Energies 17 02356 v2

energies
Article
Benedict–Webb–Rubin–Starling Equation of State + Hydrate
Thermodynamic Theories: An Enhanced Prediction Method for
CO2 Solubility and CO2 Hydrate Phase Equilibrium in Pure
Water/NaCl Aqueous Solution System
Changyu You 1,2,3,4 , Zhaoyang Chen 1,2,3, * , Xiaosen Li 1,2,3 , Qi Zhao 1,2,3,5 , Yun Feng 1,2,3,5 and Chuan Wang 1,2,3,5
1 Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China;
youcy@ms.giec.ac.cn (C.Y.); lixs@ms.giec.ac.cn (X.L.); zhaoqi@ms.giec.ac.cn (Q.Z.);
sa21178018@mail.ustc.edu.cn (Y.F.); wc1633144@mail.ustc.edu.cn (C.W.)
2 Key Laboratory of Gas Hydrate, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences,
Guangzhou 510640, China
3 Guangdong Provincial Key Laboratory of New and Renewable Energy Research and Development,
Chinese Academy of Sciences, Guangzhou 510640, China
4 University of Chinese Academy of Sciences, Beijing 100049, China
5 School of Energy Science and Engineering, University of Science and Technology of China,
Hefei 230026, China
* Correspondence: chenzy@ms.giec.ac.cn
Abstract: Accurately predicting the phase behavior and physical properties of carbon dioxide
(CO2 ) in pure water/NaCl mixtures is crucial for the design and implementation of carbon capture,
utilization, and storage (CCUS) technology. However, the prediction task is complicated by CO2
liquefaction, CO2 hydrate formation, multicomponent and multiphase coexistence, etc. In this study,
an improved method that combines Benedict–Webb–Rubin–Starling equation of state (BWRS EOS)
Citation: You, C.; Chen, Z.; Li, X.;
Zhao, Q.; Feng, Y.; Wang, C.
+ hydrate thermodynamic theories was proposed to predict CO2 solubility and phase equilibrium
Benedict–Webb–Rubin–Starling conditions for a mixed system across various temperature and pressure conditions. By modifying the
Equation of State + Hydrate interaction coefficients in BWRS EOS and the Van der Waals–Platteeuw model, this new method is
Thermodynamic Theories: An applicable to complex systems containing two liquid phases and a CO2 hydrate phase, and its high
Enhanced Prediction Method for CO2 prediction accuracy was verified through a comparative evaluation with a large number of reported
Solubility and CO2 Hydrate Phase experimental data. Furthermore, based on the calculation results, the characteristics of CO2 solubility
Equilibrium in Pure Water/NaCl and the variation of phase equilibrium conditions of the mixture system were discussed. These
Aqueous Solution System. Energies findings highlight the influence of hydrates and NaCl on CO2 solubility characteristics and clearly
2024, 17, 2356. https://doi.org/
demonstrate the hindrance of NaCl to the formation of CO2 hydrates. This study provides valuable
10.3390/en17102356
insights and fundamental data for designing and implementing CCUS technology that contribute to
Academic Editor: Alberto addressing global climate change and environmental challenges.
Maria Gambelli
Keywords: CCUS; BWRS EOS; hydrate thermodynamic theories; CO2 solubility; phase equilibrium
Received: 30 March 2024
Revised: 29 April 2024
Accepted: 2 May 2024
Published: 13 May 2024
1. Introduction
With the intensification of global climate change and the increasing severity of envi-
ronmental challenges, reducing carbon dioxide (CO2 ) emissions has become a focal point
Copyright: © 2024 by the authors. of scientific research and industrial sectors [1,2]. Carbon capture, utilization, and storage
Licensee MDPI, Basel, Switzerland. (CCUS) is a cutting-edge technological solution related to economic development and
This article is an open access article
social progress [3].
distributed under the terms and
The thermodynamic properties of CO2 –pure water/brine mixtures are crucial for
conditions of the Creative Commons
designing and implementing CCUS technology, which are influenced by the interactions
Attribution (CC BY) license (https://
among CO2 , H2 O, and saline solutes (typically represented by NaCl). The CO2 –pure
creativecommons.org/licenses/by/
water/NaCl aqueous solution mixtures involved in CCUS technology span a temperature
4.0/).
Energies 2024, 17, 2356. https://doi.org/10.3390/en17102356 https://www.mdpi.com/journal/energies

Energies 2024, 17, 2356 2 of 39
range from near the freezing point (273.15 K) to room temperature (298.15 K), and a pressure
range from atmospheric pressure (101.325 kPa) to the pressure of deep-sea water at an
average depth of 3688 m [4] (approximately 40 MPa). The possibly existing phases of the
mixtures are CO2 -rich phase (in vapor or liquid state or vapor-liquid coexistence state,
contains CO2 and H2 O, mostly CO2 ), H2 O-rich phase (in liquid state, contains CO2 , H2 O,
and possibly NaCl, mostly H2 O), and hydrate phase (in solid state, contains CO2 and H2 O).
Accordingly, CO2 solubility and NaCl fractions, which describe the composition of the
fluids in the mixture system and determined the distribution of CO2 -H2 O-NaCl in different
phases, directly impacts the performance of CCUS technology.
For instance, CO2 solubility directly affects the effectiveness, capacity, and long-term
stability of CO2 storage strategies, such as geological sequestration, mineral transformation,
and ocean storage [5,6]. The density difference between dissolved CO2 and other water
bodies in natural water systems is a primary factor in determining the mode and velocity
of CO2 migration [7]. In confined environments like rocks or geological formations, this
disparity in density significantly influences the pressure distribution and safety of the
storage zone. Hydrate-based CO2 storage technology, an emerging CCUS technology,
offers advantages including faster storage rates, higher storage capacity, excellent stability,
and cost-effectiveness [8–10].
However, the presence of dissolved CO2 is critically important for the formation of
CO2 hydrate [11]. When CO2 hydrate is present, CO2 solubility undergoes a significant
decrease with increasing pressure compared to systems without hydrates [12]. Additionally,
the solubility is controlled by the equilibrium between the pure water/NaCl aqueous
solution phase and the solid CO2 hydrate phase, whereas in systems without hydrates, the
solubility is controlled by the equilibrium between CO2 and the pure water/NaCl aqueous
solution [13]. In the presence of NaCl, the development of hydrogen bonding networks
in liquid and hydrate phases are partially impeded [14]. Moreover, water molecules
have a higher tendency to adhere to similarly polar salt ions than to nonpolar guest
molecules (such as CO2 ) [15]. As a result, the thermodynamic properties of CO2 –NaCl
aqueous solution mixtures are different from the thermodynamic properties of CO2 –pure
water mixtures.
Understanding the phase equilibrium conditions of CO2 –pure water/NaCl aqueous
solution–CO2 hydrate is a prerequisite for calculating CO2 solubility. In the meantime,
based on the CO2 solubility data, the phase equilibrium conditions of CO2 –pure wa-
ter/NaCl aqueous solution–CO2 hydrate can also be predicted. Limited experimental
studies have been conducted on CO2 solubility and phase equilibrium conditions of CO2 –
pure water/NaCl aqueous solution mixtures within the temperature and pressure range
of 273.15~298.15 K and 0.1~40 MPa due to the involved extreme environments such as
high pressure. The relevant studies we can obtain include: studies on the phase equilib-
rium conditions of CO2 –pure water [11,16–35]/NaCl aqueous solution [11,20,30–32,34–44]-
CO2 hydrate, studies on CO2 solubility in pure water [11,45–53] and NaCl aqueous so-
lution [54] in systems without hydrates, as well as studies on CO2 solubility in pure
water [11,12,36,47,48,50,52,53,55–61] and NaCl aqueous solution [11,36,57,62] in systems
with hydrates.
Due to the difficulties in measurements, there are some discrepancies in the reported
experimental data, especially CO2 solubility data, posing challenges to the accuracy of
related research. Thus, there is an urgent need for the development of simulation and
prediction methods that can be applied to systems encompassing liquid and hydrate phases.
Table 1 presents the presently available simulation studies for forecasting CO2 solubility
in pure water/NaCl aqueous solution. Nonetheless, these studies cannot fully meet the
research needs of CCUS. For example, some prediction methods, although generally ap-
plicable to a wide range of temperature and pressure, did not consider the influence of
CO2 hydrate presence, and some early studies have a limited prediction pressure range
for low temperature conditions (below 298.15 K) due to the lack of experimental data
support. The current studies have not yet fully explored all conditions related to the CO2 –
Energies 2024, 17, 2356 3 of 39
pure water/NaCl aqueous solution mixtures involved in CCUS technology, nor have they
comprehensively addressed the vapor, liquid, and solid hydrate phases.
Table 1. Simulation studies for predicting CO2 solubility in pure water/NaCl aqueous solution.
Ref. T/K P/MPa System

[45] 274.14~351.31 0.1~12 Pure water
[46] 278.2~318.2 0.1~8 Pure water
[51] 298.15~448.15 0.1~18 Pure water
[53] 274~303 1~4 Pure water
[63] 285.15~373.15 0.1~60 Pure water
[64] 271.65~373.15 0.1~100 Pure water
[65] 271.65~373.15 0.1~100 NaCl aqueous solution
[66] - - NaCl aqueous solution
[67] 273.15~723.15 0.1~150 NaCl aqueous solution
[68] 285.37~373.15 0.1~68.948 Pure water/NaCl aqueous solution
[69,70] 285.15~573.15 0.1~60 Pure water/NaCl aqueous solution
[71] 273~533 0.1~200 Pure water/NaCl aqueous solution
[54] 363 0.1~13 Pure water/NaCl aqueous solution
Above the critical
[36,72–74] temperature of CO2 and 0~50 Pure water/NaCl aqueous solution
below 283.15 K
[75] 274~300 0.1~100 Pure water/Sea water
Pure water/Aqueous solution containing Na+ , K+ , Ca2+ ,
[76] 273~533 0.1~200
Mg2+ , Cl− , and SO4 2−
Pure water/NaCl, KCl, MgCl2 , CaCl2 , NaNO3 , KNO3 ,
[77] 298~423 0.1~40
Mg(NO3 )2 , and Na2 CO3 aqueous solution
Pure water/NaCl, KCl, MgCl2 , CaCl2 , MgSO4 , K2 SO4 ,
[78] 273.15~473.65 0.092~71.231
NaHCO3 , Na2 SO4 , and mixed salt aqueous solution
In order to overcome the mentioned challenges, this study modified and combined
the BWRS EOS (Benedict–Webb–Rubin–Starling equation of state) with hydrate thermo-
dynamic theories for the prediction of CO2 solubility in pure water/NaCl aqueous solu-
tion systems with and without hydrates, under the temperature and pressure range of
273.15~298.15 K and 0.1~40 MPa, as well as the phase equilibrium conditions of CO2 –pure
water/NaCl aqueous solution–CO2 hydrate. The discrepancy between the reported ex-
perimental results and the calculation results were compared to assess the effectiveness
of the methods proposed. Furthermore, CO2 solubility characteristics and the variation
of phase equilibrium conditions of CO2 –pure water/NaCl aqueous solution–CO2 hydrate
were described. This study is beneficial for the development of CCUS related technologies.
2. Theory and Methods

Note: The complex calculation processes involving iterative procedures in this study
have been organized into flowcharts to enhance the readability (presented in Appendix B to
avoid an overly lengthy main text). The flowcharts comprise the following: Figure A1 (for
the calculation of density of i-rich phase and vapor pressure of component i, corresponding
to Sections 2.1.1 and 2.3.1), Figure A2 (for the calculation of CO2 solubility in systems
without hydrates, corresponding to Section 2.3.2), Figure A3 (for the calculation of CO2
solubility in systems with hydrates, corresponding to Section 2.5.1), Figure A4 (for the
calculation of d∆µ, corresponding to Section 2.5.2), Figure A5 (for the calculation of phase
equilibrium temperature of CO2 –pure water or NaCl aqueous solution–CO2 hydrate,
corresponding to Section 2.5.3), Figure A6 (for the calculation of KCO2 −H2 O in systems
without hydrates, corresponding to Section 2.6), Figure A7 (for the calculation of KCO2 −H2 O
in systems with hydrates, corresponding to Section 2.6).
Energies 2024, 17, 2356 4 of 39
2.1. BWRS EOS

