by water vaporization and

11 salinity concentrating can result in the formation damage [30, 31]. Borgia et al. [12] revealed

12 that the geothermal reservoir could even become unusable after less than 1 year because of

13 salt precipitation. On the other hand, water content in the CO2 rich phase determines the

14 capacity of injected CO2 to dry the formations [11, 32, 33] and influences the type of chemical

15 interactions between CO2 and reservoir rocks [11, 34, 35, 36]. Therefore, the understanding of

16 both the compositions of aqueous phase and CO2 rich phase at geological conditions is of

17 fundamental and practical importance [1, 11].

18 Until now, a large abundant of numerical studies on phase equilibrium behaviors in

19 CO2+water system have been performed, which rely on the accurate prediction of fugacity of

20 CO2 and water in different phases. However, the iterative algorithms are necessary both in the

21 fugacity simulation based on equations of state (EOS) and in the updating of phase

22 composition according to the criterion of fugacity equality. The disadvantage of such models

23 is the computational complexities and expense when they are used for large-scale multiphase

24 flow simulation in geological engineering applications [6, 11, 37]. The next-generation

25 reservoir simulator needs massively parallel computing [38]. In the existing multiphase flow

26 algorithm framework, the computational efficiency of phase equilibrium model is one of the

3
 1 controlling factors for rapid large-scale field simulation [39]. Moreover, functional

2 smoothness and continuity of mutual solubility of CO2 and water is crucial to the formulation

3 of the numerical problem. Because the Jacobian-based numerical formulation can be

4 interrupted and damaged by non-convergent results after multiple iterations or by

5 discontinuous derivatives caused by the discontinuous functional parameters [40].

6 Another issue is the accuracy of phase equilibrium models. Few models can

7 simultaneously predict CO2 solubility in aqueous phase and water content in CO2 rich phase

8 [41]. Furthermore, it is difficult to accurately analyze the phase behaviors of water and CO2

9 over a large temperature, pressure and ionic composition (T–P–msalt) range [37]. Based on

10 Peng−Robinson equation of state (PR EOS) and Henry’s law, Li and Ngheim [42] developed

11 a model to estimate the solubility of CO2 in water blow 473 K, in which the scaled-particle

12 theory was incorporated to analyze the effect of NaCl. However, Duan et al. [41] revealed that

13 the simulation results of Li and Ngheim [42] were not accurate enough. Harvey and Prausnitz

14 [43] proposed a model to predict CO2 solubility in pure water and brine at elevated pressures,

15 but it overestimated by more than 10–20% in the NaCl solutions. Using the Patel–Teja

16 equation of state (PT EOS), Zuo and Guo [44] established a model to simulate the gas

17 solubility in electrolyte solutions. The simulated results indicated that its simulation error was

18 larger than 12% in 20 wt.% NaCl solutions at high pressure, and larger than 6% in 6 wt.%

19 NaCl solution at moderate pressures. Yuanhui et al. [45] reviewed the previous phase

20 equilibrium models for CO2+H2O and CO2+H2O+NaCl systems at 273.15-473.15K, 0-60MPa.

21 It was concluded that more accurate thermodynamic calculation at temperature-pressure

22 conditions of above 398.15K and 31.5 MPa was necessary. Bahadori et al. [46] presented a

23 polynomial equation to estimate the solubility of CO2 in NaCl solutions. However, the

24 application scope of the model is limited to 300–400 K, 50–700 bar and 0–4 mol kg−1. Hu et

25 al. [47] demonstrated that many cubic EoS and virial EoS were adequate to simulate the

26 phase-partitioning properties in CO2+H2O and CO2+NaCl+H2O systems. Nevertheless, the

4
 1 simulation results at high pressure was found to be unacceptable [17]. Akinfiev and Diamond

2 [19] compiled a databank of 508 experimental measurements of CO2 solubility assembled

3 from 21 literature studies, and established an accurate γ-φ (fugacity-activity) model that was

4 suitable for blow 100 MPa and 100 °C. Furthermore, the model can only roughly estimate the

5 composition of CO2-rich phase. Sorensen et al. [48] developed the CO2 solubility models in

6 pure water at 348-623 K and 1.6-140 MPa, and in NaCl solutions at 298-523 K and 0.1-138.2

7 MPa. However, the average simulation errors of CO2 solubility can reach 37% and 20.3% in

8 pure water and NaCl solutions, respectively. Mao et al. [49] proposed an accurate model to

9 predict the CO2 solubility in water and NaCl solutions, but it cannot be used to estimate the

10 water content in CO2 rich phase or the CO2 solubility in other brines. Spycher et al. [6, 11]

11 developed a model of mutual solubility for CO2+water system. The model relies on the

12 Redlich–Kwong equation of state to estimate the fugacity coefficients of CO2-rich phase, and

13 the method of equilibrium constant to estimate the activity coefficients of vapor and liquid

14 CO2 in aqueous phase. Furthermore, the Pitzer expression was incorporated to characterize

15 the salting-out effects. However, the model employs different model parameters for different

16 CO2 phases and temperature ranges with a valid pressure range of 0-60 MPa [9, 17]. Dubessy

17 et al. [50] established a thermodynamic model to predict the properties of vapor-liquid

18 equilibria in CO2+H2O+NaCl system. However, the equation is only valid for 0-30 MPa.

19 Similarly, Portier and Rochelle [51] presented a thermodynamic model to calculate the CO2

20 solubility in pure water and NaCl solutions with a valid range of 0-300 °C and 0.1-30MPa. Li

21 and Yang [10] presented a symmetric approach to calculate the mutual solubility in CO2+H2O

22 system, in which the Peng−Robinson equation of state (PR EOS) with a new alpha function

23 and binary interaction parameter was employed. However, this model based on the

24 fugacity-fugacity approach is insufficient to obtain accurate results for strongly non-ideal

25 fluid mixture of CO2 and water, and cannot analyze the effect of salts. Combining an equation

26 of state for pure CO2 and the Pizter interaction expression, Duan and Sun [41] developed a

5
 1 CO2 solubility model in pure water and brine with a valid range of 273-533 K and 0-200 MPa.

2 However, Hou et al. [52] claimed that their experimental measurements disagreed

3 significantly with the simulated results generated by the model of Duan and Sun [41]. Since

4 most of the CO2 solubility data used in fitting the model parameters was for NaCl solution,

5 the model simulation results were indicated to be less accurate in KCl solutions than those in

6 NaCl solutions [52]. Furthermore, the model of Duan and Sun [41] is not suitable for the

7 estimation of water content in CO2 rich phase. Recently, Darwish and Hilal [37] proposed a

8 simple model for the prediction of CO2 solubility in NaCl solutions, but it required the

9 availability of CO2 solubility in pure water.

10 The preliminary analysis indicates that most of the traditional models (1) involve

11 computationally complexities and inefficiency for their incorporation into multiphase flow

12 simulation; (2) consider only CO2 solubility in pure water or NaCl solutions; and (3) are

13 difficult to cover a large T-P-msalts range to obtain accurate results. In this study, a simple

14 model for the prediction of phase-partitioning properties in the systems of CO2+H2O and

15 CO2+Brine containing Na+, K+, Ca2+, Mg2+, Cl-, and SO42- is proposed with a valid range of

16 0–250 °C and 0–200 MPa. More importantly, the model is explicit in mutual solubility

17 without iteration and its derivatives are smooth and continuous, which makes it

18 computationally efficient for its incorporation into the multiphase flow simulators.

19 2. Model development

20 An abundant of experimental studies have been carried out to obtain a thorough

21 understanding of the phase equilibrium properties in CO2+H2O system. If the system pressure

22 is lower than the saturated vapor pressure of water, the fluid mixture is in single vapor phase.

23 As the pressure increases, the fluid system splits into two immiscible phases including the

24 aqueous phase and CO2-rich phase. Besides, the CO2-rich phase is vapor, liquid or

25 supercritical depending on the temperature and pressure. The CO2 solubility and water content

26 generally increase with a higher temperature and pressure until approaching a fully miscible

6
 1 phase above 300 °C and ~56.7 MPa [1, 53]. In this study, the oriented temperature and

2 pressure range is 0-250 °C and 0-200 MPa, in which the CO2-rich and water-rich phases are

3 commonly immiscible.

4 2.1 CO2 Solubility in water

5 Regarding the strongly non-ideal fluid mixture consisting of CO2 and water, the

6 composition of different phases varies with temperature and pressure in a complicated manner

7 [11, 18, 54].

8 (i) Overall, the CO2 fugacity in CO2-rich phase increases with pressure, leading to a

9 gradual increase of CO2 solubility. As the system temperature increases, the CO2 solubility

10 first decreases and then increases. Because the variation of temperature can influence both the

11 non-ideal mixing behaviors of CO2 rich phase and the associating and asymmetric forces

12 between polar molecules in aqueous phase.

13 (ii) The CO2 solubility undergoes an abrupt change with pressure near the phase

14 transition point of the CO2 rich phase. However, this local change caused by phase transition

15 will gradually vanish with increasing temperature [6]. Because variations in the

16 thermos-physical properties of the CO2 rich phase while transferring from vapor phase to

17 supercritical phase at high temperature, are not such large as those while transferring from

18 vapor phase to liquid phase at low temperature.

19 An accurate model of CO2 solubility should not only correspond to the overall variation

20 trend over a wide temperature and pressure range, but also embody the local abrupt changes at

21 specific thermodynamic conditions. A feasible method in the traditional models is adopting

22 different model parameters for different CO2 phases or different temperature-pressure ranges

23 [11, 55, 56]. However, the smoothness and continuity of functional derivative is difficult to be

24 guaranteed. It may lead to an ill-conditioned Jacobian matrix in large-scale multiphase flow

25 simulations [39, 40]. Considering the continuity of functional value and its derivative, a

26 piecewise function is proposed:

7
  π  
  + CT6 ln ( P + CT7 ) − CT6 ln ( CT7 )
P
CT1 P + CT2 P + CT3 P sin   if Psat < P ≤ P0
2 2 2

1 mCO 2

=  2  CT5 P + 1   (1)
 1 CT6 P CT4 CT6 P0
m |
 CO 2 P = P0 + mC
'
( P − P0 ) + ( CT4 −1)
− if P > P0
 CT4 P0 + CT7 P0
2
P0 + CT7 CT4
2

2 where mCO2 is the CO2 solubility, mol/kg; P is pressure, MPa; Psat is saturated vapor pressure

3 of water, MPa. P0 is the pressure at which the variation trend of CO2 solubility undergoes an

4 abrupt change, MPa. In this study, the expression of P0 is as follows:

5 12.1147 (2)
P0 = 16.208 6 −
1 + exp ( 0.0 49635 T − 2 .80 34 )

6 where T is temperature, °C.

