energies

Article
Thermodynamic Modeling of
CO2-N2-O2-Brine-Carbonates in Conditions
from Surface to High Temperature and Pressure
Jun Li 1, *, Raheel Ahmed 2 and Xiaochun Li 1
1 State Key Laboratory of Geomechanics and Geotechnical Engineering, Institute of Rock and Soil Mechanics,
Chinese Academy of Sciences, Wuhan 430071, China; lijun2009s@gmail.com
2 Dimue Technology Ltd. Co., Wuhan 430000, China; Raheel.Ahmed@dimue.com
* Correspondence: lijun2009s@gmail.com; Tel.: +86-181-6256-8012




Received: 22 August 2018; Accepted: 27 September 2018; Published: 1 October 2018


Abstract: Nitrogen (N2 ) and oxygen (O2 ) are important impurities obtained from carbon dioxide
(CO2 ) capture procedures. Thermodynamic modeling of CO2 -N2 -O2 -brine-minerals is important
work for understanding the geochemical change of CO2 geologic storage with impurities. In this
work, a thermodynamic model of the CO2 -N2 -O2 -brine-carbonate system is established using the
“fugacity-activity” method, i.e., gas fugacity coefficients are calculated using a cubic model and
activity coefficients are calculated using the Pitzer model. The model can calculate the properties
at an equilibrium state of the CO2 -N2 -O2 -brine-carbonate system in terms of gas solubilities,
mineral solubilities, H2 O solubility in gas-rich phase, species concentrations in each phase, pH and
alkalinity. The experimental data of this system can be well reproduced by the presented model,
as validated by careful comparisons in conditions from surface to high temperature and pressure.
The model established in this work is suitable for CO2 geologic storage simulation with N2 or O2
present as impurities.

Keywords: thermodynamic modeling; CO2 geologic storage; CO2 -N2 -O2 -brine-carbonates;
fugacity; activity

1. Introduction
Carbon emission reduction is becoming a more and more important topic for the sustainable
development of human beings. Carbon capture and storage (CCS) has been validated as a useful
method for reducing carbon emission and the clean use of fossil energy. High cost is one of the main
barriers for commercial use of CCS. In the whole chain of CCS, more than half of the cost is consumed
by carbon dioxide (CO2 ) capture, because a high purity of CO2 is usually used for real CO2 storage
projects [1]. Lowering the CO2 purity could be a way to reduce the CO2 capture cost.
According to an International Energy Agency Greenhouse Gas R&D Programme (IEAGHG)
report [2], even though there are various impurities obtained from CO2 capture techniques, the main
impurities are nitrogen (N2 ) and oxygen (O2 ). When CO2 is injected with impurities, fluid properties
such as gas density, viscosity and gas-water-mineral interactions could be different [3,4] compared
to the injection of pure CO2 . The presence of impurities decreases CO2 solubility in brine and also
affects H2 O contents in non-aqueous phase. A change in fluid property also affects fluid migration and
CO2 storage capacity in subsurface porous media. When O2 is injected with CO2 into the subsurface
reservoir, the oxidation-reduction environment is changed, which triggers related water-mineral
interactions. In this case, water properties (such as composition, pH and alkalinity), porosity and
permeability vary consequently [5,6].

Energies 2018, 11, 2627; doi:10.3390/en11102627 www.mdpi.com/journal/energies

Energies 2018, 11, 2627 2 of 18

Thermodynamic modeling of CO2 -impurities-brine systems is essential work for understanding