EOSs commonly used to predict the thermodynamic properties of CO2 -related real
fluids including Cubic-type EOSs (PR, RK, SRK, GCEOS, etc.), Virial-type EOSs (LKP,
BWRS, etc.), and SAFT-type EOSs (PC-SAFT, tPC-SAFT, SAFT-LJ, HRX-SAFT, SAFT-RPM,
SAFT-VR, etc.) [79–81]. Among them, Cubic-type EOSs are widely used due to their
simplicity in form [80]. Virial-type EOSs attract attention for their rigorous theoretical
basis [82]. SAFT-type EOSs are renowned for their calculations of polymer mixtures and, to
a lesser extent, aqueous systems [83]. However, most EOSs cannot accurately predict the
thermodynamic properties of liquid fluids, and their prediction accuracy tends to decrease
as the CO2 content increases [80]. BWRS EOS, the most representative Virial-type EOSs [80],
stands out as the first and most well-known EOS that can be applied to both vaporous
and liquid fluids [84,85]. It performs highly for specific mixtures, such as synthetic gases,
CO, CO2 , H2 , H2 O, etc. [86–88]. Therefore, this study selected the BWRS EOS as the
fundamental equation for calculating fluid properties.
The basic form of the BWRS EOS [84] is as follows:

P = ρRT + B0 RT − A0 − CT02 + D 0
3 − E0
4 ρ 2 + bRT − a − d ρ3
T
T 3 T (1)
+α a + Td ρ6 + cρ 1 + γρ2 exp −γρ2

T2
where P represents system pressure, MPa; T represents system temperature, K; ρ rep-

resents the molar density of the fluid, mol·mL−1 ; R is the ideal gas constant, which is
8.314 J·mol−1 ·K−1 ; and B0 , A0 , C0 , γ, b, a, α, c, D0 , d, E0 are 11 parameters related to the
fluid itself.
If the fluid consists of a single component, the parameters B0i , A0i , C0i , γi , bi , ai , αi , ci ,
D0i , di , and E0i for component i can be calculated based on its critical density (ρci ), critical
temperature (Tci ), acentric factor (ωi ) (listed in Table 2), and the universal parameters A j
and Bj (listed in Table 3) as follows:
ρci · B0i = A1 + B1 ωi (2)
ρci A0i
= A2 + B2 ωi (3)
RT ci
ρci C0i
= A3 + B3 ωi (4)
RTci3
ρ2ci γi = A4 + B4 ωi (5)
ρ2ci bi = A5 + B5 ωi (6)
ρ2ci ai
= A6 + B6 ωi (7)
RT ci
ρ3ci αi = A7 + B7 ωi (8)
ρ2ci ci
= A8 + B8 ωi (9)
RT 3ci
ρci D0i
= A9 + B9 ωi (10)
RT 4ci
ρ2ci di
= A10 + B10 ωi (11)
RT 2ci
ρci E0i
= A11 + B11 ωi exp(−3.8ωi ) (12)
RT 5ci
Energies 2024, 17, 2356 5 of 39
Table 2. Critical parameters and acentric factors of CO2 and H2 O [84].
Component i
Critical Parameters and Acentric Factors
CO2 H2 O
ρci /mol·L−1 10.638 17.857
Tci /K 304.09 647.3
ωi 0.21 0.344
Pci /MPa 7.376 22.048
Table 3. The values of universal parameters A j and Bj [84].
Universal Parameters
Subscript j
Aj Bj
1 0.4436900 0.115 449
2 1.2843800 −0.920731
3 0.3563060 1.708710
4 0.5449790 −0.270896
5 0.5286290 0.349621
6 0.4840110 0.754130
7 0.0705233 −0.044448
8 0.5040870 1.322450
9 0.0307452 0.179433
10 0.0732828 0.463492
11 0.0064500 −0.022143
If the fluid consists of multiple components, the 11 parameters in the BWRS EOS can
be calculated based on the 11C parameters of C individual components and the proportion
(qi ) of each component in a particular phase of the mixed fluid using mixing rules [88]
as follows:
C
B0 = ∑ qi B0i (13)
i=1
c c
∑ ∑ qi qk A0i A0k (1 − Kik )
1 1
2 2
A0 = (14)
i =1 k =1
c c
∑ ∑ qi qk C0i2 C0k2 (1 − Kik )3
1 1
C0 = (15)
i =1 k =1
!2
c 1
γ0 = ∑ q i γi 2
(16)
i =1
!3
c 1
b= ∑ q i bi 3
(17)
i =1
!3
c 1
a= ∑ qi ai 3
(18)
i =1
!3
c 1
α= ∑ qi αi 3
(19)
i =1
!3
c 1
C= ∑ qi Ci 3
(20)
i =1
c c
∑ ∑ qi qk D0i D0k (1 − Kik )4
1 1
2 2
D0 = (21)
i =1 k =1
Energies 2024, 17, 2356 6 of 39
!3
c 1
d= ∑ qi di 3
(22)
i =1
c c
∑ ∑ qi qk E0i E0k (1 − Kik )5
1 1
2 2
E0 = (23)
i =1 k =1
where the scripts i and k represent components i and k, and Kik represents the interaction
coefficient between component i and k. How to acquire Kik through experimental data will
be discussed in Section 2.6.
2.1.1. Calculation of Fluid Density

When P, T, and qi are all determined, using the Newton iteration method helps achieve
rapid convergence in calculating fluid density from BWRS EOS [89]. The BWRS EOS can
be reformulated as a function of density [90]:

F (ρ) = ρRT + B0 RT − A0 − CT02 + D 0
3 − E0
4 ρ2
T T
+ bRT − a − Td ρ3 + α a + Td ρ6 (24)
3
+ cρ 1 + γρ2 exp −γρ2 − P

T2
A reasonable density root makes F (ρ) equal to zero. The derivative form of expression
(24) is given as follows:

F′ (ρ) = RT + 2ρ B0 RT − A0 − CT02 + D 0
3 − E0
4
T T
+3 bRT − a − Td ρ2 + 6α a + Td ρ5
2 6
(25)
− 2cγT2ρ exp −γρ2

2
+ 3cρ 1 + γρ2 exp −γρ2

T2
The iterative equation for density roots is:
F( ρ )
ρ n +1 = ρ n − (26)
F′ ( ρ )
An initial density value is required for the iteration process. In some cases, Equation (24)
may have multiple real roots, and the choice of the initial density value impacts the iteration
results. Using the density of ideal fluids as the initial density value for vaporous fluids:
P
ρ0V = (27)
RT
Using the weighted result of the Rackett equation [91] as the initial density value for
the liquid fluids:
c
qi ρci
ρ0L = ∑ 2 (28)
i =1 |(1− TT ) 7 |
(0.29056 − 0.08775ωi ) ci
Assume the phase state of the fluid before calculating its density. In this study, for
the CO2 -rich phase and the H2 O-rich phase, the vapor pressures of the predominant
components were used as criteria in the phase determination process. For example, if the
system pressure is greater than the vapor pressure of pure CO2 , it is assumed that the CO2 -
rich phase is in a liquid state, and ρ0L is taken as the initial value for the density calculation.
Otherwise, ρ0V is taken as the initial value for the density calculation. The calculation
methods of vapor pressure of pure CO2 and H2 O will be introduced in Section 2.3.1.
Energies 2024, 17, 2356 7 of 39
2.1.2. Calculation of Fugacity Coefficients and Fugacity

The fugacity coefficient φ can be expressed as [84]:
1
Rρ ρ
ln φ = Z − 1 − ln Z + RT ( P − ρRT ) ρ2
0
P
= −ln ρRT

+ R2 B0 R − AT0 − Tc03 + D 0
4 − E0
T 5 ρ (29)
T
+ 2R3
bR − Ta − Td2 ρ2 + 5RT 6α
a + Td ρ5
h 2 i
c γρ 2 4 2
+ γRT 3 1+ 2 + γ ρ − 1 exp − γρ
where Z represents the compressibility factor, which is defined as:
P
Z= (30)
ρRT
The fugacity ( f ) of a single-component fluid satisfies:
f = φP (31)
For a fluid consisting of multiple components, the fugacity coefficient (φi ) of compo-
nent i can be expressed as [92]:

1
R ρ ∂P
lnφi = RT 0 ∂qi T,ρ,q − ρRT ρρ2 − ln Z
( k ̸ =i )
k
P
= −ln ρRT + ρ( B0 + B0i )
(
C h 1
1
+ RT 2ρ ∑ qk −( A0k A0i ) 2 (1 − Kik )
k =1
1 1
− (C0kTC20i ) ( D0k D0i ) 2
2
(1 − Kik )3 + T3
(1 − Kik )4
1
− (E0kTE40i )
2
(1 − Kik )5
1
" #
2 31 13 ( d2 d i ) 3
+ 3ρ2 b2 b i RT − a2 a i − T
1
" #
5 1 ( d2 d i ) 3
+ 3αρ
5 a2 a i 3 + T
(32)
5
1
+ 3ρ5 a + Td α2 αi 3

1
"
3(C2 Ci ) 3 ρ2 1−exp(−γρ2 )
+ T2 γρ2
#
− 12 exp −γρ2

"
1
2C γi 2
− γT2 γ 1 − 1 + γρ2
#)

+ 21 γ2 ρ4 exp −γρ2

The fugacity ( f i ) of component i satisfies [93]:
ln f i = lnφi + lnP + lnqi (33)
2.2. Principle of Phase Equilibrium

In an equilibrium system, the fugacity of each component in all phases must be equal.
Energies 2024, 17, 2356 8 of 39
Take superscripts “V”, “L”, “H2 O-rich” and “CO2 -rich” to denote vapor phase, liquid
phase, H2 O-rich phase, and CO2 -rich phase, respectively.
For component i in a vapor-liquid equilibrium system:
f iV = f iL (34)
For components H2 O and CO2 in an equilibrium system of CO2 -pure water/NaCl

aqueous solution mixture without hydrates:
H2 O−rich CO2 −rich
fH 2O
= fH2O
(35)
H2 O−rich 2 −rich
f CO 2
= f CO
CO2 (36)
For components H2 O and CO2 in an equilibrium system of pure water/NaCl aqueous
solution-CO2 hydrate:
2 O−rich
H
fH 2O
= fH
H2 O (37)
2 O−rich
H
f CO 2
= fH
CO2 (38)
For components H2 O and CO2 in an equilibrium system of CO2 -CO2 hydrate:
H CO2 −rich
fH 2O
= fH 2O
(39)
2 −rich
H
f CO2
= f CO
CO2 (40)
In the equations above, the fugacity in the fluid phases, including vapor and liquid
phase in a single-component system, as well as the CO2 -rich and H2 O-rich phase in multi-
component systems, can all be calculated using the BWRS EOS.
2.3. Thermodynamic Properties of Systems without Hydrates

2.3.1. Calculation of Vapor Pressure of Component i
The calculation methods of the vapor pressure of component i, Pi∗ , is as follows.
Firstly, an initial value for iteration can be calculable by using the following equation:
T
7(1+ωi )(1− ci )
T
Pi*0 = Pci · Pci −1 = Pci ·10 3 (41)
where Pci represents the critical pressure, MPa, and its value is listed along with ωi and Tci
in Table 2. The relation between Pci and ωi , Tci , and T, is provided by Edmister [94].
Then, use Pi0∗ to calculate the fugacity of component i in vapor phase f V and liquid
i
L
phase f i until Equation (34) is satisfied. If it is not satisfied, the following iterative equation
is used to calculate a new vapor pressure until Equation (34) is satisfied:
!
* * ln f iV − ln f iL
Pin+1 = Pin 1 − (42)
ZiV − ZiL
where ZiV and ZiL represent the compressibility factors of the vapor and liquid phases,
respectively.
2.3.2. CO2 Solubility in Pure Water/NaCl Aqueous Solution