7 Eq. (1) is the main controlling equation for CO2 solubility. It meets the following criteria:

8 (i) CO2 solubility is continuous at different pressures; and (ii) it is equal to zero at 0 MPa.

9 Considering the smoothness of functional derivative at P0, the expression of m’C can be

10 developed:

CT6
mC' = mCO
'
|
2 P = P0
−
P0 + CT7
2

11 (3)
 π P0  π P0 π P0 
= 2CT1 P0 + CT2 + CT3 sin  + cos  
  2 CT5 P0 + 1  2 ( CT5 P0 + 1)  2 CT5 P0 + 1  
2

12 where CT1, CT2, CT3, CT4, CT5, CT6 and CT7 are the temperature-related parameters. The

13 previous studies indicated that CO2 solubility first increases and then decreases with

14 increasing temperature [18]. Here, a combination of polynomial and logarithmic functions is

15 used to estimate the parameters CT1 - CT7:

x4
16 x = x0 + x1T + x2T 2 + x3T 3 + + x5 ln (T ) (4)
T

17 where x0-x5 are constants, fitted by experimental measurements of CO2 solubility.

18 2.2 Water content in CO2

19 Similar to the CO2 solubility, the water content in CO2 rich phase is a function of

20 temperature and pressure. Here, the variation rules and controlling mechanism for water

8
 1 content in CO2 are analyzed as follows:

2 (i) Overall, the water content in CO2 rich phase first decreases and then approaches to

3 constant with increasing pressure [11]. Because the saturated vapor pressure of water is

4 constant at a specific temperature. It means that the proportion of water partial pressure in the

5 total pressure decreases gradually as the total pressure increases.

6 (ii) The water content increases abruptly as the phase transition of CO2 rich phase occurs

7 [6]. However, the abrupt increase of CO2 content during phase transition becomes unobvious

8 as increasing temperature.

9 Based on the aforementioned analysis, the following model for water content is

10 proposed:

  
C P sin  π CT5 PCO2  +  1
− 1  C +1 if Psat < P ≤ P0
 T3  2 CT5 PCO + 1  
( )  T4
CT7
11   2  
1 + CT6 PCO2
 (5)
YH 2O =
 π CT5 PCO2   
{ }
 1
( )
CT1 1 − exp CT2 PCO2 − P0  + CT3 P sin 
2
 +  − 1 CT4 + 1 if P > P0

 
  2 + 1 
( ) 
CT7
  C P
T5 CO2   1 + CT6 PCO2
 

12 where YH2O is the mole fraction of water in CO2 rich phase, mol/mol; PCO2 is the partial

13 pressure of CO2 in gas phase, MPa. The proposed model meets the following criteria: (i) Both

14 the functional value and functional derivative are continuous at different pressures; and (ii) it

15 is equal to one at 0 MPa.

16 The expressions for temperature-related parameters (CT1, CT2, CT3, CT4, CT5, CT6 and CT7)

17 are written as follows:

18 x = x0 + x1T + x2T 2 + x3T 3 + x4T x5 (6)

19 where x0-x5 are constants, fitted by the experimental measurements of water content. It should

20 be noted that the constants in Eq. (6) are different with those in the model of CO2 solubility.

21 2.3 Model parameters determination

22 2.3.1 Development of experimental databank

23 The model parameters in phase equilibria model should be determined by experimental

9
 1 measurements. Therefore, the quality of experimental data influences the accuracy of the

2 model calculation [10, 11, 19, 52, 54].

3 Regarding CO2 and water system, a databank of updated experimental data available is

4 developed, which contains 1573 measurements of CO2 solubility and 671 measurements of

5 H2O content assembled from 73 literature experimental studies.

6 Different experimental methods were employed to obtain these measurements, including

7 volumetric expansion [17, 57, 58, 59], water trapping [60-65], gas chromatography [52, 66,

8 67, 68], synthetic method [69-72], Raman spectroscopy [7, 37, 73], and calorimetric

9 technique [74]. Overall, most of the data are consistent with each other over a wide

10 temperature and pressure range. The reliability and consistency of experimental

11 measurements has been widely analyzed in previous studies [4, 11, 41] and this topic is

12 beyond the scope of this work. The details of the developed databank for CO2+water system

13 are presented in Appendix 1.

14 2.3.2 Determination procedures of model parameters

15 The Newton-Rapson iterative algorithm is used to determine the model parameters based

16 on the developed experimental databank [75, 76]. Considering the heterogeneous distribution

17 of experimental data over the oriented temperature and pressure range, the model parameters

18 are firstly fitted by the simulated results of previous model and then corrected by the

19 experimental data. The detailed procedure is described as follows:

20 (1) The model developed by Spycher and Pruess [11] is one of the most commonly used

21 mutual solubility models in geological field [9, 20, 24], although it may be not accurate above

22 60 MPa. Here, the predicted CO2 solubility and water content by Spycher and Pruess [11] are

23 used to determine the initial values of parameters in our model.

24 (2) The model parameters are corrected by the developed databank of experimental

25 measurements. In this process, the simulated results in step (1) are used as the initial value for

26 parameter determination during the Newton-Rapson iterations.

10
1 Following the aforementioned method, the parameters in our model are determined and

2 shown in Table1.

11
1 Table 1 Model parameters for mutual solubility of CO2+H2O system

Model Parameter x0 x1 x2 x3 x4 x5
CT1 1.0373789E-07 1.5044258E-08 -8.4848531E-11 1.5282742E-13 2.2136688E-07 -2.3462305E-07
CT2 -0.8934504 8.6407834E-03 -3.2540648E-05 -1.4988959E-08 4.5710836E-02 4.0081990E-05
CT3 0.5729271 -3.3513558E-03 -8.4827891E-06 1.5150345E-07 -5.7929902E-02 3.8959479E-05
CO2
CT4 1.012116 -1.5057825E-03 1.6628096E-05 -1.0011081E-07 -3.9395094E-02 -1.6943612E-04
solubility
CT5 0.6804949 4.0800871E-03 1.8079967E-05 -4.3441358E-08 1.8997839E-02 -1.7145340E-04
CT6 2.130724 -1.0764878E-03 5.3542022E-05 -2.1669502E-07 1.007592 1.0387723E-03
CT7 0.9707671 2.7750955E-02 -8.2421283E-05 1.2260193E-07 0.8249869 1.0547936E-03
CT1 2.0688743E-03 -4.4394596E-05 1.7300747E-06 -2.8236741E-09 -1.4611128E-12 4.0
CT2 6.6550930E-02 -9.6381214E-04 5.0556039E-06 -9.2780007E-09 90308.46 -4.029780
CT3 -1.4181999E-02 7.3038931E-04 -2.6147475E-05 1.4154445E-07 -2.3146336E-10 4.0
H2O
CT4 0.9864178 5.6851849E-04 -2.3684432E-05 1.2538675E-07 -2.5681130E-10 4.0
Content
CT5 4.116291 -8.8728063E-02 1.2406416E-03 -5.9699876E-06 8.6668730E-09 4.0
CT6 3.7947281E-02 2.4881836E-03 -4.2507397E-05 5.7203442E-07 -1.3066513E-09 4.0
CT7 1.735499 -1.6130313E-02 1.0576388E-04 -1.7351347E-07 -9.7407872E-11 4.0
2

12
 1 3. Model validation and evaluation

2 3.1 Comparison with experimental measurements

3
4 Fig. 1. Overall model performance for phase equilibria of CO2+H2O system. The experimental

5 measurements are adopted from the developed databank in Appendix A.

6 Using the proposed model, the mutual solubility for CO2+H2O system is estimated and

7 compared with the experimental measurements as shown in Fig. 1.

8 The x-coordinate in Fig.1 represents the mole fraction of CO2 in aqueous phase and CO2

9 rich phase. A series of curves on the left are the bubble point lines, while those on the right are

10 the dew point lines. At the region between the bubble point curves and dew point curves, the

11 fluid system is in two immiscible phases.

12 As shown in Fig.1, blow 250 °C and 200 MPa, our simulated results are in good

13 agreement with the experimental measurements. The average simulation error of CO2

14 solubility in aqueous phase is 6.899%, whereas that of water content in CO2 rich phase is

15 9.67%. Except for the capacity of our model, the quality of experimental measurements is

16 also a considerable factor for the simulation accuracy. Compared to that of CO2 solubility, the

17 accurate determination of water content is much more difficult [77], leading to a larger

18 calculation deviation for the composition of CO2-rich phase.

19 In order to further evaluate the model performance for the phase partitioning behaviors

13
1 of CO2+water system, the simulated results are compared to the experimental data assembled

2 from different literature studies at different temperatures (low temperature: 0-50 °C; moderate

3 temperature: 50-150 °C; high temperature: 150-250 °C).

4 3.1.1 CO2 solubility

5 3.1.1.1 0 °C-50 °C

14
 1
2 Fig. 2 CO2 solubility in aqueous phase at 0 °C -50 °C

3 Fig. 2 shows the comparison of the simulated results and measured data of CO2
4 solubility at 0 °C -50 °C. Overall, there is a good agreement between the published
5 experimental data and our computed data.
6 As seen, the CO2 solubility increases gradually in a nonlinear manner. An obvious
7 inflection point for the increasing trend can be found when the CO2-rich phase transfers from
8 the vapor phase to the liquid or supercritical phase. The proposed model can accurately
9 characterize the influence of phase transition on CO2 solubility.
10 However, slight uncertainty remains especially at 25 °C, owing to quite significant
11 discrepancies between the literature sources. The discrepancies were mainly generated by the
12 difference between experimental principles, procedures and measurement accuracy [1, 10, 19].
13 Since the reliability of phase partitioning data has been comprehensively analyzed by several
14 researchers [4, 6, 11, 41], a critical evaluation is beyond the scope of this paper.
15 3.1.1.2 50 °C -150 °C

16

15
 1

2
3 Fig. 3 CO2 solubility in aqueous phase at 50 °C -150 °C

4 50°C-150°C is the commonly encountered temperature region in geological engineering

5 applications. The CO2 solubility in aqueous phase at 50 °C-150 °C is analyzed in Fig. 3. As

6 seen, the CO2 solubility is generally less than 3 mol/kg at moderate temperature, with a good

7 agreement between published experimental and model data.