subsurface fluid transport. It mainly consists of the modeling of phase partitioning, density and
viscosity. Soreide and Whitson [7] constructed mutual solubility of multi-gases (including CO2 , CH4 ,
H2 S and N2 ) and brine systems. The model shows good accuracy at low temperature and pressure
with a salinity less than 2 (molal). Li et al. [3] made modifications and achieved good accuracy at wider
ranges of temperature, pressure and salinity for CO2 -CH4 -H2 S-brine systems. Gas solubility modeling
of CO2 , N2 and O2 in water and brine has been performed by Duan and Sun [8], Mao and Duan [9] and
Geng and Duan [10] based on comprehensive reviews of experimental data. These models can reproduce
most of the experimental data over wide ranges of temperature, pressure and salinity. However, they can
only consider single gas component cases, and cannot calculate multi-gas and brine system equilibria.
Tan et al. [11] developed a model for CO2 , SO2 and brine system equilibria using a “cubic plus association”
(CPA) method. Sun and co-workers developed an improved “Statistical Associating Fluid Theory”
(SAFT) model for CO2 -brine and water-hydrocarbon systems by introducing a Lennard-Jones (LJ) term
(SAFT-LJ models, [12–14]). CPA and SAFT type models usually have high computation accuracy, but are
time-consuming and are not practical for reservoir simulation implementations.
Carbonates (including calcite, magnesite and dolomite) are important minerals for CO2
geologic storage. When CO2 is injected into porous media with carbonate minerals,
dissolution of carbonates into aqueous phase is enhanced. Water property (such as pH,
ion concentration, density and viscosity), porosity and permeability are affected consequently.
Thermodynamic modeling work for CO2 -brine-mineral systems began in the 1980s. Harvie and
Weare [15] and Harvie et al. [16] used the Pitzer model to predict mineral solubility in the
system Na-K-Mg-Ca-H-Cl-SO4 -OH-HCO3 -CO3 -CO2 -H2 O. Moller [17], Greenberg and Moller [18],
and Christov and Moller [19] further consider the temperature effects for model parameters of
the system. The pressure effects are not considered in these models. Duan and Li [20] proposed
a thermodynamic model for the quaternary system CO2 -H2 O-NaCl-CaCO3 which predicts the
solubility of calcite, CO2 and other properties over wide ranges of temperature and pressure.
Li and Duan [21] extended the model to a quinary system with CaSO4 included. Gypsum and anhydrite
dissolution, precipitation and interactions with CO2 and H2 O can be considered in the model.
This work discusses the phase partitioning modeling of the CO2 -N2 -O2 -brine system based on
careful review and validation with experimental data at high temperature, pressure and salinity.
The model is then extended to CO2 -N2 -O2 -brine-carbonates phase equilibria. Calcite, magnesite and
dolomite are considered to be carbonate minerals of this system. The calculation results given by the
model are compared with existing experimental data such as mineral solubilities with CO2 contained,
CO2 solubility in brine saturated with minerals, water pH, and ion concentrations at various pressures
and temperatures.

2. Thermodynamic Modeling of CO2 -N2 -O2 -Brine Equilibria

When gas components (CO2 , N2 and O2 ) are dissolved in brine, chemical potentials approach
equality, and the whole system approaches an equilibrium state. The Henry constant [21] is defined as:

fi
KH = (1)
ai

where KH is the Henry constant; fi is the gas fugacity of component i; ai is activity of component i in
water phase. This equation is valid only when the system is at equilibrium state.
Furthermore, f i = Pyi φi , where yi is the mole fraction of component i in gas phase and φi is
fugacity coefficient of component i in gas phase. For activity ai = mi γi , where mi is the molality of
component i in aqueous phase, and γi is the activity coefficient of component i in aqueous phase.
From Duan and Li [20], KH is the function of temperature and pressure:

K H ( T, P) = K H ( T, Pre f ) × exp( PF ) (2)

Energies 2018, 11, 2627 3 of 18

where Pre f is pressure at reference state and is usually set as 1 atm. PF is Poynting factor, which is
defined as,
wP V Vm
m
PF = dP = ( P − Pre f ) (3)
Pre f RT RT
R is gas constant and Vm is partial molar volume. Vm is average partial molar volume. From Equations
(1) to (3), solubility of component i can be calculated as,

Pyi φi
mi =   (4)
V ( P− P )
γi K H ( T, Pre f ) exp m,i RT re f

In this work, fugacity coefficients are calculated based on the Peng-Robinson (PR) [22] equation.
The related parameters for CO2 , N2 , O2 , and H2 O can be found in Tables 1 and 2. Activity coefficients
are calculated by the Pitzer [23] model. The model parameters, as well as KH and Vm , are discussed in
Section 2. The related experimental work of the concerned fluid system is used for the parameterization
of the model.