The equilibrium constant of component i between the CO2 -rich phase and H2 O-rich
phase, Ki , is giving by its general expression:
H2 O−rich
fi
2 O−rich
y xi φH
Ki = i = = i
(43)
CO2 −rich 2 −rich
xi fi φCO
i
yi
Energies 2024, 17, 2356 9 of 39
where yi and xi represent the mole fractions of component i in the CO2 -rich phase and
H2 O-rich phase, respectively.
The relationship between the total mole fraction of component i in the fluid phase, zi ,
and the molar phase fraction, N, is given by:
zi = NCO2 −rich yi + NH2 O−rich xi (44)
yi and xi can be calculated using Ki , zi , and NCO2 −rich as follows:
Ki z i
yi = (45)
1 + NCO2 −rich (Ki − 1)
zi
xi = (46)
1 + NCO2 −rich (Ki − 1)
Subtracting the above two equations gives the Rachford–Rice equation [95]:
c c
z ( K − 1)
∑(yi − xi ) = ∑ 1 + NCOi −irich (Ki − 1) =0 (47)
i i 2

To use the Newton iteration method to calculate NCO2 −rich , define F NCO2 −rich :
c
z ( K − 1)
∑ 1 + NCOi −irich (Ki − 1)

F NCO2 −rich = (48)
i 2

A reasonable NCO2 −rich value makes F NCO2 −rich equal to zero. An initial value for
NCO2 −rich is chosen as:
c
1
NCO2 −rich 0 = 0.5∑ (49)
i
1 − Ki
The derivative form of expression (48) is:
c
zi ( K i − 1 ) 2
F ′ NCO2 −rich = −∑

2 (50)
i 1 + NCO2 −rich (Ki − 1)
The iterative equation for NCO2 −rich is:

F NCO2 −rich
NCO2 −rich n+1 = NCO2 −rich n − (51)
F ′ NCO2 −rich

The steps to predict the mole fractions of component i in the CO2 -rich phase and
H2 O-rich phase, yi and xi , are as follows:
(1) Assume initial values for Ki ; recommended values are 62 and 0.001 for CO2 and for
H2 O, respectively.
(2) Calculate NCO2 −rich using Equations (48)–(51).
(3) Calculate yi and xi using Equations (45) and (46).
(4) Use the method described in Section 2.4.2 to calculate f iH2 O−rich and f iCO2 −rich until
Equations (35) and (36) are satisfied. If they are not satisfied, modify yi and xi and
repeat steps (2) to (3) until they are satisfied. Based on multiple actual simulation
results, the recommended method for modifying Ki is:
f iH2 O−rich
Kin+1 = Kin (52)
f iCO2 −rich
Energies 2024, 17, 2356 10 of 39
CO2 solubility in pure water/NaCl aqueous solution, SCO2 , is:

xCO2
SCO2 = (53)
xH2 O
2.4. Hydrate Thermodynamic Theories

CO2 hydrate is a type I hydrate, containing 46 H2 O molecules [29]. The H2 O molecules
form 2 small cavities and 6 large cavities that can store guest molecules (normally not all
cavitied are filled with CO2 ) [96]. According to the fundamental equation of chemical poten-
tial, the fugacity of a certain component in system-A can be calculated by the fugacity of this
component in system-B and the chemical potential difference of this component between
these two systems. The hydrate thermodynamic theories provide the chemical potential
difference of component H2 O in the empty hydrate cavities (without guest molecules) and
a specific system, which can be used to calculate the fugacity of H2 O in a specific system.
2.4.1. Van der Waals–Platteeuw Model

The Van der Waals–Platteeuw (VdWP) model [96] gives the chemical potential differ-
ence of H2 O in empty hydrate cavities and in hydrate cavities that contain guest molecule
k (∆µH,1
H2 O ) as follows: !
2 c
H2 O = − RT ∑ v j ln 1 −
∆µH,1 ∑ θkj (54)
j =1 k =1
f k Cj
θkj = ( j = S, L) (55)
1 + f k Cj
where “S” denotes small cavities and “L” denotes large cavities. v j represents the moles of
j-type hydrate cavities formed by 1 mole of H2 O molecules. For CO2 hydrate and other type
I hydrates, the moles of small cavities is 1/23 and the moles of large cavities is 3/23 [96].
θkj represents the occupancy of component k in j-type hydrate cavities. f k represents the
fugacity of the guest molecule k. For equilibrium system containing CO2 hydrate, f k refers
H , f H2 O−rich , or f CO2 −rich ; the last two can be calculated using BWRS EOS. C is the
to f CO 2 CO2 CO2 j
Langmuir constant, and in this study, it was calculated using three methods that will be
introduced in Section 2.4.2.
For CO2 hydrate and other type I hydrates, the expression for ∆µH,1 H2 O can be organized as:
RT h i
∆µH,1
H2 O = ln (1 + f k CS )(1 + f k CL )3 (56)
23
2.4.2. Calculation of Langmuir Constants

Cj can be obtained through experimental data fitting or derived from thermodynamic
theory. However, due to variations in experimental conditions and theoretical assumptions,
different studies may yield different values of Cj . In order to ascertain the most suitable
value of Cj for the research systems of the present study, three classical research methods
for calculating Cj were compared.
The first method refers to [97,98], and the calculation is as follows:

1.6464 2799.66
CS = exp (57)
100000 T − 15.9

0.8507 3277.9
CL = exp (58)
0.101325T T
The second method refers to [99], and the calculation is as follows:

0.0000566 4182.52 44770
CS = exp + (59)
T T T2
Energies 2024, 17, 2356 11 of 39

0.007879 0.00364536 31390
CL = exp + (60)
T T T2
The third method refers to [98,99], and the calculation is as follows:

0.0000566 4182.52 44770
CS = exp + (61)
T T T2

0.8507 3277.9
CL = exp (62)
0.101325T T
2.4.3. Saito Model and Its Modification

Saito et al. [100] provided a model to calculate the chemical potential difference of H2 O
in empty hydrate cavities and in pure water (∆µH,2 H2 O ). Holder et al. [101] further organized
and improved the model, which is expressed as:
∆µH,2 ∆µ0H2 O Z T
∆hH2 O
Z P
∆VH2 O

H2 O
= − dT + dP (63)
RT RT T0 RT 2 P0 RT
Z T
∆hH2 O = ∆h0H2 O + ∆CPH O dT (64)
T0 2
Z T
∆CPH = ∆CP0H − 0.141dT (65)
2O 2 O
T0
where the superscript 0 represents the reference state (temperature of 273.15 K and pressure
of 0 MPa). ∆µ0H2 O represents the chemical potential difference of H2 O in empty hydrate
cavities and pure water at the reference state, and ∆h0H2 O and ∆CP0H O represent the enthalpy
2
and molar heat capacity difference of H2 O in hydrate phase and pure water at the reference
state. For type I hydrates, their values are taken as 1264.13 J·mol−1 , −4861.03 J·mol−1 , and
−38.13 J·mol−1 ·K−1 , respectively [98]. ∆hH2 O , ∆VH2 O , and ∆CPH O represent the enthalpy,
2
volume, and molar heat capacity difference of empty hydrate cavities and pure water in
any state.
∆VH2 O is often considered a constant value [101,102]. This is a result of assuming that
−1
the difference between the density of empty hydrate cavities (ρEHH , g·mL ) and pure water
(ρH2 O−pure ) do not vary with temperature and pressure, which makes ∆VH2 O independent
of guest molecules and theoretically can be used for the calculation of all Type I hydrates.
However, the actual ρH2 O−pure varies with temperature and pressure conditions, and recent
research results [103] have shown that ρEHH relates to the type of guest molecules, as well as
temperature and pressure conditions. Therefore, to expand the applicable temperature and
pressure range of the above model and improve its accuracy, this study did not consider
∆VH2 O to be constant, but calculated it according to its original definition as follows:
MH2 O 1
∆VH2 O = EH
− (66)
ρH ρH2 O−pure
where MH2 O represents the relative molecular mass of H2 O, which is taken as 18 g·mol−1 .
ρH2 O−pure is calculated using the BWRS EOS. A set of data for ρEH H under different tem-
perature and pressure conditions is provided in reference [103]. Based on these data, an
equation is fitted to calculate ρEH
H , with a goodness of fit of 0.99452 and a residual sum of
squares of 0.00101302.
EH
∆ρH = 0.97477609 − 0.00071519T + 0.00086046lnP (67)
Energies 2024, 17, 2356 12 of 39
The expression for ∆µH,2

H2 O can be organized as:
∆µ0H O

∆µH,2
H2 O = T T0
2
+∆h0H2 O 1
T − 1
T0

T0 T0
+∆CP0H −
ln +
T 1
2 O T (68)
T02
+0.0705 T − T + 0.141T0 ln TT0

M
+ ρHEH2 O − ρH O1−pure ( P − P0 )
H 2
2.4.4. Calculation of H2 O Fugacity in CO2 Hydrate Phase

Based on the thermodynamic theory mentioned above, the fugacity of H2 O in CO2
H , can be expressed as:
hydrate phase, f H 2O
∆µH,1
H2 O
H EH −
fH2O
= fH2O
e RT (69)
EH represents the fugacity of H O in empty hydrate phase:

In the equation, f H2O 2
∆µH,2
H O−pure ( H2 O
EH
fH = f H22O e RT ) (70)
2O
H O−pure
where f H22O represents the fugacity of H2 O in pure water.
H can be rearranged as follows:
The expression for f H2O
∆µH,2
H O−pure ( H2 O
EH
fH = f H22O e RT ) (71)
2O
2.5. Thermodynamic Properties of Systems with Hydrates

2.5.1. CO2 Solubility in Pure Water/NaCl Aqueous Solution
Reasonable CO2 solubility equalizes the two values of f H H calculated by using
2O
Equations (37) and (71).
The steps for predicting the mole fractions of component i, xi in H2 O-rich phase are
as follows:
H O−pure
(1) Use the method described in Section 2.1 to calculate ρH2 O−pure and f H22O .
(2) Calculate ∆µH,2
H2 O using Equation (68).
(3) Assume an initial value for xi , recommended values are 0.03 and 0.97 for CO2 and for
H2 O, respectively.
H2 O−rich H2 O−rich
(4) Use the method described in Section 2.1.2 to calculate f CO 2
and f H 2O
.
(5) H using Equation (37) and denote it as f H,1 .
Calculate the first value of f H2O H2 O
Calculate the second value of f H2O H2 O
H,1 H,2
(8) Compare f H 2O
and f H 2O
; if they are not equal, modify xi using the following equation
and repeat steps (4) to (7) until they are equal:
H,2
fH 2O
xCO2 n+1 = xCO2 n H,1
(72)
fH 2O
xH2 O n+1 = 1 − xCO2 n+1 (73)

Calculate the CO2 solubility using Equation (53).
Energies 2024, 17, 2356 13 of 39
2.5.2. Modification of the VdWP Model

In this study, BWRS EOS for systems with hydrates was modified with the reported
experimental CO2 solubility data (the modification will be introduced in Section 2.6), which
only leads to accurate calculation results for pure water/NaCl aqueous solution–CO2
hydrate system. In the meantime, due to a lack of sufficient reported experimental data
on the composition of the CO2 -rich phase, BWRS EOS could not be modified to suit the
calculation for the CO2 -rich phase. Consequently, under the reported experimental phase
equilibrium conditions of CO2 –pure water/NaCl aqueous solution–CO2 hydrate, using
CO2 −rich H2 O−rich
f CO 2
to calculate ∆µH,1
H2 O will yield a different result than using f CO2 to calculate
∆µH,1
H2 O . This discrepancy was used to modify the calculation results for the VdWP model,
which will expand the application scope of the method proposed in this study to CO2 -CO2
hydrate systems and CO2 –pure water/NaCl aqueous solution–CO2 hydrate systems.
CO2 −rich
Firstly, calculate f CO 2
using the BWRS EOS modified for pure water/NaCl aque-
ous solution–CO2 hydrate system, steps are as follows:
H O−pure
H2 Ousing Equation (68).
(3) Assume an initial value for yi ; the recommended values are 0.99999999 and 0.00000001
for CO2 and for H2 O, respectively.
CO2 −rich CO2 −rich
and f H 2O
.
Calculate the first value of f H2O H2 O
CO2 −rich
H2 O with f CO2 , using Equation (56).
Calculate the second value of f H2O H2 O
H,1 H,2
(8) Compare f H 2O
and f H 2O
; if they are not equal, modify yi using the following equation
and repeat steps (4) to (7) until they are equal:
yCO2 n+1 = yCO2 n − 0.00000001 (74)
yH2 O n+1 = 1 − yCO2 n+1 (75)