8 Compared to pressure, CO2 solubility is less sensitive to temperature at 50 °C -150 °C.

9 As shown in Fig. 3, CO2 solubility increases from 2.0 mol/kg to 2.5mol/kg when the

10 temperature increases from 50 °C to 150 °C at 100 MPa. The CO2 solubility increases

11 gradually as pressure increases, but the variation rate decreases.

16
1 3.1.1.3 150 °C -250 °C

4
5 Fig. 4 CO2 solubility in aqueous phase at 150°C-250°C

6 Fig.4 shows the comparison of simulated results and measured data of CO2 solubility at

7 150 °C -250 °C. At high temperature, the simulated results of our model are closely consistent

8 with the experimental data.

9 As seen, CO2 solubility increases gradually with pressure and shows a high sensitivity to

17
 1 temperature. At 100 MPa, it increases from 3.25 mol/kg to 12.0 mol/kg when the temperature

2 increases from 150 °C to 250 °C.

3 3.1.2 H2O content

4 3.1.2.1 0 °C -50 °C

6
7 Fig. 5 Water content in the CO2 rich phase at 0 °C -50 °C

8 Fig. 5 shows the comparison of the simulated results and measured data of water content

9 in the CO2 rich phase at 0 °C - 50 °C. The simulated results generated by our model are in

10 good agreement with the experimental data in the literature. As pressure increases, water

11 content in the CO2 rich phase first decreases rapidly and then approaches to constant. Because

12 the increase of system pressure can lead to a decrease of the proportion of water saturated

13 vapor pressure in CO2 rich phases.

14 A rapid increase of water content with pressure is found near the point of phase transition

15 of the CO2 rich phase. This phenomenon can be accurately estimated using the proposed

18
 1 model.

2 3.1.2.2 50 °C -150 °C

5
6 Fig. 6 Water content in the CO2 rich phase at 50 °C -150 °C

7 The water content in aqueous phase at 50 °C-150 °C is analyzed in Fig. 6. The proposed

8 model is in good agreement with the experimental data at the moderate temperature region.

9 The extrapolative capacity of the proposed model is acceptable when the pressure is extended

10 to 350 MPa.

19
 1 At 150 °C, our model results differ significantly from the measurement of Takenouchi

2 and Kennedy [60], and agree well with the experimental data adopted from other literature

3 studies. This inconsistency has also been noticed in several studies [4, 6, 41, 71, 78], which

4 claimed that the measurements of Takenouchi and Kennedy [60] may be not accurate due to

5 the imperfect experimental procedures.

6 3.1.2.3 150 °C -250 °C

8
9 Fig. 7 Water content in the CO2 rich phase at 150°C -250°C

10 At 150 °C -250 °C, the water content in the CO2 rich phase is shown in Fig. 7. As seen,

11 the phase composition of the CO2 rich phase changes significantly with temperature at this

12 thermodynamic region. The water content increases by 150 percent when the temperature

13 increases from 200 °C to 250 °C. Furthermore, the developed model agrees well with the

14 measurements in available literature studies, except for those of Takenouchi and Kennedy

20
 1 [60].

2 3.2 Comparison with other models

3 3.2.1 CO2 solubility

4
5 Fig. 8 Comparison of CO2 solubility simulated by the proposed model and other models. DS2003
6 represents the model of Duan and Sun [41]; and SP2010 represents the model of Spycher and Pruess [11].

7 The theoretical models for mutual solubility of CO2+water system fall into two distinct

8 categories: fugacity-fugacity (φ-φ) approach and fugacity-activity (φ-γ) approach [1, 52]. The

9 model of Spycher and Pruess [11] using an φ-γ approach is one of the most commonly used

10 and cited models in geological-related field [9, 20, 24]. The model of Li and Yang [10] uses a

11 classical φ-φ approach, in which a modified Peng–Robinson EOS is developed to

12 simultaneously estimate the fugacity of CO2 and water in aqueous phase and CO2 rich phase.

13 Validation and comparison of the proposed model against literature measurements and other

14 models of Spycher and Pruess [11] and Li and Yang [10] is preformed to evaluate the

15 performance of these models, as shown in Fig. 8.

16 At low and moderate temperatures (50 °C and 150 °C), all the models can accurately

17 reproduce the CO2 solubility at different pressures, while our model shows a better agreement.

18 At high temperature (250 °C), the simulated results of Li and Yang [10] significantly deviate

19 from the experimental measurements. The model of Spycher and Pruess [11] shows a good

20 agreement blow 60 MPa, but it differs greatly above 60 MPa. By compassion, our model has a
21
 1 better accuracy at the wide pressure range of 0-200 MPa. For example, at 250 °C and 150

2 MPa, the simulation errors for Spycher and Pruess [11], Li and Yang [10], and our model are

3 -85%, 89% and 0.1%, respectively.

4 3.2.2 H2O content

5
6 Fig. 9 Comparison of H2O content simulated by the proposed model and other models. DS2003
7 represents the model of Duan and Sun [41]; and SP2010 represents the model of Spycher and Pruess [11].

8 Fig. 9 shows the comparison between measured data and simulated results of different

9 models. As seen, all the models can accurately reproduce the H2O content blow 150 °C. At

10 high temperatures (above 150 °C), the deviation of Li and Yang [10] significantly increases,

11 whereas our model and Spycher and Pruess [11] exhibit good agreements with the measured

12 data. At 250 °C, the accuracy of our model is slightly better than other models.

13 Validation of the model calculations against updated experimental data available and

14 other models indicates that the proposed model is capable of simultaneously predicting the

15 compositions of CO2-rich and water-rich phases with a comparable or better accuracy.

16 Besides, the extrapolative capacity of the model for water content prediction is verified at

17 high pressure. More importantly, our model is explicit, computational efficiently, and doesn't

18 require iterative algorithms, which greatly facilitates its incorporation into a multiphase flow

19 simulator.

22
 1 3.3 Phase diagram of CO2+H2O system

2
3 Fig. 10 Phase diagram of CO2 solubility in the aqueous phase

4 Fig. 10 shows the phase diagram of CO2 solubility. In the color region, the fluid mixture

5 is split into two immiscible phases. When the saturated vapor pressure of water is larger than

6 the system pressure, only a single vapor phase is stable, as shown by the gray region in the

7 figure.

8 As indicated by the contour lines, CO2 solubility increases gradually with increasing

9 pressure, but the increasing rate is smaller at higher pressure. Furthermore, CO2 solubility first

10 decreases and then increases with temperature increasing, showing a more sensitivity to

11 temperature above 150 °C.

12
13 Fig. 11 Phase diagram of water content in the CO2 rich phase

23
 1 Fig. 11 shows the phase diagram of water content in the CO2-rich phase. As seen, the

2 water content increases gradually with temperature, and the increasing rate is larger at higher

3 temperature. At a specific temperature, the water content first rapidly decreases and then

4 approaches to constant at high pressure.

5 Although there exists an abrupt change in CO2 solubility and water content near the

6 phase transition point of the CO2-rich phase, the fluid composition of different phases should

7 be a continuous function of temperature and pressure. The proposed model maintains the

8 continuity and smoothness of functional value and its derivative, as indicated by its

9 controlling equations and the simulated results in Figs. 10 and 11.

10 In order to accurately predict the phase equilibria behaviors, different model parameters

11 are commonly used in traditional models [11, 55, 56] according to the transition of CO2-rich

12 phase and temperature range. However, if the functional derivative is not continuous, the

13 Jacobian-based simulation formulation can be damaged and its incorporation into a

14 large-scale simulator may be infeasible [40].

15 4. Extension of the model to CO2 solubility in brine

16 The fluid system that is consist of CO2 and water commonly contains salts in typical

17 geological applications such as CO2 geological storage in saline aquifers or disposal in deep

18 sea [1, 2, 4, 6-9]. The most commonly encountered ions are Na+, K+, Ca2+, Mg2+, Cl- and

19 SO42-. Dissolution and ionization of salts in aqueous phase has a small influence on the

20 composition of CO2-rich phase [1, 11], but significantly affects the CO2 solubility in aqueous

21 phase.

22 4.1 Modelling formulation

23 The dissolved salt can decrease gas solubility via increasing the relative activity

24 coefficient of gas components in aqueous phase. A straightforward approach to estimate the

25 effect of salting out is Setschenov-type model, in which log (mCO2 in pure water/ mCO2 in brine) =

24
 1 Setschenov constant × salt molality. However, this approach may be not accurate enough over

2 a wide temperature and pressure range [37].

3 Considering the interactions between cations, anion and gas in the aqueous phase, Pitzer

4 and Mayorga [79] developed a theoretical model of the relative activity coefficient based on

5 the analysis of excess Gibbs energy of an aqueous. It has been widely used in the previous

6 numerical studies of gas solubility [11, 41]. One of the representative works was performed

7 by Duan and Sun [41], in which an accurate correlation containing 20 parameters was

8 developed to analyze the effect of NaCl on CO2 solubility.

9 Regarding the aqueous phase containing Na+, K+, Ca2+, Mg2+, Cl- and SO42-, a simple

10 model for CO2 solubility in brine is proposed:

11 {
mCO2 , salts = mCO2 / exp ( λ + ξ mCl ) ( mNa + CK mK + CCa mCa + CMg mMg ) + CSO4 mSO4 } (7)

12 λ = λATK + λB + λC / TK (8)

13 where mCO2, salts is the CO2 solubility in brines, mol/kg; CK, CCa, CMg and CSO4 represent the

14 degree of different ions affecting CO2 solubility compared to Na+; ξ represents the parameter

15 of ternary interaction between C1-, cations and CO2; λ is the parameter of binary interaction

16 between salt and CO2, which is a function of temperature; TK is the temperature, K.