2.1. Fugacity Coefficients

The two-parameter cubic form equation of state has been widely used in the oil and gas
industry for phase properties and flash calculations [22,24,25], and has shown good accuracy for
non-polar molecules. In this work, fugacity coefficients of gaseous species are calculated using the
Peng-Robinson [22] model of the form as follows:

RT a( T )
P= − (5)
Vm − b Vm (Vm + b) + b(Vm − b)

where a( T ) = a( Tc )α( Tr , ω ); a(Tc ) is the Van der Waals’ attraction factor at a critical temperature
R2 T 2
defined as a( Tc ) = 0.45724 Pc c , where Pc is critical pressure; b = 0.07780 RT c
Pc ; Tr is reduced temperature
T
Tr = Tc ; Tc is critical temperature; ω is acentric factor; α( Tr , ω ) is a dimensionless function of relative
temperature and acentric factor.
When gaseous phase has more than one component, the mixing rule is considered for parameters
“a” and “b”.
a = ∑ ∑ yi y j aij (6)
i j

b= ∑ bi y i (7)
i
√
where aij = ai a j (1 − δij ) and δij is binary interaction coefficient of species i and j; yi is mole fraction
of species i in gaseous phase.
The parameters (critical temperature Tc , critical pressure Pc , and acentric factor ω) used in PR [22]
EOS for each individual component are listed in Table 1.

Table 1. Parameters of each component for PR EOS.

Tc (K) Pc (bar) ω
CO2 304.2 a 73.83 a 0.2236 a
N2 126.2 b 34.0 b 0.0377 b
O2 154.6 b 49.8 b 0.021 b
H2 O 647.3 a 221.2 a 0.3434 a
a: from Soreide and Whitson [7]; b : from PHREEQC database [26].

The binary interaction parameters (δij ) used PR EOS are listed in Table 2.
Energies 2018, 11, 2627 4 of 18

Table 2. Binary interaction parameters for PR EOS.

δij H2 O CO2 N2 O2
H2 O - 0.1896 a b 0.20863 c
0.32547
CO2 0.1896 a - −0.007 d 0.1140 d
N2 0.32547 b −0.007 d - −0.0119 c
O2 0.20863 c 0.1140 d −0.0119c -
a: from Soreide and Whitson [7]; b : from Ziabakhsh-Ganji and Kooi [27]; c : from Wang et al. [28]; d: from Li and Yan [29].

2.2. Equilibrium Constant

From Equations (2) and (3), equilibrium constant can be expressed as,
!
Vm,i ( P − Pre f )
Ki = K H ( T, Pre f ) exp (8)
RT

where i denotes a component (i = H2 O, CO2 , N2 , and O2 ).

For H2 O, the equation from previous work [3,4] is used,

( P − 1)( a6 + a7 T )
 
2 3 4
K H2 O = ( a1 + a2 T + a3 T + a4 T + a5 T ) exp (9)
RT

where a1 – a7 are the parameters found in Li et al. [3].

For CO2 , N2 and O2 , Equation (8) is used for the equilibrium constant. K H ( T, Pre f ) is calculated
following Appelo [30]:

A2 A
log(K H ( T, Pre f )) = A0 + A1 T + + A3 log( T ) + 24 + A5 T 2 (10)
T T

where A0 – A5 are the parameters found in Appelo [30], listed in Table 3. Also, Vm,i is calculated as
follows:
!
100a2,i a3,i 104 a4,i
Vm,i = 41.84 0.1a1,i + + + − ωi × QBrn (11)
2600 + P ( T − 288) (2600 + P)( T − 288)

where a1,i – a4,i and ω i are the parameters found in Appelo [30], listed in Table 3, and QBrn is the Born
function, which can be found in Helgson et al. [31].

Table 3. Parameters for equilibrium constants of CO2 , N2 and O2 .