CO2 −rich
.
CO2 −rich
(10) Calculate the first ∆µH,1
H2 O with f CO2 using Equation (56).
And then, use the method described in Section 2.5.1 to predict xCO2 and xH2 O at pure
water/NaCl aqueous solution–CO2 hydrate equilibrium, and calculate the second ∆µH,1 H2 O
H2 O−rich
with f CO 2
following steps (4) to (6) in Section 2.5.1. Finally, denote the difference of
the two ∆µH,1
H2 O values as d∆µ, and fit d∆µ as a function of temperature (T) and the mass
fraction of NaCl in aqueous solution (SNaCl, , wt%).
CO2 −rich
After this modification, when using f CO 2
to calculate ∆µH,1
H2 O with Equation (56),
add d∆µ from the result for subsequent calculations.
2.5.3. Phase Equilibrium Conditions of CO2 –Pure Water/NaCl Aqueous Solution–CO2

Hydrate
The steps for predicting the phase equilibrium temperature T eq of CO2 –pure wa-
ter/NaCl aqueous solution–CO2 hydrate at a specific pressure P are as follows:
(1) Assume an initial value for T eq , such as 273.15 K.
(2) Use the method described in Section 2.5.1 to predict xCO2 and xH2 O , and calculate the
H2 O−rich
first ∆µH,1
H2 O with f CO2 , following steps (4) to (6) in Section 2.5.1.
(3) Follow steps (1) to (10) in Section 2.5.2 to calculate a ∆µH,1
H2 O value and add a d∆µ value
to it as the second value of ∆µH,1
H2 O .
Energies 2024, 17, 2356 14 of 39
(4) Compare the difference between the two ∆µH,1 H2 O values; if they are not equal, modify
T eq with the following equation and repeat steps (2) to (3) until they are equal:
T eq n+1 = T eq n + 0.01 (76)
2.6. Modification of BWRS EOS

When calculating the properties of mixed fluids, some of the parameters in the BWRS
EOS are influenced by the interaction coefficient between component i and component k,
Kik [88]. The Kik value ranges from 0 to 1, and a higher value indicates a greater influence
of the mixing effect on the thermodynamic properties of the mixed fluids calculated by
the BWRS EOS. When the thermodynamic properties of two fluids are similar and their
interaction is weak, the differences in thermodynamic properties between their mixtures
and the original fluids will also be smaller. The current reported Kik value is 0 for CO2 and
H2 O [90]. However, with this value, the BWRS EOS is often unsolvable when calculating
the thermodynamic properties of CO2 -pure water/NaCl aqueous solution mixtures involv-
ing liquid and hydrate phases. This limitation not only hinders comprehension of fluid
properties but also restricts the practical application of the BWRS EOS. To overcome this
re f
limitation, the reported experimental CO2 solubility (SCO2 ) data were used to modify the

Kik value ( KCO2 −H2 O .
For the equilibrium system of CO2 –pure water/NaCl aqueous solution mixtures
without hydrates, the modification steps are as follows:
(1) Assume an initial value for KCO2 −H2 O ; the recommended value is 0.3.
(2) Use the method described in Section 2.3.2 to predict the mole fraction of CO2 and
H2 O in the H2 O-rich phase, xCO2 and xH2 O , at pure water/NaCl aqueous solution
equilibrium.
(3) cal ) using Equation (53).
Calculate CO2 solubility (SCO 2
cal with S re f
(4) Compare SCO 2 CO2 ; if they are not equal, modify KCO2 −H2 O using the following
equation and repeat steps (2) and (3) until they are equal:
KCO2 −H2 O n+1 = KCO2 −H2 O n − 0.00001 (77)
For the equilibrium system of CO2 –pure water/NaCl aqueous solution mixtures with
hydrates, the modification steps are as follows:
H O−pure
(3) Assume an initial value of 0.2 for KCO2 −H2 O .
re f
(4) Calculate xCO2 and xH2 O according to SCO2 as follows:
re f
SCO2
xCO2 = re f
(78)
SCO2 + 1
1
xH2 O = re f
(79)
SCO2 +1
H2 O−rich H2 O−rich
and f H 2O
.
(6) H value and denote it as f H,1 .
Use Equation (37) to calculate the first f H2O H2 O
(8) H value and denote it as f H,2 .
Use Equation (71) to calculate the second f H2O H2 O
H,1 H,2
(9) If f H 2O
is not equal to f H2O
, modify KCO2 −H2 O using Equation (77) and repeat steps
(5) to (8) until they are equal.
Energies 2024, 17, 2356 15 of 39
Fit KCO2 − H2 O as a function of temperature (T), pressure (P), and the mass fraction of
NaCl in aqueous solution (SNaCl ).
2.7. Statistics and Screening of Reported Experimental Data

The reported experimental data, including CO2 solubility and the phase equilibrium
conditions of CO2 –pure water/NaCl aqueous solution–CO2 hydrate, within the temper-
ature range of 273.15~298.15 K and the pressure range of 0~40 MPa, are summarized
in Tables A1–A3. Research systems were distinguished based on whether they contain
hydrates and NaCl.
Although this study focuses on the temperature range of 273.15~298.15 K and pressure
range of 0.01~40 MPa, if the experimental research in the relevant literature involves both
within this range and beyond, the data from the literature were used to modify the BWRS
EOS and hydrate thermodynamic model except for some obviously abnormal values, which
is to ensure the internal consistency of the prediction methods proposed in this study and
expand their extrapolation capability.
The studies of CO2 solubility in pure water in systems without hydrates [11,33,45–53]
consists of 361 data points in total. The overall temperature range of the studies is
273.15~573.15 K and the pressure range is 0.01~120 MPa. Among these, the
literature [46,47,49,50,52] provides a relatively rich amount of data with 251 data points
in total that cover the temperature range of 273.15~573.15 K and the pressure range of
0.01~120 MPa. These data from selected studies were used to modify the BWRS EOS and
to evaluate the fitting accuracy. Data from the remaining studies [11,45,48,51,53,104] were
used to evaluate the prediction accuracy.
The studies of CO2 solubility in NaCl aqueous solutions in systems without hy-
drates [54] consist of 44 data points in total. The overall temperature range of the study is
293.08~353.23 K, the pressure range is 1.02~14.29 MPa, and the NaCl mass fraction range is
1.02~14.29 wt%. All of the data were used to modify the BWRS EOS and to evaluate the
fitting accuracy.
The studies of CO2 solubility in pure water in systems with hydrates [11,12,36,47,
48,50,52,53,55–59,61,62] consist of 285 data points in total. The overall temperature range
of the studies is 273.15~293.15 K and the pressure range is 1.33~120 MPa. The data in
studies [52,55,59] exhibits significant deviations from the data in other studies and were not
used to modify BWRS EOS and evaluate the fitting accuracy. Studies [12,56,58,61] provide
a relatively rich amount of data with 251 data points in total that covers the temperature
range of 273.15~289.05 K and pressure range of 1.874~90 MPa. These data from selected
studies were used to modify the BWRS EOS and to evaluate the fitting accuracy. Data from
the remaining studies [11,36,48,50,53,57,62] were used to evaluate the prediction accuracy.
The studies of CO2 solubility in NaCl aqueous solution in systems with
hydrates [11,36,57,62] consist of 70 data points in total. The overall temperature range
of the studies is 271.45~281.15 K, the pressure range is 1.45~21.79 MPa, and the NaCl mass
fraction range is 1~5.844 wt%. All of the data were used to modify the BWRS EOS and to
evaluate the fitting accuracy.
The studies of the phase equilibrium conditions of CO2 -pure water-CO2
hydrate [11,16–35] consist of 252 data points in total. The overall temperature range
of the studies is 269.45~294 K and the pressure range is 0.825~494 MPa. However, there
are only 32 data points within the wide pressure range of 40~494 MPa. Considering that
this pressure range is not within the scope of this study, 220 data from these studies within
the temperature range of 269.45~286.2 K and the pressure range of 0.825~37.2 MPa were
selected to modify the BWRS EOS and to evaluate the fitting accuracy.
The studies of the phase equilibrium conditions of the CO2 –NaCl aqueous solution–
CO2 hydrate [11,20,30–32,34–43] consist of 231 data points in total. The overall temperature
range of the studies is 254.75~284.6 K, the pressure range is 0.703~60.14 MPa, and the
NaCl mass fraction range is 2~25 wt%. All of the data were used to modify the hydrate
thermodynamic models and to evaluate the fitting accuracy.
Energies 2024, 17, 2356 16 of 39
3. Results and Discussion

In this study, modifications were made to the BWRS EOS and VdWP models. At the
same time, three different methods were used to calculate the Langmuir constants. For
convenience, these methods are denoted as method 1, 2, and 3 in the later text.
3.1. Modification of BWRS EOS

The interaction coefficient between CO2 and H2 O KCO2 −H2 O ) in the BWRS EOS was
fitted and expressed as a function of temperature (T), pressure (P) and the mass fraction of
NaCl in aqueous solution (SNaCl ). The fitting equations are shown in Table 4. The calculated
KCO2 −H2 O based on experimental data are very different from the original KCO2 −H2 O value
0 [90], which demonstrate exactly as introduced in detail in 2.5 that this modification is
necessary for calculating the thermodynamic properties of CO2 –pure water/NaCl aqueous
solution mixtures involving liquid and hydrate phases. This is because as the pressure
increases, the difference of thermodynamic properties between the actual fluid and ideal
fluid increases. At the same time, the presence of hydrogen bonds between CO2 and
the pure water/NaCl aqueous solution, as well as the hydrogen bonds in the hydrate
cavities, exacerbates this difference. As a result, predicting the thermodynamic properties
of CO2 -pure water/NaCl aqueous solution mixtures with liquid phase or hydrate phase
is difficult using the general EOS. And therefore, in the application of BWRS EOS, the
interaction between CO2 and pure water/NaCl aqueous solution should not be ignored for
the system of CO2 –pure water/NaCl aqueous solution mixtures containing a liquid phase
and a hydrate phase.
Table 4. Fitting equations of KCO2 −H2 O regarding temperature, pressure, and NaCl mass fraction.
System Method KCO2 −H2 O Equation

−0.00000000489913 × T 3 + 0.00000576416 × T 2 − 0.00234000 × T − 0.00223000 × lnP +
Without hydrate -
0.433930 − SNaCl × (0.00160000 − 0.00000805212 × T + 0.0000000264483 × P)
0.406830 − 0.00102000 × T + 0.00000888515 × P − SNaCl ×
With hydrate 1
(0.023930 − 0.0000884302 × T + 0.0000400857 × P)
0.350280 − 0.000795855 × T + 0.00000215094 × P − SNaCl ×
2
(0.0149300 − 0.0000576566 × T + 0.0000539784 × P)
0.398170 − 0.000998231 × T + 0.00000629555 × P − SNaCl ×
3
(0.0166500 − 0.0000638813 × T + 0.0000545214 × P)
Theoretically, the closer the thermodynamic properties of the two fluids are, and the
smaller the interactions are, the less difference there will be between the thermodynamic
properties of their mixtures and the original fluids; correspondingly, the value of KCO2 −H2 O
will be smaller. At normal temperature and pressure, CO2 is in a vapor state with relatively
large intermolecular distances. In contrast, the pure water/NaCl aqueous solution remains
in a liquid state with a lower molecular kinetic energy. The thermodynamic properties of
CO2 and water/NaCl aqueous solution exhibit a significant disparity. As the temperature
and pressure increase, the kinetic energy of the H2 O molecules increase and the intermolec-
ular distances of CO2 decrease, respectively, both effects narrowing the thermodynamic
properties gap between vaporous CO2 and the pure water/NaCl aqueous solution, and
therefore, KCO2 −H2 O decreases. The KCO2 −H2 O fitting equation for the system without
hydrates and NaCl reflects this rule, which is conductive to better reflecting the interaction
between CO2 and pure water/NaCl aqueous solution, thereby improving the accuracy of
predicting the thermodynamic properties of their mixtures. However, this rule does not
apply to systems containing hydrate. This is because the formation of strong hydrogen
bonds within the hydrate cavities reduces the influence of pressure on the size of the
hydrate cavities and the distance between the CO2 and H2 O molecules. Similarly, the rule
does not hold true for NaCl-containing systems, as the presence of ions complicates the
thermodynamic properties of the system.
Energies 2024, 17, 2356 17 of 39
3.2. Calculation Results of CO2 Solubility