17 In this study, an experimental databank of CO2 solubility in brine was developed

18 assembled from the updated literature studies available. The details of the databank are

19 presented in Appendix 2. Using a Newton-Rapson iterative algorithm, the parameters in the

20 model of CO2 solubility in brine was determined, as shown in Table 2.

21 Table 2. Parameters of CO2 solubility in brines

Parameter Value Parameter Value

CK 6.2753068E-01 λA -2.3447473E-03
CCa 2.3350395 λB 1.5231928
CMg 2.1883697 λC -3.0944008E02
CSO4 2.5412610E-01 ξ 5.7587599E-03

25
 1 As shown in Table 2, the relationship between different model parameters is CCa > CMg >

2 2 > 2CK. It indicates that the descending order of salting out effect of chlorine brines on CO2

3 solubility is CaCl2, MgCl2, NaCl and KCl with same ionic strength. More details will be

4 demonstrated in the following analysis.

5 4.2 Comparison with experimental data in different brines

6 The proposed model is compared and validated against literature data and other previous

7 models. The detailed simulation errors for different aqueous solutions are shown in Table 3.

8 For a specific solution, the experimental data are adopted from different literature studies, as

9 shown in Appendix 2.

10 Compared to other models, the correlation developed by Duan and Sun [41] is most

11 accurate for CO2+H2O+NaCl system. The average simulation error of our model for CO2

12 solubility in NaCl solution is 7.34%, which lies between those of Spycher and Pruess [11] and

13 Duan and Sun [41]. However, our model can turn into a simple function of mNa, λ, and ξ,

14 which contains only several parameters for the NaCl solution. Furthermore, the proposed

15 model is more accurate for other aqueous solutions of single salt except for NaCl. Because

16 most of the data used in developing the correlation of Duan and Sun [41] and Spycher and

17 Pruess [11] is obtained in NaCl+H2O+CO2 system, which can inevitably influence its

18 accuracy for other solutions, such as KCl [58].

19 Regarding all the experimental measurements in aqueous solutions containing Na+, K+,

20 Ca2+, Mg2+, Cl- and SO42-, the proposed model generates an average simulation error of 8.08%

21 and is more accurate than other models.

22 Table 3 Simulation errors of CO2 solubility in different brines

Temperature This
Salts Pressure (MPa) Exe DS2003 SP2010
(°C) model
NaCl 5-300 0.19-60 703 5.20% 9.37% 7.34%
KCl 23.85-159.95 0.1-54.83 252 14.88% 9.84% 12.27%
CaCl2 34.85-151.5 1.52-71.23 225 4.90% 11.43% 4.51%

26
 MgCl2 36.37 -151.53 1.25-54.48 74 6.92% 9.22% 5.45%
Na2SO4 13.82-160 0.42-13.11 215 27.33% 33.57% 11.77%
NaCl+KCl 35.75- 151.52 1.07 -17.16 22 4.39% 6.28% 6.99%
NaCl+CaCl2 45-149.85 1.01-19.93 32 3.73% 6.28% 7.21%
KCl+CaCl2 45 2.09-15.87 8 5.37% 5.96% 5.92%
NaCl+KCl+CaCl2 35-149.85 1 -19.97 99 3.46% 3.11% 5.88%
NaCl+KCl+
50 -150 10.02- 57.10 18 7.87% 12.82% 6.54%
CaCl2+MgCl2
Sum 1648 9.56% 12.4% 8.08%

1 Note: Exe is the number of experimental measurements; DS2003 represents the model of Duan and Sun
2 [41]; SP2010 represents the model of Spycher and Pruess [11].

3 4.3 Simulation analysis

4
5 Fig. 12 Comparison between simulated and measured data of CO2 solubility in 1mol/kg NaCl solution.
6 The experimental data are adopted from Carvalho et al. [8], Jacob and Saylor [9], Guo et al. [20], Yan et al.
7 [24], Takenouchi and Kennedy [61], Koschel et al. [74], and Messabeb et al. [80].

8 With regard to CO2 solubility in 1 mol/kg NaCl solution, the comparison of the literature

9 experimental data and simulated results of different models is shown in Fig. 12. Overall, a

10 good agreement can be found at different temperatures and pressures in the figure.

11 Similar to that in pure water, the CO2 solubility in brine increases gradually with

12 pressure and goes through an abrupt change in the variation trend near the phase transition

13 boundary. Furthermore, the CO2 solubility first increases and then decreases with temperature

27
 1 increasing.

2
3 Fig. 13 Comparison between simulated and measured data of CO2 solubility in NaCl and KCl solutions at
4 50 °C. The experimental data are adopted from Yan et al. [24], Messabeb et al. [80], Mousavi et al. [81] and
5 Hou et al. [82].

6 Fig. 13 represents the comparison between the simulated and measured data of CO2

7 solubility in NaCl and KCl solution at 50 °C. For a specific solution, the CO2 solubility

8 decreases gradually with the increase of salt concentration. As shown in Fig. 13, the CO2

9 solubility in NaCl solution is considerably lower than that in KCl solution. It indicates that the

10 salting out effect of Na+ is larger than that of K+.

11
12 Fig. 14 Comparison between simulated and measured CO2 solubility in MgCl2 and CaCl2 solutions at

28
 1 100 °C. The experimental data are adopted from Mousavi et al. [81] and Prutton and Savage [83].

2 Fig. 14 represents the comparison between the simulated and measured CO2 solubility in

3 MgCl2 and CaCl2 solutions at 100 °C. As seen, the CO2 solubility decreases gradually with an

4 increase of MgCl2 and CaCl2 concentrations. At the identical temperature and pressure, the

5 solubility of CO2 in 3.90 mol/kg CaCl2 solution is slightly lower than that in 4.29 mol/kg

6 MgCl2 solution. It indicates that the salting-out effect of Ca2+ is larger than that of Mg2+.

7
8 Fig. 15 Comparison between simulated and measured CO2 solubility in the solutions of mixed salts. The
9 experimental data are adopted from Poulain et al. [54], Liu et al. [58], and Mousavi et al. [81].

10 Fig. 15 shows the comparison between simulated and measured CO2 solubility in the

11 solutions of mixed salts. CO2 solubility decreases with the total ionic strength increasing.

12 Furthermore, the effect of temperature on single salt solutions is similar to that on mixed salts

13 solutions. In general, the proposed model can accurately reproduce the CO2 solubility in

14 different brines.

15 The aforementioned analysis indicates that our proposed model is capable of predicting

16 both the solubility of CO2 in brine and water content in gas rich phase with accuracy better

17 than that made by traditional theoretical models over a wide T-P condition (0–250 °C, 0–200

18 MPa). In addition to the good consistency with experimental database, the model could be

19 easily incorporated into a large-scale simulation owing to its computational efficient,

29
 1 derivative-continuous and non-iterative characteristics. In future studies, we will explore its

2 extension to various systems composed of other gases and complicated solutions, providing a

3 rapid prediction of phase equilibrium behaviors in different scientific and engineering fields.

4 5. Conclusions

5 In this work, a simple model for the phase-partitioning behaviors in the systems of

6 CO2+H2O and CO2+Brine system containing Na+, K+, Ca2+, Mg2+, Cl-, and SO42- is proposed.

7 The proposed model is explicit, derivative-continuous, computationally efficient, which

8 doesn't require iterative algorithms for its use.

9 Assembled from updated literature experimental studies available, the databank of phase

10 equilibria properties in CO2+H2O and CO2+Brine systems was built. Validation of the model

11 calculations against available experimental data and other models indicates that the proposed

12 model is capable of predicting CO2 solubility in pure water and brine, and H2O content in

13 CO2 rich phase with a better or comparable accuracy over a wide T-P-msalts conditions (0–

14 250 °C, 0–200 MPa, different contents of mixed salts).

15 The simulated results show that our proposed model can precisely reproduce the abrupt

16 changes of mutual solubility near the phase transition point of the CO2-rich phase.

17 Furthermore, the descending order of salting-out effect of chlorine brines on CO2 solubility

18 is CaCl2, MgCl2, NaCl and KCl with the same ionic strength.

19 Appendix A-Experimental databank of phase equilibria in CO2+H2O system

20 In this study, a databank for experimental measurements of phase equilibrium in CO2+

21 H2O system is developed. The temperature and pressure condition of the developed databank

22 is shown in Fig. A-1.

23 The measurements of CO2 solubility in aqueous phase are assembled from 51 literature

24 studies available while those of H2O content in CO2 rich phase are collected from 22

25 published experimental studies. The details of the experimental information including authors,

30
1 measurements number, temperature and pressure ranges are shown in Table A-1 and Table

2 A-2.

3
4 Fig. A-1 Measurements of CO2 solubility in pure water
5 Table A-1. Experimental databank of CO2 solubility in pure water
No. Author Exp Temperature/°C Pressure/MPa
1 Al Ghafri et al. [84] 8 50 - 50 2.1 - 18.7
2 Bamberger et al. [64] 29 50.05 - 79.95 4.1 - 14.1
3 Bando et al. [85] 12 30 - 60 10.0 - 20.0
4 Bastami et al. [86] 10 55 - 102 6.9 - 20.7
5 Bermejo et al. [72] 26 23.58 - 96.5 1.6 - 8.3
6 Blencoe et al. [53] 8 300 - 300 27.6 - 56.7
7 Briones et al. [87] 8 50 - 50 6.8 - 17.7
8 Carvalho et al. [8] 66 10.09 - 90.27 0.3 - 12.1
9 Caumon et al. [88] 22 65 - 65 0.3 - 19.5
10 Chapoy et al. [71] 27 0.99 - 78.16 0.2 - 9.3
11 Dhima et al. [89] 7 71 - 71 10.0 - 100.0
12 Dohrn et al. [90] 5 50 - 50 10.1 - 30.4
13 D'souza et al. [91] 4 50 - 75 10.1 - 15.2
14 Ellis, A. J. [92] 36 114 - 348 0.5 - 16.4
15 Ferrentino et al. [59] 18 35 - 50 7.6 - 13.1
16 Gillepsie and Wilson [93] 33 15.6 - 260 0.7 - 20.3
17 Greenwood et al. [94] 16 11.85 - 24.85 5.0 - 40.0
18 Guo et al. [7] 131 0 - 300 10.0 - 120.0
19 Han et al. [95] 28 40.05 - 70.05 4.3 - 18.3