A0 A1 A2 A3 A4 A5 a1 a2 a3 a4 ω
−1.9194
CO2 −10.52624 2.3547 × 10−2 3972.8 0 −5.8746 × 105 × 7.29 0.92 2.07 −1.23 −1.6
10−5
N2 58.453 −1.818 × 10−3 −3199 −17.909 27,460 0 7 0 0 0 0
O2 7.5001 −7.8981 × 10−3 0 0 −2.0027 × 105 0 5.7889 6.3536 3.2528 −3.0417 −0.3943

2.3. Activity Model

Activity or activity coefficient is an important parameter to describe the deviation of solvent and
aqueous species from ideal solution at a given temperature and pressure. The Pitzer [23,32,33] model is
an accurate model for calculating the activity of water and various aqueous species especially to high
salinity of brine. This activity model has wide application to water-salt-mineral system computation
and modeling at different temperatures and pressures [16–21,34]. These applications have shown the
success of the Pitzer [23] model. In this work, the Pitzer [23] model is used to calculate aqueous species
activity coefficients. The details of Pitzer [23] equations have been discussed in previous research
Energies 2018, 11, 2627 5 of 18

papers [20,21]. When gas components are dissolved in water, it is assumed that they are in the form of
neutral species in aqueous phase. The Pitzer [23] equation of neutral species is as follows [8]:

ln γi = ∑ 2mc λi−c + ∑ 2ma λi−a + ∑ ∑ mc ma ζ i−a−c (12)

c a c a

where γi is the activity coefficient of component i; i = CO2 , N2 , or O2 ; λi−c , λi−a and ζ i−a−c are the
Pitzer interaction parameters; mc and m a are the aqueous species molality; “c” denotes cation species
and “a” denotes anion species. In this work, λi−c , λi−a and ζ i− a−c are parameterized from the gas
solubility experimental data.
The fitting equation of Pitzer interaction parameters follows Appelo [30]:

1 1 T 1 1
Param = b0 + b1 × ( − ) + b2 × ln( ) + b3 × ( T − TR ) + b4 × ( T 2 − TR 2 ) + b5 × ( 2 − 2 ) (13)
T TR TR T TR

where b0 – b5 are fitting parameters; T is temperature in (K); TR = 298.15 (K). The parameters are listed
in Table 4.

Table 4. Parameters of Pitzer interaction equations for gas components and main ion species.

. b0 b1 b2 b3 b4 b5
λCO2 − Na+ a 0.085
λCO2 − Mg+2 a 0.183
λCO2 −Ca+2 a 0.183
λCO2 −SO−2 a 0.075
4
λCO2 −K+ a 0.051
λ N2 − Na+ b 0.1402 −595 −4.025 0.01044 −2.131 × 10−6 49,970
λ N2 − Mg+2 b 0.2804 −1190 −8.05 0.02088 −4.262 × 10−6 99,940
λ N2 −Ca+2 b 0.2804 −1190 −8.05 0.02088 −4.262 × 10−6 99,940
λ N2 −K+ b 0.1402 −595 −4.025 0.01044 −2.131 × 10−6 49,970
λ N2 −SO−2 b 0.0371
4
λO2 − Na+ c 0.19997
λO2 − Mg+2 c 0.31715
λO2 −Ca+2 c 0.35135
λO2 −K+ c 0.15022
λO2 −SO−2 c 0.14383
4
b
ζ CO2 − Na+ −SO−2
4
−0.015
b
ζ N2 − Na+ −SO−2
4
−1.16 × 10−2
ζ N2 − Na+ −Cl − b −0.58 × 10−2
ζ N2 −K+ −Cl − b −0.58 × 10−2
ζ N2 −K+ −SO−2 b −1.16 × 10−2
4
ζ N2 −Ca+2 −Cl − b −1.16 × 10−2
ζ N2 −Ca+2 −SO−2 b −2.32 × 10−2
4
ζ N2 − Mg+2 −Cl − b −1.16 × 10−2
ζ N2 − Mg+2 −SO−2 b −2.32 × 10−2
4
a: from Appelo [30]; b : this work; c : from Geng and Duan [10].