Figure 1 displays a scatter plot comparing the reported experimental values of CO2
solubility (horizontal axis) with the calculated values of this study (vertical axis), illustrating
the correlation between the two sets of results. As shown in Figure 1a,b, for a system
without hydrates and NaCl, except for a few points, the vast majority of points align closely
along the line of y = x. This alignment suggests a strong consistency between the calculated
CO2 solubility values and the experimental values. In Figure 1c,d, it can be observed that
Energies 2024, 17, x FOR PEER REVIEW 18 of 41
the calculation effects of the three calculation methods with different Langmuir constants
values (introduced in Section 2.4.2) are nearly identical for both the pure water system
and NaCl aqueous solution system with hydrates. While the calculated CO2 solubility
solubility values match most of the experimental values, they significantly deviate from
values match most of the experimental values, they significantly deviate from some of the
some of the experimental values due to large variations in data from different studies. The
experimental values due to large variations in data from different studies. The calculation
calculation methods proposed in this study reconciled the discrepancies among the dif-
methods proposed in this study reconciled the discrepancies among the different studies.
ferent studies.
Figure
Figure 1. 1. Correlationbetween
Correlation between the
thereported
reportedexperimental
experimental values and and
values the calculated valuesvalues
the calculated of CO2of CO
2
solubility in pure water/NaCl aqueous solution. (a) Pure water system without hydrates; (b) NaCl
solubility in pure water/NaCl aqueous solution. (a) Pure water system without hydrates; (b) NaCl
aqueous solution system without hydrates; (c) pure water system with hydrates; (d) NaCl aqueous
aqueous
solutionsolution system
system with without hydrates; (c) pure water system with hydrates; (d) NaCl aqueous
hydrates.
solution system with hydrates.
Figure 2 shows the calculated values of CO2 solubility in different systems and some
Figureexperimental
reported 2 shows thevalues.
calculated values
The trend of of
COCO 2 solubility
2 solubility in different
calculated in this systems and some
study is con-
reported experimental
sistent with most of the values. Thedata.
experimental trend In of CO2water
a pure solubility
system calculated in this
without hydrates study is
(Fig-
ure 2a), the
consistent calculated
with most oftrend of CO2 solubility
the experimental closely
data. In aaligns with experimental
pure water system without data, ex-
hydrates
hibiting
(Figure 2a), anthe
increase with decreasing
calculated trend of temperature
CO2 solubility and increasing pressure.
closely aligns withInexperimental
a pure water data,
system with hydrates (Figure 2b), data from references [56,61]
exhibiting an increase with decreasing temperature and increasing pressure. clearly show a decreaseInina pure
CO 2 solubility as the temperature rises. However, the influence of pressure remains am-
water system with hydrates (Figure 2b), data from references [56,61] clearly show a decrease
biguous, with varying trends reported across different sources, including some showing
in CO2 solubility as the temperature rises. However, the influence of pressure remains
no clear pattern (reference [11]). To resolve the ongoing controversy regarding the pres-
ambiguous, with varying trends reported across different sources, including some showing
sure effect, reference [61] measured CO2 solubility across a wide range of temperatures
noand
clear pattern(276.15~289.05
pressures (reference [11]). To resolve
K, 3~90 the ongoing
MPa), revealing a slightcontroversy regarding
decrease in solubility the pres-
with
sure effect, reference [61] measured
increasing pressure. The findings appear to CO solubility across a wide range of temperatures
2 be reliable and it can be explained that CO2 is
and pressures
more (276.15~289.05
stably encaged K, 3~90
in hydrate MPa),
cavities revealing
at high pressurea condition.
slight decrease in solubility
Additionally, data with
from reference [52] suggest that in a pure water system with hydrates, CO2 solubility fol-
lows a similar trend to that observed in a system without hydrates, increasing with de-
creasing temperature and increasing pressure. We speculate that in the experiments re-
ported by reference [52], hydrates may not have formed despite conditions favoring its
formation, potentially leading to discrepancies in their measurements compared to other
Energies 2024, 17, 2356 18 of 39
increasing pressure. The findings appear to be reliable and it can be explained that CO2
is more stably encaged in hydrate cavities at high pressure condition. Additionally, data
from reference [52] suggest that in a pure water system with hydrates, CO2 solubility
follows a similar trend to that observed in a system without hydrates, increasing with
decreasing temperature and increasing pressure. We speculate that in the experiments
Energies 2024, 17, x FOR PEER REVIEW reported by reference [52], hydrates may not have formed 19despite of 41 conditions favoring its
formation, potentially leading to discrepancies in their measurements compared to other
sources. In summary, the trends reported in references [56,61] regarding the variation of
sources. InCO 2 solubility
summary, withreported
the trends temperature and pressure
in references are deemed
[56,61] regarding credible.
the variation of The calculation results
CO2 solubility with
are in temperature
alignment and pressure
with are deemed
these findings, credible. Thethat
confirming calculation results
CO2 solubility increases with higher
are in alignment with these findings, confirming that CO2 solubility increases with higher
temperatures and
temperatures and lower pressures.
lower pressures.
Figure 2. Cont.
Energies 2024, 17, 2356 19 of 39
Figure 2. CO2 solubility in pure water/NaCl aqueous solution. (a) Pure water system without hy-
Figure 2. CO solubility in pure water/NaCl aqueous solution. (a) Pure water system with-
drates; (b) pure water system2 with hydrates; (c) NaCl aqueous solution system without hydrates;
out hydrates;
(d) NaCl aqueous (b) pure
solution system withwater
hydrates.system
Hollowwith
circle hydrates; (c) NaCl
symbols represent aqueous solution system without
experimental
[11,36,45–50,52,53,56,60,61]
hydrates; (d)data. NaCl aqueous solution system with hydrates. Hollow circle symbols represent
experimental [11,36,45–50,52,53,56,60,61] data.
In a NaCl aqueous solution system without hydrates (Figure 2c), CO2 solubility in-
creases with decreasing temperature, increasing pressure, and decreasing NaCl mass frac-
tion. In a NaClIn a NaCl
aqueous aqueous
solution systemsolution system
with hydrates without
(Figure 2d), COhydrates (Figure 2c), CO2 solubility
2 solubility in-
increases
creases with with
increasing decreasing
temperature. temperature,
At low increasing
pressure, the solubility pressure,
decreases and decreasing NaCl mass
with in-
creasing NaCl mass fraction,
fraction. but ataqueous
In a NaCl high pressure, it increases
solution with increasing
system NaCl mass
with hydrates (Figure 2d), CO2 solubility
increases with increasing temperature. At low pressure, the solubility decreases with
increasing NaCl mass fraction, but at high pressure, it increases with increasing NaCl mass
fraction. As the NaCl mass fraction increases, the degree of increase in CO2 solubility with
increasing pressure also increases. Under high-pressure conditions, particularly in a system
with hydrates (Figure 2b,d), the impact of pressure is found to be lower when compared
to a low-pressure system without hydrates (Figure 2a,c). These findings suggest that the
existence of hydrates and NaCl in the system alters the solubility characteristics of CO2 .
Table 5 summarizes the fitting and prediction accuracy of the methods proposed in
this study for calculating CO2 solubility in a pure water/NaCl aqueous solution. The fitting
accuracy is assessed by comparing the calculated results with the original data used for
Energies 2024, 17, 2356 20 of 39
fitting. The results show that for a pure water system, the fitting accuracy, measured by the
mean of the average absolute relative deviation (AARD), ranges from 4.318% to 4.472%.
For a NaCl aqueous solution system, the fitting accuracy ranges from 4.318% to 8.472%
(AARD). The prediction accuracy is assessed by comparing the calculated results with data
that were not involved in the fitting process. The results show that for a pure water system,
the prediction accuracy ranges from 7.912 to 17.231% (AARD). Among the three methods
used to calculate Langmuir constants, method 1 exhibited the highest prediction accuracy,
followed by method 2, and then method 3. But the overall difference is not significant.
Table 5. The calculation effect of CO2 solubility.
Fitting Data Fitting Prediction Prediction

System Methods
Points Accuracy/% Data Points Error/%
Pure water without hydrates - 251 5.293 114 7.912

NaCl aqueous solution without hydrates 44 4.318 - -
Pure water with hydrates 1 119 5.953 118 12.930
2 119 4.549 118 15.174
3 119 4.538 118 15.154
NaCl aqueous solution with hydrates 1 70 7.500 - -
2 70 8.459 - -
3 70 8.472 - -
The discrepancy statistics across different studies can be found in Tables A1 and A2.
Given that the methods proposed in this study are informed by reported experimental
data, they possess a high level of credibility. Consequently, the CO2 solubility charac-
teristics identified in the literature with smaller AARDs exhibit a degree of consistency,
while those identified in the literature with larger AARDs demonstrate discrepancies from
other sources.
Before modifications were made to the BWRS EOS, it was not suitable for calculating
CO2 solubility in systems containing a liquid phase and hydrate phase. However, after
modifications, using the BWRS EOS combined with hydrate thermodynamic theories can
now predict the CO2 solubility in complex systems. The fitting accuracy and prediction
accuracy reached the level of experimental accuracy.
3.3. Modification of VdWP Model

As described in Section 2.5.2, the customized parameter d∆µ is employed to reconcile
the discrepancy between the two ∆µH,1 H2 O values calculated using the fugacity of CO2 in
the CO2 -rich phase and in a pure water/NaCl aqueous solution, respectively. The fitting
equations of d∆µ are presented in Table 6, which are derived from fitting the reported
experimental data of the phase equilibrium conditions of a CO2 –pure water/NaCl aqueous
solution–CO2 hydrate.
Table 6. Fitting equations of d∆µ.
Method d∆µ Equation
1 730 − 2.8 × T + (0.0422 − 0.000646061 × SNaCl − 0.0000390636 × T ) × T × SNaCl

2 1600 − 6.49 × T + (52.48028 + 0.42275 × SNaCl − 0.10537 × T ) × SNaCl
3 820 − 3 × T + (30.37533 + 0.15524 × SNaCl − 0.005197 × T ) × SNaCl
Table 6. Fitting equations of 𝑑𝛥𝜇.
Method 𝒅𝚫𝝁 Equation