31
 20 Hou et al. [52] 42 25 - 175 1.1 - 17.6
21 Houghton et al. [96] 171 0 - 100 0.1 - 3.6
22 Jacob and Saylor [9] 50 23.85 - 23.85 1.4 - 12.4
23 Kiepe et al. [97] 43 40.05 - 120.02 0.0 - 9.3
24 King et al. [98] 27 15 - 25 6.1 - 24.3
25 Koschel et al. [74] 8 49.95 - 99.95 2.1 - 20.2
26 Liu et al. [58] 31 35 - 55 2.1 - 16.0
27 Lucile et al. [66] 30 25 - 120 0.5 - 5.1
28 Malinin S. D. [99] 36 200 - 300 9.7 - 49.0
29 Mohammadian et al. [23] 20 60 - 80 0.1 - 21.3
30 Mousavi [81] 8 50 - 100 7.9 - 52.4
31 Müller et al. [100] 20 100 - 200 0.3 - 8.0
32 Nakayama et al. [101] 6 25.05 - 25.05 3.6 - 11.0
33 Nighswander et al. [57] 33 79.7 - 198.1 2.0 - 10.2
34 Prutton and Savage [83] 26 101 - 120 2.3 - 70.3
35 Qin et al. [102] 7 50.45 - 102.65 10.6 - 49.9
36 Rumpf et al. [22] 7 50.01 - 50.03 1.1 - 5.8
37 Sako et al. [67] 7 75.15 - 148.25 10.2 - 19.7
38 Savary et al. [103] 3 150 - 150 11.3 - 33.7
39 Shagiakhmetov and Tarzimanov [104] 6 100 - 150 10.1 - 60.1
40 Stewart and Munjal [62] 12 0 - 25 1.0 - 4.6
41 Takenouchi and Kennedy [60] 116 110 - 350 10.0 - 150.0
42 Takenouchi and Kennedy [61] 21 150 - 300 10.0 - 60.0
43 Teng et al. [105] 40 4.85 - 24.85 5.0 - 40.0
44 Todheide and Franck [106] 104 50 - 350 20.0 - 350.0
45 Tong et al. [18] 18 101 - 101.84 7.2 - 27.3
46 Truche et al. [73] 7 200 - 280 3.1 - 13.2
47 Valtz et al. [68] 47 5.07 - 45.08 0.5 - 8.0
48 Wiebe [107] 73 0 - 100 2.5 - 70.9
49 Wiebe and Gaddy [108] 29 50 - 100 2.5 - 70.9
50 Yan et al. [24] 18 50.05 - 140.05 5.0 - 40.0
51 Zawisza and Malesinska [109] 33 50 - 200 0.2 - 5.4
1 Note that Exp is the number of measurements in the literature study.

2 Table A-2. Experimental databank of H2O content in the CO2 rich phase
No. Author Exp Temperature/° Pressure/MPa

32
 C
1 Bamberger et al. [64] 29 50.05 - 79.95 4.1 - 14.1
2 Briones et al. [87] 8 50 - 50 6.8 - 17.7
3 Caumon et al. [88] 21 100 - 100 0.5 - 20.1
4 Dohrn et al. [90] 5 50 - 50 10.1 - 30.4
5 D'souza et al. [91] 4 50 - 75 10.1 - 15.2
6 Gillepsie and Wilson [93] 33 15.6 - 260 0.7 - 20.3
7 Hou et al. [52] 39 25 - 175 1.1 - 17.5
8 Jackson et al. [110] 2 50 - 75 34.5 - 34.5
9 Kim et al. [77] 26 10.05 - 38.85 8.1 - 20.1
10 King et al. [98] 41 15 - 40 5.2 - 20.3
11 King Jr and Coan [111] 22 25 - 100 1.7 - 5.1
12 Malinin [99] 26 200 - 300 19.5 - 58.8
13 Meyer and Harvey [112] 58 10 - 80 0.5 - 5.0
14 Mousavi [81] 14 100 - 150 1.6 - 55.2
15 Müller et al. [100] 20 100 - 200 0.3 - 8.1
16 Qin et al. [102] 7 50.45 - 102.65 10.6 - 49.9
17 Sako et al. [67] 8 75.15 - 148.25 10.2 - 20.9
18 Song and Kobayashi [113] 19 12 - 31.06 0.7 - 13.8
19 Takenouchi and Kennedy [60] 116 110 - 350 10.0 - 150.0
20 Todheide and Franck [106] 104 50 - 350 20.0 - 350.0
21 Valtz et al. [68] 30 5.07 - 45.07 0.5 - 8.0
22 Wiebe and Gaddy [114] 39 25 - 75 0.1 - 70.9

1 Note that Exp is the number of measurements in the literature study.

2 Appendix B-Experimental databank of phase equilibria in CO2+Brine system

3 The databank for experimental measurements of CO2 solubility in brines containing Na+,

4 K+, Ca2+, Mg2+, Cl-, or SO42- is developed, which is assembled from 28 literature studies

5 available. The temperature and pressure condition of the developed databank is shown in Fig.

6 B-1. The details of the experimental information including authors, measurements number,

7 temperature and pressure ranges are shown in Table B-1.

33
1
2 Fig. B-1 Experimental points of CO2 solubility in brines
3 Table B-1 Measurements of CO2 solubility in brines containing Na+, K+, Ca2+, Mg2+, Cl-, or SO42-
No. Salts Authors Exp. Temperature/°C Pressure/MPa
1 NaCl Bando et al. [85] 36 30 -60 10 -20
2 NaCl Carvalho et al. [8] 44 19.93- 80.08 1.02- 14.29
3 NaCl Guo et al. [20] 142 5 -200 10 -40
4 NaCl Hou et al. [82] 36 50 -150 2.61 -18.21
5 NaCl Jacob and Saylor [9] 28 23.85 -23.85 1.72 -10.69
6 NaCl Kiepe et al. [97] 63 40.23- 79.93 0.19 -10.1
7 NaCl Koschel et al. [74] 14 49.95 -99.95 5 -20.24
8 NaCl Liu et al. [58] 8 45 -45 2.1 -15.83
9 NaCl Messabeb et al. [80] 40 50- 150 4.99 -20.23
10 NaCl Mohammadian et al. [23] 42 60- 80 2.1 -21.3
11 NaCl Nighswander et al. [57] 32 80 -200.5 2.11- 10.03
12 NaCl Rumpf et al. [22] 63 39.99- 159.93 0.47-9.64
13 NaCl Savary et al. [103] 6 120 -120 12.5 -30.5
14 NaCl Yan et al. [24] 35 50.05- 140.05 5 -40
15 NaCl Mousavi et al. [81] 85 5 -150 0.90- 57.24
16 NaCl Takenouchi and Kennedy [61] 29 150- 300 10- 60
17 KCl Hou et al. [82] 24 50 -100 2.92- 18.22
18 KCl Jacob and Saylor [9] 20 23.85 -23.85 2.1 -9.65
19 KCl Pérez-Salado Kamps et al. [69] 93 39.95 -159.95 0.41- 9.40
20 KCl Kiepe et al. [97] 88 40.01 -80.25 0.09 -10.51
21 KCl Liu et al. [58] 8 45 -45 2.09 -15.81
22 KCl Mousavi et al. [81] 19 50- 150 8.21- 54.83

34
 23 CaCl2 Bastami et al. [86] 22 55- 102 6.89 -20.68
24 CaCl2 Liu et al. [58] 8 45- 45 2.09 -15.86
25 CaCl2 Prutton and Savage [83] 116 75.5- 121 1.52- 71.23
26 CaCl2 Tong et al. [18] 36 34.85 -151.49 1.53 -37.99
27 CaCl2 Mousavi et al. [81] 43 50 -150 6.52- 59.59
28 MgCl2 Tong et al. [18] 39 36.37 -151.53 1.25 -34.93
29 MgCl2 Mousavi et al. [81] 35 50- 150 8.23 -54.48
30 Na2SO4 Bermejo et al. [72] 113 13.82 -95.66 1.98 -13.11
31 Na2SO4 Rumpf and Maurer [115] 102 39.96 -160.01 0.42 -9.71
32 NaCl+KCl Liu et al. [58] 8 45 -45 2.48 -15.99
33 NaCl+KCl Tong et al. [18] 14 35.75- 151.52 1.07 -17.16
34 NaCl+CaCl2 Liu et al. [58] 8 45 -45 2.46- 16.02
35 NaCl+CaCl2 Poulain et al. [54] 24 49.85 -149.85 1.01 -19.93
36 KCl+CaCl2 Liu et al. [58] 8 45 2.09-15.87
37 NaCl+KCl+CaCl2 Liu et al. [58] 75 35- 55 1.34 -15.85
38 NaCl+KCl+CaCl2 Poulain et al. [54] 24 49.85 -149.85 1 -19.97
NaCl+KCl+
39 Mousavi et al. [81] 18 50 -150 10.02- 57.10
CaCl2+MgCl2

1 Note that Exp. is the number of measurements in the literature study.

2 Acknowledgements

3 This work was supported by the National Natural Science Foundation of China (Major

4 Program, 51991363; General Program, 51974350), the CNPC's Major Science and

5 Technology Projects (ZD2019-184-003).

6 Parts of this work were carried out in 2018-2019 by the senior author (Xiaohui Sun)

7 while he was a visiting scholar at Lawrence Berkeley National Laboratory. We thank Curtis M.

8 Oldenburg and Lehua Pan (LBNL) for their hospitality, assistance, and weekly group

9 meetings where some of these methods were first presented.