2.4. Gas-Brine Mutual Solubility Reproduction

To validate the above thermodynamic model, comparisons are made between the gas-brine
mutual solubility calculated from this model and existing experimental data including CO2 -brine,
N2 -brine, O2 -brine and multi-gas-brine systems.
The experimental work for CO2 -brine system is extensive and substantial, with a wide range
of temperatures, pressures and water salinities. A comparison of the CO2 -brine system mutual
solubility obtained from the experimental data and the model proposed in this work is shown
in Figure 1. The experimental data for validation was mainly obtained from Todheide and
Franck [35], Takenochi and Kennedy [36], Malinin and Savelyeva [37], Malinin and Kurorskaya [38],
mutual solubility calculated from this model and existing experimental data including CO2-brine,
N2-brine, O2-brine and multi-gas-brine systems.
The experimental work for CO2-brine system is extensive and substantial, with a wide range of
temperatures, pressures and water salinities. A comparison of the CO2-brine system mutual
solubility
Energies 2018,obtained
11, 2627 from the experimental data and the model proposed in this work is shown in
6 of 18
Figure 1. The experimental data for validation was mainly obtained from Todheide and Franck [35],
Takenochi and Kennedy [36], Malinin and Savelyeva [37], Malinin and Kurorskaya [38],
Tabasinejad
Tabasinejad et et al.
al. [39].
[39]. As
As shown
shown inin the
the comparison,
comparison, the
the model
model can
can well
well reproduce
reproduceCOCO22 solubility
solubility in
in
aqueous
aqueous phase with pressure ranging from 1 to more than 1000 (bar), temperature range from
phase with pressure ranging from 1 to more than 1000 (bar), temperature range from 00 to
to
more ◦
more thanthan250250( C),
(°C),NaCl
NaClmolality range
molality fromfrom
range 0 to more
0 to than
more6 than
(molal). The H2 OThe
6 (molal). solubility in CO2 -rich
H2O solubility in
phase can also be well reproduced by this model.
CO2-rich phase can also be well reproduced by this model.

Figure 1.
Figure 1. CO
CO22-brine
-brine system
system mutual
mutual solubility
solubility from
from experimental
experimental data [35–39] (dots)
data [35–39] (dots) and
and results
results
calculated by this model (lines) at various temperatures, pressures and salinities. (a) CO
calculated by this model (lines) at various temperatures, pressures and salinities. (a) CO2 solubility in
2 solubility in
pure water. (b) CO
pure water. (b) CO2 2 solubility in NaCl solutions varying with pressure at different temperature
at different temperature and and
NaClmolality.
NaCl molality.(c)(c)
CO2CO 2 solubility
solubility in solutions
in NaCl NaCl solutions varying
varying with NaClwith NaCl
molality molalitytemperatures
at different at different
temperatures
and pressures. and
(d) Hpressures.
2 O solubility(d)in H
CO2O -rich
2 solubility
phase in
at CO 2-richpressures
different phase at
anddifferent pressures
temperatures. and
temperatures.
A comparison of the mutual solubility of N2 -brine obtained from the experimental data and the
resultsA calculated
comparison byofthis
thework,
mutual solubility
is shown of N2-brine
in Figure obtained
2. The from the
experimental experimental
data datainand
of N2 solubility the
water
results
or NaClcalculated by this
solutions are fromwork,
Weibeisetshown
al. [40]inand
Figure 2. The experimental
Mishnima et al. [41]. Thedata of N2 solubility
experimental data ofinHwater
2 O in
or2 -rich
N NaClphase
solutions are Althaus
is from from Weibe et al.Namiot
[42] and [40] and Mishnima
and Bondarevaet al. [41].
[43]. It isThe experimental
shown data of
that the model of H 2O
this
work can well reproduce the experimental work at a wide range of temperatures, pressures and salinities.
Energies 2018, 11, x 7 of 18
Energies 2018, 11, x 7 of 18
in N2-rich phase is from Althaus [42] and Namiot and Bondareva [43]. It is shown that the model of
in Nwork
this 2-rich phase is from Althaus [42] and Namiot and Bondareva [43]. It is shown that the model of
can well reproduce the experimental work at a wide range of temperatures, pressures and
this work
Energies 2018,can
salinities. well reproduce the experimental work at a wide range of temperatures, pressures7 of
11, 2627 and18
salinities.