1 730 − 2.8 × 𝑇 + (0.0422 − 0.000646061 × 𝑆 − 0.0000390636 × 𝑇) × 𝑇 × 𝑆
Energies22024, 17, 2356 1600 − 6.49 × 𝑇 + (52.48028 + 0.42275 × 𝑆 − 0.10537 × 𝑇) × 𝑆
21 of 39
3 820 − 3 × 𝑇 + (30.37533 + 0.15524 × 𝑆 − 0.005197 × 𝑇) × 𝑆
3.4.
3.4.Calculation
CalculationResults
ResultsofofCO
CO22–Pure
–PureWater/NaCl
Water/NaClAqueous
AqueousSolution–CO
Solution–CO2 2Hydrate
HydratePhase
Phase
Equilibrium
EquilibriumConditions
Conditions
The
The horizontal
horizontal axis
axis of
of Figure
Figure 33 displays
displays the
the reported
reported experimental
experimental values
values for
for the
the
phase
phase equilibrium
equilibrium temperature
temperature of CO22–pure water/NaCl
water/NaClaqueous
aqueous solution–CO
solution–CO22 hydrate
hydrate
at
ataaspecific
specificpressure,
pressure, while
while the
the vertical
verticalaxis
axisshows
showsthe the values
valuescalculated
calculatedby bythe
themethods
methods
proposed
proposed in this study at the same pressure. For a pure water system, the calculated
study at the same pressure. For a pure water system, the calculated results re-
sults closely
closely matchmatch the experimental
the experimental results
results as depicted
as depicted in Figure
in Figure 3a. On3a.
theOn the other
other hand, hand,
for an
for
NaClan NaCl
aqueousaqueous solution
solution system, system, the calculations
the calculations usingusing
methodmethod
3 most3 most closely
closely alignalign
with
with the experimental
the experimental results,
results, while while
method method 1 overestimates
1 overestimates and method
and method 2 underesti-
2 underestimates the
phase the
mates equilibrium temperature
phase equilibrium at a specific
temperature at pressure,
a specific as shown in
pressure, as Figure
shown 3b.
in Figure 3b.
Correlationbetween
Figure3.3. Correlation
Figure betweenthethereported
reportedexperimental
experimentalvalues
valuesand
andthe
thecalculated
calculatedvalues
valuesof
ofthis
this
study
study on phaseequilibrium
on the phase equilibriumtemperature
temperature of of
COCO
2 –pure
–pure
2 water/NaCl
water/NaCl aqueous
solution–CO 2 hy-
hydrate
2
drate
underunder specific
specific pressure
pressure conditions.
conditions. (a) Pure
(a) Pure waterwater system;
system; (b) NaCl
(b) NaCl aqueous
aqueous solution
solution system.
system.
Figure44illustrates
Figure illustratesthe thecalculated
calculatedvalues
valuesforforthe
thephase
phaseequilibrium
equilibriumconditions
conditionsof ofCOCO2–2 –
pure water/NaCl aqueous solution–CO hydrate, alongside
pure water/NaCl aqueous solution–CO2 2hydrate, alongside some reported experimental some reported experimental
values.AsAs
values. shown
shown in Figure
in Figure 4a, calculated
4a, the the calculated
trendtrend
of theof the phase
phase equilibrium
equilibrium line is
line is almost
almost consistent
consistent with thewith reportedthe reported experimental
experimental values. Invalues.
the lowIntemperature
the low temperature region
region of Figure
of Figure
4a, 4a, equilibrium
the phase the phase equilibrium
line changes line changessmoothly.
relatively relatively Assmoothly. As the temperature
the temperature gradually
gradually increases, the phase equilibrium line begins to extend and
increases, the phase equilibrium line begins to extend and intersect with the CO2 liquefac- intersect with the CO2
tion line (calculated using the method described in Section 2.3.1). In the right region region
liquefaction line (calculated using the method described in Section 2.3.1). In the right of the
of the intersection
intersection point, thepoint,trendtheof trend of the equilibrium
the phase phase equilibrium line changes
line changes significantly,
significantly, and evenand
even a slight increase in temperature can lead to a rapid increase in
a slight increase in temperature can lead to a rapid increase in the phase equilibrium pres- the phase equilibrium
pressure,
sure, whichwhich
suggests suggests the difficulties
the difficulties faced faced by liquid
by liquid CO2 inCO 2 in forming
forming hydrates.hydrates.
As shown As
shown in Figure 4b, as the NaCl mass fraction increases, the phase
in Figure 4b, as the NaCl mass fraction increases, the phase equilibrium line shifts to the equilibrium line shifts
to the
left, left, indicating
indicating that it that
is moreit is more difficult
difficult for COfor2 CO 2 hydrates
hydrates to formto form
and and easier
easier for for
them them
to
to decompose.
decompose.
The fitting accuracy of the phase equilibrium conditions of CO2 –pure water/NaCl
aqueous solution–CO2 hydrate is detailed in Table 7. For a pure water system, the three
methods proposed in this study exhibit similar effects, and the fitting accuracy reached the
level of experimental accuracy. Specifically, the fitting accuracy for method 1 is equal to
that of method 3, and both are superior to method 2. For a NaCl aqueous solution system,
method 3 performs the best in terms of fitting accuracy, while method 1 and 2 have lower
fitting accuracy. The detailed discrepancy statistics across different studies can be found
in Table A3.
Energies 2024, 17, x 2024,
Energies FOR PEER REVIEW
17, 2356 23 of 41 22 of 39
Figure 4. Phase equilibrium conditions of CO2–pure water/NaCl aqueous solution–CO2 hydrate. (a)
Figure 4. Phase equilibrium conditions of CO2 –pure water/NaCl aqueous solution–CO2 hydrate.
Pure water system; (b) aqueous solution system with different NaCl mass fractions. Hollow circle
(a) Pure water system; (b) aqueous solution system with different NaCl mass fractions. Hollow circle
symbols represent experimental [11,16,17,19–40,44,73] data.
symbols represent experimental [11,16,17,19–40,44,73] data.
The fitting accuracy of the phase equilibrium conditions of CO2–pure water/NaCl
aqueous solution–CO2 hydrate is detailed in Table 7. For a pure water system, the three
methods proposed in this study exhibit similar effects, and the fitting accuracy reached
the level of experimental accuracy. Specifically, the fitting accuracy for method 1 is equal
to that of method 3, and both are superior to method 2. For a NaCl aqueous solution sys-
tem, method 3 performs the best in terms of fitting accuracy, while method 1 and 2 have
Energies 2024, 17, 2356 23 of 39
Table 7. Calculation effect of CO2 –water/NaCl aqueous solution–CO2 hydrate phase equilibrium
conditions.
System Methods Fitting Data Points Fitting Accuracy/%

Pure water with hydrates 1 220 0.243
2 220 0.245
3 220 0.243
NaCl aqueous solution with hydrates 1 231 1.190
2 231 1.095
3 231 0.210
4. Conclusions
An improved method was proposed to predict CO2 solubility and phase equilibrium
conditions for CO2 –pure water/NaCl aqueous solution mixtures across various temper-
ature and pressure conditions. The core of this method is to modify and combine BWRS
EOS with hydrate thermodynamic theories. In the improved method, BWRS EOS was
modified by fitting the interaction coefficients based on reported experimental data of CO2
solubility, which solved the limitation that the conventional BWRS EOS is not suitable for
calculating CO2 solubility, especially in systems involving liquid and hydrate phases. The
VdWP model was also modified by fitting the data of phase equilibrium conditions for
CO2 –pure water/NaCl aqueous solution–CO2 hydrate, and three different methods were
used to calculate the Langmuir constants.
The prediction accuracy was evaluated by comparison and analysis of the differences
between a large number of reported experimental data and the calculation results. The
results verified that the fitting accuracy and prediction accuracy matched the experimental
standards, and the improved method is useful for the prediction of CO2 solubility and phase
equilibrium conditions for the mixture system with and without CO2 hydrate presence.
The calculation results highlight the influence of hydrates and NaCl on CO2 solubility
characteristics. In pure water without hydrates, CO2 solubility increases as the temperature
decreases and the pressure increases. Conversely, in pure water with hydrates, it decreases
as the temperature decreases and the pressure increases. In NaCl aqueous solution without
hydrates, CO2 solubility increases with decreasing temperature, increasing pressure, and
decreasing NaCl mass fraction. In NaCl aqueous solution with hydrates, at high pressure, it
increases as the temperature and NaCl mass fraction increase; at low pressure, it decreases
with the NaCl mass fraction. Compared to low-pressure systems without hydrates, the
impact of pressure is relatively smaller in high-pressure systems with hydrates. Further-
more, the calculated results clearly demonstrate the hindrance of NaCl to the formation of
CO2 hydrates.
This study will be beneficial for the development of CCUS related technologies.
Author Contributions: Conceptualization, Z.C. and X.L.; Data curation, Q.Z.; Formal analysis,
Y.F. and C.W.; Funding acquisition, X.L.; Investigation, Y.F. and C.W.; Methodology, C.Y.; Project
administration, Z.C.; Resources, C.Y.; Software, C.Y.; Supervision, Z.C. and X.L.; Validation, C.Y.
and Q.Z.; Visualization, C.Y. and Q.Z.; Writing—original draft, C.Y. and Q.Z.; Writing—review
and editing, C.Y., Z.C. and X.L. All authors have read and agreed to the published version of the
manuscript.
Funding: We are grateful for the support of the Special Project for Marine Economy Development
of Guangdong Province (GDNRC [2024]33), the Fundamental Research & Applied Fundamental
Research Major Project of Guangdong Province (2023B0303000021), the National Key Research and
Development Program of China (2021YFC2800902), and the Guangdong Special Support Program-
Local innovation and entrepreneurship team project (2019BT02L278).
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Conflicts of Interest: The authors declare no conflicts of interest.
Energies 2024, 17, 2356 24 of 39
Nomenclature
P system pressure, MPa

T system temperature, K
ρ molar density of fluid, mol·mL−1
R ideal gas constant, 8.314 J·mol−1 ·K−1
i, k components i and k
B0 , A0 , C0 , γ, b, a, α, c,
parameters in the BWRS EOS
D0 , d, E0
B0i , A0i , C0i , γi , bi , ai , αi ,
parameters in the BWRS EOS related to component i
ci , D0i , di , E0i
ρci critical density of component i, mol·L−1
Tcii critical temperature of component i, K
ωi acentric factor of component i,
Pci critical pressure of component i, MPa
A j , Bj universal parameters for the calculation of parameters in the BWRS EOS
qi proportion of component i in a particular phase of the mixed fluid, mol%
Kik interaction coefficient between component i and k
F (ρ) function form of BWRS EOS
F′ ( ρ ) derivative form of F (ρ)
ρn density calculated from the ‘n’-th iteration, mol·mL−1
ρ n +1 density calculated from the ‘n + 1’-th iteration, mol·mL−1
ρ0V initial density value for iteration for vaporous fluids, mol·mL−1
ρ0L initial density value for iteration for liquid fluids, mol·mL−1
φ fugacity coefficient
Z compressibility factor
f fugacity, MPa
φi fugacity coefficient of component i
fi fugacity of component i, MPa
f iV fugacity of component i in vapor phase, MPa
f iL fugacity of component i in liquid phase, MPa
H2 O−rich
fH fugacity of H2 O in H2 O-rich phase, MPa
2O
CO2 −rich
fH fugacity of H2 O in CO2 -rich phase, MPa
2O
H2 O−rich
f CO fugacity of CO2 in H2 O-rich phase, MPa
2
CO2 −rich
f CO fugacity of CO2 in CO2 -rich phase, MPa
2
fHH fugacity of H2 O in hydrate phase, MPa
2O
H
f CO fugacity of CO2 in hydrate phase, MPa
2
Pi∗ vapor pressure of component i, MPa
Pi*0 initial value of Pi∗ for iteration, MPa
ZiV compressibility factor of vapor phase of the fluid of component i
ZiL compressibility factor of liquid phase of the fluid of component i
Pi*n Pi∗ calculated from the ‘n’-th iteration
Pi*n+1 Pi∗ calculated from the ‘n + 1’-th iteration
Ki equilibrium constant of component i between CO2 -rich phase and H2 O-rich phase
yi mole fraction of component i in CO2 -rich phase, mol%
xi mole fraction of component i in H2 O-rich phase, mol%
zi total mole fraction of component i in fluid phase, mol%
NCO2 −rich molar phase fraction of CO2 -rich phase
NH2 O−rich molar phase fraction of H2 O-rich phase
F NCO2 −rich function form of the Rachford-Rice equation
F ′ NCO2 −rich

derivative form of F NCO2 −rich
NCO2 −rich 0 Initial value of NCO2 −rich for iteration
NCO2 −rich n NCO2 −rich calculated from the ‘n’-th iteration
NCO2 −rich n+1 NCO2 −rich calculated from the ‘n + 1’-th iteration
f iH2 O−rich fugacity of i in H2 O-rich phase, MPa
Energies 2024, 17, 2356 25 of 39
f iCO2 −rich fugacity of H2 O in CO2 -rich phase, MPa