10 References

11 [1] Springer, R. D., Wang, Z., Anderko, A., et al. A thermodynamic model for predicting mineral
12 reactivity in supercritical carbon dioxide: I. Phase behavior of carbon dioxide–water–chloride salt
13 systems across the H2O-rich to the CO2-rich regions. Chemical Geology, 2012, 322: 151-171.
14 [2] Bachu, S. Sequestration of CO2 in geological media in response to climate change: road map for

35
 1 site selection using the transform of the geological space into the CO2 phase space. Energy
2 Conversion and Management, 2002, 43: 87–102.
3 [3] Bachu, S., Adams, J. J. Sequestration of CO2 in geological media in response to climate change:
4 capacity of deep saline aquifers to sequester CO2 in solution. Energy Conversion and
5 Management, 2003, 44: 3151–3175.
6 [4] Diamond, L. W., Akinfiev, N. N. Solubility of CO2 in water from− 1.5 to 100 C and from 0.1 to
7 100 MPa: evaluation of literature data and thermodynamic modelling. Fluid phase equilibria,
8 2003, 208(1-2): 265-290.
9 [5] Shukla, R., Ranjith, P. G., Haque, A., et al. A review of studies on CO2 sequestration and caprock
10 integrity. Fuel, 2010, 89(10): 2651-2664.
11 [6] Spycher, N., Pruess, K., Ennisking, J., et al. CO2-H2O mixtures in the geological sequestration of
12 CO2. I. Assessment and calculation of mutual solubilities from 12 to 100°C and up to 600 bar.
13 Geochimica et Cosmochimica Acta, 2003, 67(16): 3015-3031.
14 [7] Guo H., Chen Y., Hu Q., Lu W., Ou W., Geng L. Quantitative Raman spectroscopic investigation of
15 geo-fluids high-pressure phase equilibria: Part I. Accurate calibration and determination of CO2
16 solubility in water from 273.15 to 573.15 K and from 10 to 120 MPa. Fluid Phase Equilibria,
17 2014, 382: 70-79.
18 [8] Carvalho P. J., Pereira L. M., Gonçalves N. P., Queimada A. J., Coutinho J. A. Carbon dioxide
19 solubility in aqueous solutions of NaCl: Measurements and modeling with electrolyte equations
20 of state. Fluid Phase Equilibria, 2015, 388: 100-106.
21 [9] Jacob R., Saylor B. Z. CO2 solubility in multi-component brines containing NaCl, KCl, CaCl2 and
22 MgCl2 at 297 K and 1–14 MPa. Chemical Geology, 2016, 424: 86-95.
23 [10] Li X., Yang, D. Determination of Mutual Solubility between CO2 and Water by Using the Peng–
24 Robinson Equation of State with Modified Alpha Function and Binary Interaction Parameter.
25 Industrial & Engineering Chemistry Research, 2013, 52(38): 13829-13838.
26 [11] Spycher, N., Pruess, K. A Phase-Partitioning Model for CO2–Brine Mixtures at Elevated
27 Temperatures and Pressures: Application to CO2-Enhanced Geothermal Systems. Transport in
28 Porous Media, 2010, 82(1): 173-196.
29 [12] Borgia, A., Pruess, K., Kneafsey, T. J., Oldenburg, C. M., Pan, L. Numerical simulation of salt
30 precipitation in the fractures of a CO2-enhanced geothermal system. Geothermics, 2012, 44:
31 13-22.
32 [13] Zhao, Y., Cao, H., Xie, Y., Yuan, J., Ji, Z., Yan, Z. Mechanism studies of a CO2 participant
33 softening pretreatment process for seawater desalination. Desalination, 2016, 393: 166-173.
34 [14] El-Naas, M. H., Mohammad, A. F., Suleiman, M. I., Al Musharfy, M., Al-Marzouqi, A. H. A new
35 process for the capture of CO2 and reduction of water salinity. Desalination, 2017, 411: 69-75.
36 [15] Dindi A, Quang D V, AlNashef I, Abu-Zahra M. R. M. A process for combined CO2 utilization
37 and treatment of desalination reject brine. Desalination, 2018, 442: 62-74.

36
 1 [16] Dajnak D, Lockwood F C. Use of thermal energy from waste for seawater desalination.
2 Desalination, 2000, 130(2): 137-146.
3 [17] Zhao, H., Fedkin, M., Dilmore, R., et al. Carbon dioxide solubility in aqueous solutions of sodium
4 chloride at geological conditions: Experimental results at 323.15, 373.15, and 423.15 K and 150
5 bar and modeling up to 573.15 K and 2000 bar. Geochimica et Cosmochimica Acta, 2015:
6 165-189.
7 [18] Tong, D., Trusler, J. M., Vega-Maza, D. Solubility of CO2 in aqueous solutions of CaCl2 or MgCl2
8 and in a synthetic formation brine at temperatures up to 423 K and pressures up to 40 MPa.
9 Journal of Chemical & Engineering Data, 2013, 58(7): 2116-2124.
10 [19] Akinfiev, N. N., Diamond, L. W. Thermodynamic model of aqueous CO2–H2O–NaCl solutions
11 from -22 to 100° C and from 0.1 to 100 MPa. Fluid Phase Equilibria, 2010, 295(1): 104-124.
12 [20] Guo, H., Huang, Y., Chen, Y., Zhou, Q. Quantitative raman spectroscopic measurements of CO2
13 solubility in nacl solution from (273.15 to 473.15) K at p = (10.0, 20.0, 30.0, and 40.0) MPa.
14 Journal of Chemical & Engineering Data, 2016, 61(1): 466-474.
15 [21] Hassanpouryouzband, A., Farahani, M. V., Yang, J., Tohidi, B., Chuvilin, E., Istomin, V.,
16 Bukhanov, B. Solubility of flue gas or carbon dioxide-nitrogen gas mixtures in water and aqueous
17 solutions of salts: Experimental measurement and thermodynamic modeling. Industrial &
18 Engineering Chemistry Research, 2019, 58(8): 3377-3394.
19 [22] Rumpf, B., Nicolaisen, H., Öcal, C., Maurer, G. Solubility of carbon dioxide in aqueous solutions
20 of sodium chloride: experimental results and correlation. Journal of solution chemistry, 1994,
21 23(3): 431-448.
22 [23] Mohammadian, E., Hamidi, H., Asadullah, M., Azdarpour, A., Motamedi, S., Junin, R.
23 Measurement of CO2 solubility in NaCl brine solutions at different temperatures and pressures
24 using the potentiometric titration method. Journal of Chemical & Engineering Data, 2015, 60(7):
25 2042-2049.
26 [24] Yan, W., Huang, S., Stenby, E. H., et al. Measurement and modeling of CO2 solubility in NaCl
27 brine and CO2–saturated NaCl brine density. International Journal of Greenhouse Gas Control,
28 2011, 5(6): 1460-1477.
29 [25] Zhang, L., Cui, G., Zhang, Y., Ren, B., Ren, S., Wang, X. Influence of pore water on the heat
30 mining performance of supercritical CO2 injected for geothermal development. Journal of CO2
31 Utilization, 2016, 16: 287-300.
32 [26] Enick, R. M., Klara, S. M. Effects of CO2 Solubility in Brine on the Compositional Simulation of
33 CO2 Floods. SPE Reservoir Engineering, 1992, 7(02): 253-258.
34 [27] Chang, Y., Coats, B. K., Nolen, J. S., et al. A Compositional Model for CO2 Floods Including CO2
35 Solubility in Water. SPE Reservoir Evaluation & Engineering, 1998, 1(02): 155-160.
36 [28] Kwak, J. H., Hu, J. Z., Hoyt, D. W., Sears, J. A., Wang, C. M., Rosso, K. M., Felmy, A. R. Metal
37 carbonation of forsterite in supercritical CO2 and H2O using solid state Si-29, C-13 NMR

37
 1 spectroscopy. Journal of Physical Chemistry C, 2010, 114: 4126–4134.
2 [29] Kwak, J. H., Hu, J. Z., Turcu, R. V. F., Rosso, K. M., Ilton, E. S., Wang, C., Sears, J. A.,
3 Engelhard, M. H., Felmy, A. R., Hoyt, D. W. The role of H2O in the carbonation of forsterite in
4 supercritical CO2. International Journal of Greenhouse Gas Control, 2011, 5: 1081–1092.
5 [30] Ott, H., Roels, S. M., De Kloe, K. Salt precipitation due to supercritical gas injection: I.
6 Capillary-driven flow in unimodal sandstone. International Journal of Greenhouse Gas Control,
7 2015, 43: 247-255.
8 [31] Borgia, A., Pruess, K., Kneafsey, T. J., Oldenburg, C. M., Pan, L. Simulation of CO2-EGS in a
9 fractured reservoir with salt precipitation. Energy Procedia, 2013, 37: 6617-6624.
10 [32] Giorgis, T., Carpita, M., Battistelli, A., et al. 2D modeling of salt precipitation during the injection
11 of dry CO2 in a depleted gas reservoir. Energy Conversion and Management, 2007, 48(6):
12 1816-1826.
13 [33] Hurter, S., Labregere, D., Berge, J. Simulations of dry-out and halite precipitation due to CO2
14 injection. Geochimica Et Cosmochimica Acta, 2007, 71: A426–A426.
15 [34] Moore, J., Adams, M., Allis, R., Lutz, S., Rauzi, S. Mineralogical and geochemical consequences
16 of the long-term presence of CO2 in natural reservoirs: an example from the Springerville–St.
17 Johns Field, Arizona, and New Mexico, USA. Chemical Geology, 2005, 217(3-4): 365-385.
18 [35] Rosenbauer, R. J., Koksalan, T., Palandri, J. L. Experimental investigation of CO2–brine–rock
19 interactions at elevated temperature and pressure: Implications for CO2 sequestration in
20 deep-saline aquifers. Fuel processing technology, 2005, 86(14-15): 1581-1597.
21 [36] Palandri, J. L., Rosenbauer, R. J., Kharaka, Y. K. Ferric iron in sediments as a novel CO2 mineral
22 trap: CO2–SO2 reaction with hematite. Applied Geochemistry, 2005, 20(11): 2038-2048.
23 [37] Darwish, N. A., Hilal, N. A simple model for the prediction of CO2 solubility in H2O–NaCl
24 system at geological sequestration conditions. Desalination, 2010, 260(1): 114-118.
25 [38] Pathak, V., Palaschak, C., Martinez, O., et al. Solving the Challenges of Short and Long-Term
26 Production Forecasting and Uncertainty Using a Fully-Coupled Implicit Integrated Production
27 Modelling System. SPE-181427-MS, 2016.
28 [39] Pruess, K., Oldenburg, C. M., Moridis, G. J. TOUGH2 user's guide version 2. Berkeley:
29 Lawrence Berkeley National Lab, 1999.
30 [40] Reagan, M. T., Moridis, G. J., Seim, K. S., et al. Fast parametric relationships for the large-scale
31 reservoir simulation of mixed CH4-CO2 gas hydrate systems. Computers & Geosciences, 2017:
32 191-203.
33 [41] Duan, Z., Sun, R. An improved model calculating CO2 solubility in pure water and aqueous NaCl
34 solutions from 273 to 533 K and from 0 to 2000 bar. Chemical Geology, 2003, 193(3): 257-271.
35 [42] Li, Y., Ngheim, L. X. Phase equilibria of oil, gas and water/brine mixtures from a cubic equation
36 of state and Henry’s law. The Canadian Journal of Chemical Engineering, 1986, 64: 486– 496.
37 [43] Harvey, A. H., Prausnitz, J. M. Thermodynamics of high-pressure aqueous systems containing