Figure 2. N2-brine mutual solubility obtained from experimental data [40–43] (dots) and the results
Figure 2. N
Nby
2-brine mutual solubility obtained from experimental data [40–43] (dots) and the results
Figure 2.
calculated 2 -brine mutual
the model atsolubility obtained
various values from experimental
of temperature, data
pressure [40–43]
and (dots)
salinity. and
(a) N the results
2 solubility in
calculated
calculated
water. (b) byby the model
N2 the modelin atNaCl
at various
various values varying
values of temperature,
of temperature, pressure
pressure and
(c)and salinity. (a)
N2 salinity. (a)
inNN 2 solubility in
solubility solutions with pressure. solubility 2 solubility
NaCl in
solutions
water.
water.
varying (b)
(b) NN2 solubility
with solubility in
in NaCl
NaCl solutions
at 1 solutions varying
(d) Hvarying with pressure.
with pressure. (c)
N2-rich(c) NN2 solubility
solubility inin NaCl
NaCl solutions
solutions
2 NaCl molality atm. 2O solubility in phase.2
varying with NaCl molality at 1 atm. (d) H 2O solubility in N2-rich phase.
varying with NaCl molality at 1 atm. (d) H O solubility in N -rich phase.
2 2
The experimental work on the O2-brine system is not as comprehensive as on the CO2-brine
The
The
and N2-brine experimental
experimental worktemperature
systems.work
The onthe
on theO2O-brine
2-brine system
system
is lower is100
is not
than not as comprehensive
as(°C),
comprehensive
and pressure isasbelow
as on onCO
the the200CO(bar).
2-brine
2 -brine andA
and
N N
-brine
2 -brine systems.
systems. The The temperature
temperature is lower is lower
than 100 (◦ C),100
than and (°C), and
pressure pressure
is below is
200 below
(bar). A200 (bar).
comparison A
comparison
2 of the model results and experimental data obtained from Stephen et al. [44], Pray and
comparison
of the model
Stephen [45],of the Yasunishi
model
results
and results
[46] and
and experimental experimental
data obtained
is shown in Figure data
fromobtained
Stephen
3. The modelfrom al.Stephen
etcan et and
al. [44],
[44], reproduce
well Pray thePray
Stephen and
[45],
existing
Stephen
and [45], data.
Yasunishi
experimental and is
[46] Yasunishi
shown in[46] is shown
Figure in Figure
3. The model can 3. The
well model can
reproduce thewell reproduce
existing the existing
experimental data.
experimental data.

Figure 3.3. O
Figure O2-brine
-brine mutual
mutual solubility
solubility obtained
obtained from
from experimental
experimental data
data [44–46]
[44–46] (dots)
(dots) and
and the
the results
results
Figure 3. O2by
calculated 2-brine mutual solubility obtained from experimental data [44–46] (dots) and the results
the model (lines) at various values of temperature, pressure and salinity. (a) O2
calculated by the model (lines) at various values of temperature, pressure and salinity. (a) O2 solubility
calculated
solubility inby the model
water. (b) O (lines) at various values of temperature, pressure and salinity. (a) O2
2 solubility in NaCl solutions.
in water. (b) O2 solubility in NaCl solutions.
solubility in water. (b) O2 solubility in NaCl solutions.
For multi-component
For multi-componentgas gasmixture
mixtureand
and brine
brine systems,
systems, thethe experimental
experimental work
work is rare.
is rare. Liu
Liu et al.et[47]
al.
For multi-component
[47] proposed CO 2-N
gas mixture and brine systems, the experimental work is rare. Liu et al.
proposed CO2 -N 2 -H 2 O2-H 2O equilibrium
equilibrium experiments
experiments at two at two temperatures
temperatures and
and three three pressures
pressures with
with different
[47] proposed
different CO CO
-N 2-N2-H2O equilibrium experiments at two temperatures and three pressures with
gas mixture compositions. As shown in Figure 4, the experimental results can
CO 2 -N 2 gas mixture
2 2 compositions. As shown in Figure 4, the experimental results can accurately be
different CO 2-N2 gas mixture compositions. As shown in Figure 4, the experimental results can
accuratelybybethis
predicted
predicted model. by this model.
accurately be predicted by this model.
Energies 2018, 11, 2627 8 of 18