Ki n Ki calculated from the ‘n’-th iteration
Ki n +1 Ki calculated from the ‘n + 1’-th iteration
SCO2 CO2 solubility
xCO2 mole fraction of CO2 in H2 O-rich phase, mol%
xH2 O mole fraction of H2 O in H2 O-rich phase, mol%
chemical potential difference of H2 O in empty hydrate cavities and in hydrate cavities that contain
∆µH,1
H2 O guest molecule k, J·mol−1
vj moles of j-type hydrate cavities formed by 1 mole of H2 O molecules, mol
θkj occupancy of component k in j-type hydrate cavities
fk fugacity of the guest molecule k, MPa
Cj Langmuir constant
CS Langmuir constant for small cavities
CL Langmuir constant for large cavities
chemical potential difference of H2 O in empty hydrate cavities and pure water at any temperature
∆µ H,2
H2 O and pressure, J·mol−1
chemical potential difference of H2 O in empty hydrate cavities and pure water at the reference
∆µ0H2 O
temperature and pressure, 1264.13 J·mol−1
enthalpy difference of empty hydrate cavities and pure water at the reference temperature and
∆h0H2 O
pressure, −4861.03 J·mol−1
molar heat capacity difference of empty hydrate cavities and pure water at the reference temperature
∆CP0H
2O and pressure, −38.13 J·mol−1 ·K−1
enthalpy difference of empty hydrate cavities and pure water at any temperature and pressure,
∆hH2 O
J·mol−1
∆VH2 O volume difference of empty hydrate cavities and pure water at any temperature and pressure, mL
molar heat capacity difference of empty hydrate cavities and pure water at any temperature and
∆CPH2 O
pressure, J·mol−1 ·K−1
ρEH
H density of empty hydrate cavities, g·mL−1
ρH2 O−pure density of pure water, mol·mL−1
MH2 O relative molecular mass of H2 O, 18 g·mol−1
EH
fH fugacity of H2 O in empty hydrate phase, MPa
2O
H O−pure
f H22O fugacity of H2 O in pure water, MPa
H,1 H using Equation (37), MPa
fH calculated value of f H2O
2O
H,2 H using Equation (71), MPa
fH calculated value of f H2O
2O
xCO2 n xCO2 calculated from the ‘n’-th iteration, mol%
xCO2 n+1 xCO2 calculated from the ‘n + 1’-th iteration, mol%
xH2 O n xH2 O calculated from the ‘n’-th iteration, mol%
xH2 O n+1 xH2 O calculated from the ‘n + 1’-th iteration, mol%
yCO2 n yCO2 calculated from the ‘n’-th iteration, mol%
yCO2 n+1 yCO2 calculated from the ‘n + 1’-th iteration, mol%
yH2 O n yH2 O calculated from the ‘n’-th iteration, mol%
yH2 O n+1 yH2 O calculated from the ‘n + 1’-th iteration, mol%
customized parameter employed to reconcile the discrepancy of the two ∆µH,1
H2 O values calculated
d∆µ CO2 −rich H2 O−rich
with f CO 2
and f CO 2
, J·mol−1
T eq phase equilibrium temperature of CO2 –pure water/NaCl aqueous solution–CO2 hydrate, K
T eq n T eq calculated from the ‘n’-th iteration, K
T eq n+1 T eq calculated from the ‘n + 1’-th iteration, K
KCO2 −H2 O interaction coefficient between CO2 and H2 O
re f
SCO2 CO2 solubility, from references, K
cal
SCO CO2 solubility, calculation results, K
2
phase equilibrium temperature of CO2 –pure water/NaCl aqueous solution–CO2 hydrate, from
T eq−re f
references, K
phase equilibrium temperature of CO2 –pure water/NaCl aqueous solution–CO2 hydrate, calculation
T eq−cal
results, K
Energies 2024, 17, 2356 26 of 39
Appendix A
Table A1. Statistics of the reported experimental data and the discrepancy statistics across different studies for CO2 solubility without hydrates.
ref
Ref. T/K P/MPa SNaCl /wt% SCO2 ×102 /mol% Na Scal 2
CO2 ×10 /mol% MaxAE b × 102 /mol% MaxRE c /% AARD d /%
Pure water without hydrates

[45] 274.14~351.31 0.19~9.333 - 0.262~2.488 27 0.250~2.418 −0.158 −7.276 1.734
[46] 278.22~318.23 0.465~7.963 - 0.182~2.797 47 0.162~2.529 −0.268 −10.887 3.637
[47] 273.15~298.15 1.013~4.560 - 0.860~2.706 12 0.937~2.705 0.317 18.826 6.659
[48] 278.05~283.15 2~3.7 - 1.560~2.340 6 1.652~2.471 0.295 14.043 6.008
[49] 286.45~347.85 0.101 - 0.024~0.085 19 0.012~0.078 −0.012 −49.87 23.754
[50] 285.15~313.15 2.533~50.663 - 0.934~3.300 42 0.967~3.296 0.802 81.707 4.243
[51] 298.15 1.666~17.551 - 0.887~2.944 6 0.945~2.741 −0.203 −6.909 5.295
[52] 273.15~573.15 10~120 - 0.544~17.582 131 −0.013~17.286 −1.748 −102.449 3.421
[53] 274~303 1~4 - 0.492~3.440 49 0.520~2.870 −0.570 −16.569 5.539
[11] 275.15~286.15 0.77~4.65 - 0.585~2.526 22 0.875~2.621 0.460 49.537 21.506
Total 273.15~573.15 0.101~120 - 0.024~17.582 361 −0.013~17.286 −0.017 −102.449 6.060
NaCl aqueous solution without hydrates

[54] 293.08~353.23 1.02~14.29 1.461~11.688 0.700~1.800 44 0.653~2.097 0.297 16.513 4.318
Total 293.08~353.23 1.02~14.29 1.461~11.688 0.700~1.800 44 0.653~2.097 0.297 16.513 4.318
a b c
Number of data points; Maximum absolute error; Maximum relative error; d Average absolute relative deviation.
Energies 2024, 17, 2356 27 of 39
Table A2. Statistics of the reported experimental data and the discrepancy statistics across different studies for CO2 solubility with hydrates.
ref MaxAE MaxAE MaxAE

SNaCl SCO Scal
CO2 MaxRE AARD Scal
CO2 MaxRE AARD Scal
CO2 MaxRE AARD
Ref. T/K P/MPa /wt%
2 Na b ×
c /% d /%
b ×
c /% d /%
b ×
c /% d /%
×102 /mol% ×102 /mol% 102 /mol% ×102 /mol% 102 /mol% ×102 /mol% 102 /mol%
Method 1 Method 2 Method 3
Pure water with hydrates
[55] 276.15~283.05 30 - 4.660~6.870 9 1.673~2.84 1.892 −64.567 61.022 1.7.5~2.964 −4.061 −62.955 59.322 1.751~2.966 −4.057 −62.918 59.270
[12] 277.84~280.98 4.99~14.2 - 2.010~2.700 32 1.974~2.538 2.052 −10.733 7.408 2.066~2.653 −0.180 −6.712 3.552 2.068~2.653 −0.178 −6.652 3.505
[48] 273.95~282.95 2~6 - 1.560~2.810 15 1.461~2.951 0.312 12.178 6.435 1.545~3.088 0.444 17.361 6.731 1.539~3.084 0.441 17.242 6.794
[56] 273.15~283.15 7~12 - 1.184~3.330 33 1.348~2.991 −0.288 −13.398 6.691 1.425~3.129 −0.267 21.387 5.878 1.420~3.125 −0.265 20.880 5.787
[57] 279.1~281.5 10.1~20.1 - 2.270~2.710 10 2.18~2.598 0.641 −6.156 3.444 2.279~2.713 0.077 3.355 1.808 2.281~2.715 0.080 3.468 1.856
[58] 274.06~281.08 1.874~23.598 - 1.630~2.420 30 1.467~2.478 −0.179 −9.970 4.523 1.545~2.584 0.169 8.472 3.942 1.542~2.588 0.173 8.674 4.049
[60] 273.95~282.85 2~5 - 1.550~2.760 7 1.461~2.934 −0.381 −10.392 5.421 1.545~3.07 0.310 11.231 4.427 1.539~3.066 0.306 11.096 4.443
[61] 276.15~289.05 3~90 - 1.741~4.295 24 1.507~3.918 −0.167 −13.394 4.784 1.572~4.155 0.258 −9.695 4.810 1.573~4.125 0.250 −9.619 4.809
[47] 278.15 3.85035 - 2.594~2.594 1 2.044~2.044 −0.163 −21.198 21.198 2.142~2.142 −0.453 −17.445 17.447 2.142~2.142 −0.452 −17.434 17.434
[50] 285.15 20.265~30.3975 3.196~3.300 2 3.322~3.391 −0.169 6.115 3.385 3.478~3.554 0.358 11.207 8.303 3.472~3.544 0.349 10.906 8.054
[52] 273.15~283.15 10~120 2.981~4.379 14 1.272~5.001 −0.377 −70.493 39.678 1.335~5.441 −2.976 −69.038 38.413 1.332~5.325 −2.979 −69.107 38.221
[53] 274~278 1.5~4 1.743~3.440 10 1.463~2.025 −0.550 −57.476 36.678 1.546~2.122 −1.894 −55.058 33.323 1.541~2.122 −1.899 −55.202 33.442
[11] 274.15~283.15 1.33~9.11 1.389~2.578 62 1.477~3.004 0.108 0.025 14.244 1.559~3.144 0.566 29.546 19.898 1.555~3.139 0.561 29.546 19.819
[36] 274.05~280.35 8.34~21.11 1.677~2.546 11 1.458~2.378 −3.039 −13.075 7.174 1.538~2.483 −0.139 −8.287 3.593 1.534~2.486 −0.143 −8.532 3.620
[59] 278~293 6.44~29.49 2.500~3.490 24 1.936~6.613 −4.111 164.53 54.431 2.02~7.295 4.795 191.803 61.204 2.024~7.013 4.513 180.504 58.572
Total 273.15~293.15 1.33~120 1.184~6.870 285 1.272~6.613 −4.111 164.531 16.438 1.335~7.295 4.795 191.803 17.231 1.332~7.013 4.513 180.504 16.985
NaCl aqueous solution with hydrates
[11] 274.15~281.15 1.45~3.83 3~5 1.434~1.670 18 1.347~2.314 −0.385 −14.26 4.551 1.135~2.321 −0.378 −21.139 9.743 1.141~2.319 −0.38 −20.734 9.615
[57] 278.8~280.4 10.1~20.1 5.844 2.310~2.400 6 1.957~2.257 −0.414 −16.611 11.408 1.891~2.284 −0.463 −18.604 12.170 1.893~2.285 −0.465 −18.67 12.144
[60] 273.95~278.15 2~8 1~3.6 1.420~1.585 36 1.412~1.979 0.322 20.222 7.613 1.373~2.035 0.299 18.796 6.519 1.374~2.038 0.302 18.979 6.618
[36] 271.45~279.65 8.41~21.79 3~6 1.250~2.109 10 1.238~2.177 −0.444 −17.442 10.059 1.214~2.173 −0.462 −21.925 10.906 1.215~2.174 −0.458 −21.735 10.882
Total 271.45~281.15 1.45~21.79 1~5.844 1.420~2.400 70 1.283~2.314 −0.444 20.222 7.500 1.135~2.284 −0.463 −21.925 8.459 1.141~2.319 −0.465 −21.735 8.472
a Number of data points; b Maximum absolute error; c Maximum relative error; d Average absolute relative deviation.
Energies 2024, 17, 2356 28 of 39
Table A3. Statistics of the reported experimental data and the discrepancy statistics across different literatures for the phase equilibrium conditions of CO2 –
water/NaCl aqueous solution–CO2 hydrate.
MaxAE Max AARD MaxAE MaxRE AARD MaxAE MaxRE AARD

Ref. P/MPa Teq− ref /K SNaCl /wt% Na T eq− cal /K b /K RE c /% d /% T eq− cal /K b /K c /% d /% T eq− cal /K b /K c /% d /%
Method 1 Method 2 Method 3