38
 1 gases and salts. AIChE Journal, 1989, 35(4): 635– 644.
2 [44] Zuo, Y., Guo, T. M. Extension of the Patel–Teja equation of state to the prediction of the solubility
3 of natural gas in formation water. Chemical Engineering Science, 1991, 46 (12), 3251–3258.
4 [45] Yuanhui, J. I., Xiaoyan, J. I., Feng, X., et al. Progress in the study on the phase equilibria of the
5 CO2-H2O and CO2-H2O-NaCl systems. Chinese Journal of Chemical Engineering, 2007, 15(3):
6 439-448.
7 [46] Bahadori, A., Vuthaluru, H. B., Mokhatab, S. New correlations predict aqueous solubility and
8 density of carbon dioxide. International Journal of Greenhouse Gas Control, 2009, 3 (4): 474–
9 480.
10 [47] Hu, J., Duan, Z., Zhu, C. Chou, I. M. PVTx properties of the CO2–H2O and CO2–H2O–NaCl
11 systems below 647 K: Assessment of experimental data and thermodynamic models. Chemical
12 Geology, 2007, 238: 249–267.
13 [48] Sorensen, H., Pedersen, K. S., Christensen, P. L. Modeling of gas solubility in brine. Organic
14 Geochemistry, 2002, 33: 635–642.
15 [49] Mao, S., Zhang, D., Li, Y., Liu, N. An improved model for calculating CO2 solubility in aqueous
16 NaCl solutions and the application to CO2–H2O–NaCl fluid inclusions. Chemical Geology, 2013,
17 347: 43–58.
18 [50] Dubessy, J., Tarantola, A., Sterpenich, J. Modelling of liquid–vapour equilibria in the H2O–CO2–
19 NaCl and H2O–H2S–NaCl systems to 270 °C. Oil & Gas Science and Technology-Revue De L
20 Institut Francais Du Petrole, 2005, 60 (2): 339–355.
21 [51] Portier, S., Rochelle, C. Modelling CO2 solubility in pure water and NaCl-type waters from 0 to
22 300 °C and from 1 to 300 bar: application to the Utsira Formation at Sleipner. Chemical Geology,
23 2005, 217 (3–4): 187–199.
24 [52] Hou, S. X., Maitland, G. C., Trusler, J. M. Measurement and modeling of the phase behavior of
25 the (carbon dioxide+ water) mixture at temperatures from 298.15 K to 448.15 K. The Journal of
26 Supercritical Fluids, 2013, 73: 87-96.
27 [53] Blencoe, J. G., Naney, M. T., Anovitz, L. The CO2–H2O system: III. A new experimental method
28 for determining liquid-vapor equilibria at high supercritical temperatures. American Mineralogist,
29 2001, 86: 1100–1111.
30 [54] Poulain, M., Messabeb, H., Lach, A., et al. Experimental Measurements of Carbon Dioxide
31 Solubility in Na–Ca–K–Cl Solutions at High Temperatures and Pressures up to 20 MPa. Journal
32 of Chemical & Engineering Data, 2019, 64(6): 2497-2503.
33 [55] Zirrahi, M., Azin, R., Hassanzadeh, H., et al. Prediction of water content of sour and acid gases.
34 Fluid Phase Equilibria, 2010, 299(2): 171-179.
35 [56] Zirrahi, M., Azin, R., Hassanzadeh, H., et al. Mutual solubility of CH4, CO2, H2S, and their
36 mixtures in brine under subsurface disposal conditions. Fluid Phase Equilibria, 2012, 324: 80-93.
37 [57] Nighswander, J. A., Kalogerakis, N., Mehrotra, A. K. Solubilities of carbon dioxide in water and

39
 1 1 wt.% sodium chloride solution at pressures up to 10 MPa and temperatures from 80 to 200.
2 degree. C. Journal of Chemical and Engineering Data, 1989, 34(3): 355-360.
3 [58] Liu, Y., Hou, M., Yang, G., et al. Solubility of CO2 in aqueous solutions of NaCl, KCl, CaCl2 and
4 their mixed salts at different temperatures and pressures. Journal of Supercritical Fluids, 2011,
5 56(2): 125-129.
6 [59] Ferrentino, G., Barletta, D., Balaban, M. O., Ferrari, G., Poletto, M. Measurement and prediction
7 of CO2 solubility in sodium phosphate monobasic solutions for food treatment with high pressure
8 carbon dioxide. The Journal of Supercritical Fluids, 2010, 52(1): 142-150.
9 [60] Takenouchi, S., Kennedy, G. C. The binary system H2O-CO2 at high temperatures and pressures.
10 American Journal of Science, 1964, 262(9): 1055-1074.
11 [61] Takenouchi, S., Kennedy, G. C. The solubility of carbon dioxide in NaCl solutions at high
12 temperatures and pressures. American Journal of Science, 1965, 263: 445–454.
13 [62] Stewart, P. B., Munjal, P. K. Solubility of carbon dioxide in pure water, synthetic sea water, and
14 synthetic sea water concentrates at-5. deg. to 25. deg. and 10-to 45-atm. pressure. Journal of
15 Chemical and Engineering data, 1970, 15(1): 67-71.
16 [63] Malinin, S. D., Savelyeva, N. I. The solubility of CO2 in NaCl and CaCl2 solutions at 25, 50 and
17 75 C under elevated CO2 pressures. geochemistry international, 1972, 9: 410–418.
18 [64] Bamberger, A., Sieder, G., Maurer, G. High-pressure (vapor + liquid) equilibrium in binary
19 mixtures of (carbon dioxide+ water or acetic acid) at temperatures from 313 to 353 K. The
20 Journal of Supercritical Fluids, 2000, 17(2): 97-110.
21 [65] Malinin, S. D., Kurovskaya, N. A. Investigations of CO2 solubility in a solution of chlorides at
22 elevated temperatures and pressures of CO2. Geokhimiya, 1975, 4: 547–551.
23 [66] Lucile, F., Cé zac, P., Contamine, F., Serin, J. P., Houssin, D., Arpentinier, P. Solubility of carbon
24 dioxide in water and aqueous solution containing sodium hydroxide at temperatures from (293.15
25 to 393.15) K and pressure up to 5 MPa: experimental measurements. Journal of Chemical &
26 Engineering Data, 2012, 57(3): 784-789.
27 [67] Sako, T., Sugeta, T., Nakazawa, N., Okubo, T., Sato, M., Taguchi, T., Hiaki, T. Phase equilibrium
28 study of extraction and concentration of furfural produced in reactor using supercritical carbon
29 dioxide. Journal of chemical engineering of Japan, 1991, 24(4): 449-455.
30 [68] Valtz, A., Chapoy, A., Coquelet, C., Paricaud, P., Richon, D. Vapour–liquid equilibria in the
31 carbon dioxide–water system, measurement and modelling from 278.2 to 318.2 K. Fluid phase
32 equilibria, 2004, 226: 333-344.
33 [69] Pérez-Salado Kamps, Á., Meyer, E., Rumpf, B., Maurer, G. Solubility of CO2 in aqueous
34 solutions of KCl and in aqueous solutions of K2CO3. Journal of Chemical & Engineering Data,
35 2007, 52(3), 817-832.
36 [70] Mather, A. E. Franck, E. U. Phase equilibria in the system carbon dioxide–water at elevated
37 pressures. The Journal of Physical Chemistry C, 1992, 96: 6–8.