Energies 2018, 11, x 8 of 18

Figure 4. CO2-N2-H2O equilibria (i.e., CO2 and N2 mole fractions in brine varying with N2 mole
Figure 4. CO2 -N2 -H2 O equilibria (i.e., CO2 and N2 mole fractions in brine varying with N2 mole
fractionsiningas)
fractions gas) obtained
obtained from
from experimental
experimental workwork
(Liu(Liu
et al.et[47],
al. dots)
[47], dots) and
and the the calculated
calculated results results
(lines)
(lines)
by by theinmodel
the model in this
this work work atvalues
at various various values of temperature
of temperature and pressure. and(a)pressure. (a) and
at P=80 bar at P=80 bar and
T=308.15 K;
T=308.15
(b) K; bar
at P=120 (b) and
at P=120
308.15bar andat308.15
K; (c) P=160 K;
bar(c)
andat T=308.15
P=160 barK;and T=308.15K;
(d) at P=80 bar (d)
andat P=80 bar
T=318.15 K; and
(e)
atT=318.15K;
P=120 bar(e)and atT=318.15
P=120 barK;and T=318.15
(f) P=160 barK; (f) T=318.15
and P=160 barK.and T=318.15 K.

3.3.Gas-Brine-Mineral
Gas-Brine-MineralEquilibria
Equilibria
In
In this section,
section, thethemodeling
modeling andand validation
validation of gas-brine-mineral
of gas-brine-mineral equilibria
equilibria are discussed.
are discussed. When
When
CO2 isCO 2 is injected
injected into into a saline
a saline aquifer
aquifer in in industrialCO
industrial CO geologicstorage
2 2geologic storage projects, CO CO22 existence
existence
significantly
significantlyinfluences
influencesthe thewater-carbonate
water-carbonatemineral
mineralequilibrium.
equilibrium. The
The commonly
commonlyfoundfoundcarbonate
carbonate
minerals
minerals in in sedimentary
sedimentary environments
environments are arecalcite
calcite(CaCO
(CaCO 3 ),
3), magnesite
magnesite (MgCO
(MgCO3 3),), and
and dolomite
dolomite
(CaMg(CO33))22). The
(CaMg(CO The above three minerals are considered in this this work
work even
even though
though there
there are
are many
many
other
otherkinds
kindsof ofcarbonate
carbonateminerals
mineralsininnatural
naturalenvironments.
environments. The Thegas-brine
gas-brineequilibrium
equilibriummodelmodelwaswas
explainedinindetail
explained detailininSection
Section2. 2.This
This section
section will
will focus
focus onon brine-mineral
brine-mineral equilibrium
equilibrium modeling
modeling andand
its
its coupling with the gas-brine model. When the above carbonate minerals reach an equilibrium
state with water/brine at a given temperature and pressure, the following chemical reactions are
observed.:
Energies 2018, 11, 2627 9 of 18

coupling with the gas-brine model. When the above carbonate minerals reach an equilibrium state
with water/brine at a given temperature and pressure, the following chemical reactions are observed.:

CaCO3(Calcite) = CO3 2− + Ca2+ (14)

MgCO3(Magnesite) = CO3 2− + Mg2+ (15)

CaMg(CO3 )2(Dolomite) = 2CO3 2− + Ca2+ + Mg2+ (16)

CaCO3 (0) = CO3 2− + Ca2+ (17)

MgCO3 (0) = CO3 2− + Mg2+ (18)

H2 O = H+ + OH− (19)

HCO3 − = H+ + CO3 2− (20)

CO2 (0) = 2H+ + CO3 2− (21)

MgOH+ = Mg2+ + OH− (22)

CaOH+ = Ca2+ + OH− (23)

where superscript (0) denotes neutral aqueous species.