Pure water
[16] 0.974~3.85 270.34~282.16 - 10 270.94~282.35 0.60 0.222 0.084 270.94~282.34 0.60 0.222 0.070 270.93~282.16 0.59 0.218 0.060
[17] 1.31~12.87 273.6~283.6 - 13 273.6~284.19 0.80 0.283 0.106 273.6~284.19 0.68 0.240 0.100 273.59~284 0.58 0.205 0.082
[19] 1.5~3.5 274.76~281.46 - 4 274.74~281.64 0.30 0.107 0.054 274.75~281.66 0.28 0.100 0.052 274.76~281.56 0.19 0.068 0.027
[20] 1.34~2.52 273.75~279.04 - 4 273.73~279.13 0.10 0.036 0.026 273.73~279.12 0.09 0.032 0.018 273.73~279.11 0.07 0.025 0.009
[21] 1.616~4.452 275.65~283.25 - 11 275.45~283.24 −0.32 −0.115 0.040 275.45~283.25 −0.31 −0.111 0.037 275.42~283.03 −0.31 −0.111 0.057
[22] 0.825~1.708 269.45~275.75 - 10 269.45~275.94 0.19 0.069 0.011 269.43~275.93 0.18 0.065 0.010 269.45~275.85 −0.12 −0.044 0.010
[23] 2.048~4.02 277.5~282.5 - 3 277.49~282.59 0.09 0.032 0.022 277.49~282.6 0.10 0.035 0.025 277.39~282.48 −0.11 −0.040 0.017
[24] 1.42~4.37 274.3~282.9 - 9 274.29~283.19 0.29 0.103 0.046 274.29~283.1 0.20 0.071 0.038 274.3~282.99 0.09 0.032 0.017
[25] 1.66~4.03 274.02~280.12 - 12 275.7~282.64 3.78 1.368 0.805 275.6~282.64 3.69 1.336 0.792 275.62~282.44 3.59 1.299 0.759
[26] 1.81~3.83 276.45~282.05 - 7 276.44~282.34 0.29 0.103 0.052 276.44~282.23 0.19 0.067 0.039 276.35~282.15 0.10 0.036 0.018
[27] 1.04~4.509 271.6~283.2 - 44 271.49~283.38 −0.21 −0.077 0.039 271.49~283.29 −0.22 −0.081 0.039 271.48~283.09 −0.22 −0.080 0.031
[28] 1.338~8.93 273.36~283.59 - 40 273.75~283.88 2.39 0.850 0.266 273.76~283.79 2.29 0.815 0.263 273.75~283.61 2.08 0.740 0.236
[29] 4.5~37.2 283.2~286.2 - 6 283.28~286.28 0.20 0.071 0.032 283.29~286.3 0.10 0.035 0.021 283.09~286.05 −0.25 −0.088 0.045
[30] 1.04162~4.49883 271.67~283.15 - 7 271.56~283.34 0.20 0.071 0.042 271.54~283.24 −0.13 −0.048 0.032 271.56~283.14 −0.12 −0.043 0.025
[31] 1.24~3.48 273.5~281.4 - 6 273.09~281.67 −0.41 −0.150 0.063 273.1~281.58 −0.40 −0.146 0.057 273.09~281.5 −0.41 −0.150 0.039
[32] 1.51~3.9 275.12~282.41 - 9 274.8~282.4 −0.51 −0.184 0.077 274.81~282.41 −0.44 −0.159 0.076 274.82~282.29 −0.52 −0.188 0.107
[33] 1.47~4.15 274.42~282.83 - 5 274.61~282.82 0.19 0.069 0.025 274.61~282.82 0.19 0.069 0.024 274.6~282.62 −0.21 −0.075 0.059
[34] 1.542~4.155 275.05~282.65 - 6 275.05~282.84 0.29 0.104 0.039 275.04~282.83 0.29 0.104 0.035 275.02~282.65 0.19 0.068 0.026
[35] 1.747~2.023 276.15~277.15 - 6 276.13~277.35 0.20 0.072 0.026 276.13~277.34 0.19 0.069 0.025 276.04~277.24 −0.11 −0.040 0.020
[11] 1.33~3.23 274.15~281.15 - 8 273.75~281.13 −0.40 −0.146 0.057 273.73~281.03 −0.42 −0.153 0.066 273.73~280.93 −0.42 −0.153 0.077
Total 0.825~37.2 269.45~286.2 - 220 269.45~286.28 3.78 1.368 0.243 269.43~286.30 3.69 1.336 0.245 269.45~286.05 3.59 1.300 0.243
NaCl aqueous solution
[38] 1.436~3.919 272.15~279.15 2~15 21 273.44~281.24 5.79 2.128 0.836 266.83~278.43 −7.12 −2.592 0.947 272.33~279.23 −0.82 −0.300 0.086
[30] 1.164~3.983 271.67~281.15 2.5~7.5 16 271.97~282.05 2.49 0.892 0.417 269.14~280.92 −2.53 −0.931 0.473 271.36~281.43 0.48 0.172 0.07
[37] 8.500~25.000 278.09~282.51 5~10 8 282.37~284.21 4.28 1.539 1.057 274.77~281.20 −3.93 −1.406 0.83 278.58~282.50 0.49 0.176 0.105
[42] 1.517~3.227 263.2~276.1 10~20 8 271.99~279.69 9.99 3.717 2.357 255.57~273.57 −9.37 −3.486 2.038 263.89~276.68 1.39 0.517 0.245
[41] 1.866~60.14 274.84~284.6 4.3 14 275.85~284.60 6.49 2.361 0.927 273.76~282.18 −6.01 −2.148 0.904 274.86~283.20 5.39 1.961 0.813
[31] 1.310~3.590 271.4~279.4 5 5 275.99~286.00 1.80 0.644 0.543 273.59~283.17 −1.43 −0.502 0.364 274.89~284.08 0.59 0.211 0.122
[32] 0.800~4.300 267.55~282.9 5~10 20 267.94~281.98 3.49 1.259 0.635 265.42~277.89 −8.43 −2.980 0.918 266.84~279.09 −4.52 −1.598 0.179
[20] 1.162~3.907 263.29~280.92 3~20.03 25 270.42~282.01 10.38 3.890 1.173 256.04~280.78 −7.54 −2.826 0.927 264.39~281.31 1.98 0.746 0.178
[43] 1.189~2.150 258.15~262.15 25 5 270.17~275.33 13.18 5.028 3.66 249.21~262.65 −11.93 −4.551 3.449 260.72~268.18 1.29 0.492 0.234
[34] 1.151~3.701 267.45~277.35 10~15.2 13 269.43~280.85 11.67 4.503 1.639 246.80~274.42 −11.35 −4.397 2.038 258.11~277.83 −1.31 −0.490 0.203
[40] 1.283~3.617 271.85~279.05 3.5~10.5 16 272.54~280.25 4.58 1.682 0.89 265.73~278.71 −7.23 −2.634 1.051 271.44~279.44 −3.22 −1.161 0.253
[35] 1.931~2.498 276.15~277.15 2~4 12 276.55~280.65 2.20 0.790 0.297 273.13~276.95 −5.92 −2.121 0.46 276.15~277.53 −2.71 −0.971 0.154
[39] 1.370~3.730 271.8~280.2 5 4 278.34~281.50 1.30 0.464 0.439 276.42~279.08 −1.21 −0.434 0.331 277.43~280.28 0.30 0.108 0.06
[36] 0.703~29.316 254.75~280.6 5~25 29 264.34~282.40 19.47 7.438 2.353 244.90~279.78 −17.44 −6.465 2.582 254.83~281.08 −3.43 −1.272 0.251
[11] 1.450~3.830 274.15~281.15 3~8 18 274.65~282.01 16.97 6.405 1.114 246.15~280.63 −19.60 −7.375 1.127 263.33~281.23 −2.42 −0.911 0.177
[44] 0.98~3.82 266.15~279.15 3.6~10 17 268.84~281.04 3.68 1.331 0.792 262.75~279.05 −3.40 −1.277 −0.588 267.75~279.85 1.6 0.601 0.218
Total 0.703~30.615 254.75~284.6 2~25 231 264.34~286.00 19.47 7.438 1.190 244.90~283.17 −19.60 −7.375 1.095 254.83~284.08 5.39 1.961 0.210
a Number of data points; b Maximum absolute error; c Maximum relative error; d Average absolute relative deviation.
Energies 2024, 17, 2356 29 of 39
Appendix B
Appendix B
Figure A1.
Figure A1. Density
Density of
of i-rich
i-rich phase
phase and
and vapor
vapor pressure
pressure of
of component
component i.i.
Energies 2024, 17, 2356 30 of 39
Figure A2.CO
FigureA2. CO22 solubility
solubility without
without hydrates.
hydrates.
Energies 2024, 17, 2356 31 of 39
Figure
Figure A3. solubility with
A3. CO22 solubility with hydrates.
hydrates.
Energies 2024, 17, 2356 32 of 39
FigureA4.
Figure 𝑑Δ𝜇.
A4.d∆µ.
Energies 2024, 17, 2356 33 of 39
Figure
Figure A5. Phaseequilibrium
A5. Phase equilibriumtemperature
temperatureofofCO
CO 2 –pure
2–pure water
water or or NaCl
NaCl aqueous
solution–CO 2 hy-
2
hydrate.
drate.
EnergiesEnergies
2024, 17, 2356
2024, 17, x FOR PEER REVIEW 36 of 4134 of 39
Figure KCO
A6.A6.
Figure 𝐾 2 −H2 O without hydrates.
without hydrates.
Energies 2024, 17, 2356 35 of 39
Figure A7.K𝐾
FigureA7. CO2 −H2 O with
withhydrates.
hydrates.
Energies 2024, 17, 2356 36 of 39
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Energies 2024, 17, 2356. https://doi.org/10.3390/en17102356 https://www.mdpi.com/journal/energies

Ref. T/K P/MPa System

2. Theory and Methods

2.1. BWRS EOS

where P represents system pressure, MPa; T represents system temperature, K; ρ rep-

ρci · B0i = A1 + B1 ωi (2)

Table 2. Critical parameters and acentric factors of CO2 and H2 O [84].

Table 3. The values of universal parameters A j and Bj [84].

2.1.1. Calculation of Fluid Density

The iterative equation for density roots is:

2.1.2. Calculation of Fugacity Coefficients and Fugacity

where Z represents the compressibility factor, which is defined as:

The fugacity ( f ) of a single-component fluid satisfies:

The fugacity ( f i ) of component i satisfies [93]:

ln f i = lnφi + lnP + lnqi (33)

2.2. Principle of Phase Equilibrium

For components H2 O and CO2 in an equilibrium system of CO2 -pure water/NaCl

2.3. Thermodynamic Properties of Systems without Hydrates

2.3.2. CO2 Solubility in Pure Water/NaCl Aqueous Solution

zi = NCO2 −rich yi + NH2 O−rich xi (44)

yi and xi can be calculated using Ki , zi , and NCO2 −rich as follows:

The iterative equation for NCO2 −rich is:

CO2 solubility in pure water/NaCl aqueous solution, SCO2 , is:

2.4. Hydrate Thermodynamic Theories

2.4.1. Van der Waals–Platteeuw Model

2.4.2. Calculation of Langmuir Constants

2.4.3. Saito Model and Its Modification

The expression for ∆µH,2

2.4.4. Calculation of H2 O Fugacity in CO2 Hydrate Phase

EH represents the fugacity of H O in empty hydrate phase:

2.5. Thermodynamic Properties of Systems with Hydrates

xH2 O n+1 = 1 − xCO2 n+1 (73)

2.5.2. Modification of the VdWP Model

yCO2 n+1 = yCO2 n − 0.00000001 (74)

yH2 O n+1 = 1 − yCO2 n+1 (75)

2.5.3. Phase Equilibrium Conditions of CO2 –Pure Water/NaCl Aqueous Solution–CO2

T eq n+1 = T eq n + 0.01 (76)

2.6. Modification of BWRS EOS

KCO2 −H2 O n+1 = KCO2 −H2 O n − 0.00001 (77)

2.7. Statistics and Screening of Reported Experimental Data

3. Results and Discussion

3.1. Modification of BWRS EOS

System Method KCO2 −H2 O Equation

3.2. Calculation Results of CO2 Solubility

Table 5. The calculation effect of CO2 solubility.

Fitting Data Fitting Prediction Prediction

Pure water without hydrates - 251 5.293 114 7.912

3.3. Modification of VdWP Model

Table 6. Fitting equations of d∆µ.

Method d∆µ Equation

1 730 − 2.8 × T + (0.0422 − 0.000646061 × SNaCl − 0.0000390636 × T ) × T × SNaCl

Method 𝒅𝚫𝝁 Equation

System Methods Fitting Data Points Fitting Accuracy/%

P system pressure, MPa

f iCO2 −rich fugacity of H2 O in CO2 -rich phase, MPa

Pure water without hydrates

NaCl aqueous solution without hydrates