40
 1 [71] Chapoy, A., Mohammadi, A. H., Chareton, A., Tohidi, B., Richon, D. Measurement and modeling
2 of gas solubility and literature review of the properties for the carbon dioxide − water system.
3 Industrial & engineering chemistry research, 2004, 43(7): 1794-1802.
4 [72] Bermejo, M. D., Martin, A., Florusse, L. J., Peters, C. J., Cocero, M. J. The influence of Na2SO4
5 on the CO2 solubility in water at high pressure. Fluid Phase Equilibria, 2005, 238(2): 220-228.
6 [73] Truche, L., Bazarkina, E. F., Berger, G., Caumon, M. C., Bessaque, G., Dubessy, J. Direct
7 measurement of CO2 solubility and pH in NaCl hydrothermal solutions by combining in-situ
8 potentiometry and Raman spectroscopy up to 280 C and 150 bar. Geochimica et Cosmochimica
9 Acta, 2016, 177: 238-253.
10 [74] Koschel, D., Coxam, J. Y., Rodier, L., Majer, V. Enthalpy and solubility data of CO2 in water and
11 NaCl (aq) at conditions of interest for geological sequestration. Fluid phase equilibria, 2006,
12 247(1-2): 107-120.
13 [75] Doherty, J. PEST—model-independent parameter estimation. Watermark Numerical Computing,
14 Corinda 4075, Brisbane, Australia, 2008.
15 [76] Ballard A. L. Non-ideal hydrate solid solution model for a multi-phase equilibria program.
16 Golden: Colorado School of Mines, 2002.
17 [77] Kim, S., Kim, Y., Park, B. H., Lee J. H., Kang J. W. Measurement and correlation of solubility of
18 water in carbon dioxide-rich phase. Fluid Phase Equilibria, 2012, 328: 9-12.
19 [78] Dodds, W. S., Stutzman, L. F., Sollami, B. J. Carbon dioxide solubility in water, Industrial &
20 Engineering Chemistry Chemical & Engineering Data Series 1, 1956, 92-95.
21 [79] Pitzer K. S., Mayorga, G. Thermodynamics of electrolytes. II. Activity and osmotic coefficients
22 for strong electrolytes with one or both ions univalent. The Journal of Physical Chemistry, 1973,
23 77(19): 2300-2308.
24 [80] Messabeb, H., Contamine, F., Cé zac, P., Serin, J. P., Gaucher, E. C. Experimental Measurement of
25 CO2 Solubility in Aqueous NaCl Solution at Temperature from 323.15 to 423.15 K and Pressure
26 of up to 20 MPa. Journal of Chemical & Engineering Data, 2016, 61(10): 3573-3584.
27 [81] Mousavi Belfeh Teymouri, S. R. Phase equilibria measurements and modelling of CO2–rich
28 fluids/brine systems[D]. Edinburgh: Heriot-Watt University, 2017.
29 [82] Hou, S. X., Maitland, G. C., Trusler, J. M. Phase equilibria of (CO2+ H2O+ NaCl) and (CO2+
30 H2O+ KCl): Measurements and modeling. The Journal of Supercritical Fluids, 2013, 78: 78-88.
31 [83] Prutton, C. F., Savage, R. L. The solubility of carbon dioxide in calcium chloride-water solutions
32 at 75, 100, 120 and high pressures1. Journal of the American Chemical Society, 1945, 67(9):
33 1550-1554.
34 [84] Al Ghafri, S. Z., Forte, E., Maitland, G. C., Rodriguez-Henríquez, J. J., Trusler, J. M.
35 Experimental and modeling study of the phase behavior of (methane+ CO2+ water) mixtures. The
36 Journal of Physical Chemistry B, 2014, 118(49): 14461-14478.
37 [85] Bando, S., Takemura, F., Nishio, M., Hihara, E., Akai, M. Solubility of CO2 in aqueous solutions

41
 1 of NaCl at (30 to 60) C and (10 to 20) MPa. Journal of Chemical & Engineering Data, 2003,
2 48(3): 576-579.
3 [86] Bastami, A., Allahgholi, M., Pourafshary, P. Experimental and modelling study of the solubility of
4 CO2 in various CaCl2 solutions at different temperatures and pressures. Petroleum Science, 2014,
5 11(4): 569-577.
6 [87] Briones, J. A., Mullins, J. C., Thies, M. C., Kim, B. U. Ternary phase equilibria for acetic
7 acid-water mixtures with supercritical carbon dioxide. Fluid Phase Equilibria, 1987, 36: 235-246.
8 [88] Caumon, M., Sterpenich, J., Randi, A., et al. Measuring mutual solubility in the H2O–CO2 system
9 up to 200 bar and 100 °C by in situ Raman spectroscopy. International Journal of Greenhouse
10 Gas Control, 2016: 63-70.
11 [89] Dhima, A., de Hemptinne, J. C., Jose, J. Solubility of hydrocarbons and CO2 mixtures in water
12 under high pressure. Industrial & engineering chemistry research, 1999, 38(8): 3144-3161.
13 [90] Dohrn, R., Bünz, A. P., Devlieghere, F., Thelen, D. Experimental measurements of phase
14 equilibria for ternary and quaternary systems of glucose, water, CO2 and ethanol with a novel
15 apparatus. Fluid Phase Equilibria, 1993, 83: 149-158.
16 [91] D'souza, R., Patrick, J. R., Teja, A. S. High pressure phase equilibria in the carbon dioxide‐n‐
17 Hexadecane and carbon dioxide-water systems. The Canadian Journal of Chemical Engineering,
18 1988, 66(2): 319-323.
19 [92] Ellis, A. J. The solubility of carbon dioxide in water at high temperatures. American Journal of
20 Science, 1959, 257(3): 217-234.
21 [93] Gillespie, P. C., Wilson, G. M. Vapor-liquid and liquid-liquid equilibria: watermethane,
22 water-carbon dioxide, water-hydrogen sulfide, water-npentane, water-methanenpentane. Research
23 report RR-48, Gas Processors Association, Tulsa Okla., 1982.
24 [94] Clark S. P. Handbook of physical constants[M]. New Haven: Geological Society of America,
25 1966.
26 [95] Han J. M., Shin H. Y., Min B. M., Han K. H., Cho, A. Measurement and correlation of high
27 pressure phase behavior of carbon dioxide+ water system. Journal of Industrial and Engineering
28 Chemistry, 2009, 15(2): 212-216.
29 [96] Houghton, G., McLean, A. M., Ritchie, P. D. Compressibility, fugacity, and water-solubility of
30 carbon dioxide in the region 0–36 atm. and 0–100 C. Chemical Engineering Science, 1957, 6(3):
31 132-137.
32 [97] Kiepe, J., Horstmann, S., Fischer, K., Gmehling, J. Experimental determination and prediction of
33 gas solubility data for CO2+H2O mixtures containing NaCl or KCl at temperatures between 313
34 and 393 K and pressures up to 10 MPa. Industrial & Engineering Chemistry Research, 2002,
35 41(17): 4393-4398.
36 [98] King, M. B., Mubarak, A., Kim, J. D., Bott, T. R. The mutual solubilities of water with
37 supercritical and liquid carbon dioxides. The Journal of Supercritical Fluids, 1992, 5(4): 296-302.

42
 1 [99] Malinin, S. D. The system water-carbon dioxide at high temperatures and pressures. Geokhimiya,
2 1959, 3: 235–245.
3 [100] Müller, G., Bender, E., Maurer, G. Vapor liquid equilibrium in the ternary systemammonia–
4 carbon dioxide–water at high water contents in the range 373 K to 473 K. Berichte der
5 Bunsengesellschaft für Physikalische Chemie, 1988, 92: 148–160.
6 [101] Nakayama, T., Sagara, H., Arai, K., Saito, S. High pressure liquid liquid equilibria for the system
7 of water, ethanol and 1, 1-difluoroethane at 323.2 K. Fluid Phase Equilibria, 1987, 38(1-2):
8 109-127.
9 [102] Qin, J., Rosenbauer, R. J., Duan, Z. Experimental measurements of vapor–liquid equilibria of
10 the H2O+CO2+CH4 ternary system. Journal of Chemical & Engineering Data, 2008, 53(6):
11 1246-1249.
12 [103] Savary, V., Berger, G., Dubois, M., Lacharpagne, J. C., Pages, A., Thibeau, S., Lescanne, M. The
13 solubility of CO2+ H2S mixtures in water and 2 M NaCl at 120° C and pressures up to 35 MPa.
14 International journal of greenhouse gas control, 2012: 10, 123-133.
15 [104] Shagiakhmetov, R. A., Tarzimanov, A. A. Deposited document SPSTL 200 khp-D 81-1982
16 (1981). Summarized in: Sharlin, P.: Carbon Dioxide in Water and Aqueous Electrolyte Solutions.
17 Solubility Data Series, vol. 62, 383 pp. International Union of Pure and Applied Chemistry,
18 Oxford University Press (1996).
19 [105] Teng, H., Yamasaki, A., Chun, M. K., Lee, H. Solubility of liquid CO2 in water at temperatures
20 from 278 K to 293 K and pressures from 6.44 MPa to 29.49 MPa and densities of the
21 corresponding aqueous solutions. The Journal of Chemical Thermodynamics, 1997, 29(11):
22 1301-1310.
23 [106] Tödheide, K., Frank, E. U. Das Zweiphasengebiet und die kritische Kurve im System
24 Kohlendioxid–Wasser bis zu Drucken von 3500 bar. Ztschrift Für Physikalische Chemie, 1963,
25 37: 387-401.
26 [107] Wiebe, R. The Binary System Carbon Dioxide-Water under Pressure. Chemical reviews, 1941,
27 29(3): 475-481.
28 [108] Wiebe, R., Gaddy, V. L. The solubility in water of carbon dioxide at 50, 75 and 100, at pressures
29 to 700 atmospheres. Journal of the American Chemical Society, 1939, 61(2): 315-318.
30 [109] Zawisza, A., Malesinska, B. Solubility of carbon dioxide in liquid water and of water in gaseous
31 carbon dioxide in the range 0.2-5 MPa and at temperatures up to 473 K. Journal of Chemical and
32 Engineering Data, 1981, 26(4): 388-391.
33 [110] Jackson, K., Bowman, L. E., Fulton, J. L. Water solubility measurements in supercritical fluids
34 and high-pressure liquids using near-infrared spectroscopy. Analytical Chemistry, 1995, 67:
35 2368–2372.
36 [111] King Jr, A. D., Coan, C. R. Solubility of water in compressed carbon dioxide, nitrous oxide, and
37 ethane. Evidence for hydration of carbon dioxide and nitrous oxide in the gas phase. Journal of

43
 1 the American Chemical Society, 1971, (8): 1857-1862.
2 [112] Meyer, C. W., Harvey, A. H. Dew-point measurements for water in compressed carbon dioxide,
3 AIChE Journal, 2015, 61(9): 2913-2925.
4 [113] Song, K. Y., Kobayashi, R. Water content of CO2 in equilibrium with liquid water and/or
5 hydrates. SPE Formation Evaluation, 1987, 2: 500–508.
6 [114] Wiebe R., Gaddy V. L. Vapor phase composition of carbon dioxide-water mixtures at various
7 temperatures and at pressures to 700 atmospheres. Journal of the American Chemical Society,
8 1941, 63(2): 475-477.
9 [115] Rumpf, B., Maurer, G. An experimental and theoretical investigation on the solubility of carbon
10 dioxide in aqueous solutions of strong electrolytes. Berichte der Bunsengesellschaft fuer
11 physikalische chemie, 1993, 97(1): 85-97.

44