Similar to Equation (1), when an equilibrium state is reached, the following equation for each of
the above chemical reactions is applicable [30]:

Kr = ∏ a υi (24)
i

where Kr is the equilibrium constant of a chemical reaction “r”; υi is the stoichiometric coefficient of
species i of a chemical reaction “r”; ai is the activity of species i of a chemical reaction “r”. For aqueous
species i,ai = mi γi , where mi is the molality of species i, and γi is the activity coefficient of species i.
Activity of minerals is 1.
To solve the speciation of the brine-mineral system at equilibrium state at a given temperature
and pressure, K or log K and the activity coefficients of all related reactions and species should be
specified. The equilibrium constant is calculated by Equation (8) using the equilibrium constant (Kref )
at reference pressure (1 bar or water saturation pressure) and mole volume (Vm ) of the related reaction.
Kref is a function of temperature and can be expressed by Equation (10). Vm is a function of temperature
and pressure and can be expressed by Equation (11). For all the above reactions, the related parameters
required for Kref and Vm are obtained from PHREEQC database [30].
Activity coefficients (γi ) of the aqueous species are calculated from the Pitzer [23] model.
The expressions of the Pitzer [23] model can be found in Li and Duan [21]. The Pitzer parameters
(0) (1) (2) ϕ
fall into three categories: (1) β MX , β MX , β MX and C MX for each cation-anion pair of the species;
(2) θij for each cation-cation or anion-anion pair of the species; (3) ψijk for each cation-cation-anion
or anion-anion-cation triplet of the species, λni for ion-neutral pairs of the species, and ζ nij for
cation-anion-neutral triplets of the species. The Pitzer parameters of various water-salt-mineral system
have been studied since the 1980s via thermodynamic modeling in conjunction with experimental
work. Table 5 lists the sources of the Pitzer parameters for the calculations of this work system.
Energies 2018, 11, 2627 10 of 18

Table 5. Literature sources of Pitzer parameters.

Pitzer Parameters Literature Sources

(0) (1) (2) ϕ
β Ca−CO3 , β Ca−CO3 , β Ca−CO3 , CCa−CO3 Duan and Li [20]
(0) (1)
β Ca− HCO3 , β Ca− HCO3 Appelo [30]
(0) (1) ϕ
Energies 2018, 11, x −Cl , β Ca−Cl , CCa−Cl
β Ca Christov and Moller [19] 10 of 18
(0) (1) ϕ
β Mg−Cl , β Mg−Cl , C Mg−Cl Christov and Moller [19]
( (1) , C 
Mg -Cl , ,Mg
0) (0) (1)
β Mg Christov
Greenberg and Moller andChristov
[18], Moller [19]
and Moller [19]
− HCO3 β -Mg Cl
− HCO3Mg -Cl
(0)  (0) (1) ,  (1) (2)
β Ca−OHMg, -βHCO Ca3−OH Mg , β-CaHCO 3
−OH
Christov
Greenberg and Mollerand Moller
[18], [19]and Moller [19]
Christov
βHCa−-Cl − , H−CaCl-OH
(0(0)
) (1)(1) ϕ (2)
OH, ,β H CaCl -OH,C Christov
Christovand
andMoller
Moller[19]
[19]
(0) (1)
 H(0)-,Clβ,Na−H(1) , C H -−
ϕ
β Na−CO3 -Cl , CNa
CO3 Cl CO3
Polya et
Christov andal.Moller
[48] [19]
(0) (1) (1) ϕ
 Na
β Na− HCO3 (0)
, β ,
-CO 3 Na −Na  HCO3
-CO 3
,
, CC Na −
Na -CO HCO3
3
Polya
Polyaetetal.al.[48]
[48]
(0(0)
) (1)(1) ϕ 
βNa Na− OH3, ,β Na
- HCO  Na−-OH , C CNa
HCO 3 , Na −OH- HCO 3
Pabalan and Pitzer
Polya et al. [48] [49]
(0)(0) (1) ϕ
 Na−-Cl
β Na , β  (1) , C C−Cl Pitzer
and[50]
OH , Na −-Cl
Na OH , Na Na -OH Pabalan Pitzer [49]
θ H − Na , θOH (0)−Cl , θOH (1) −CO3  , θCl −CO3 ,
 ,  , C Li and Duan
Pitzer [34]
[50]
HCO3 ,θ HCO3−CO3
θCl −Na -Cl Na -Cl Na -Cl

 H - Na , OH -Cl , θOHCa-CO

−H 3 ,, θCa
Cl − Na
-CO 3 , Cl - HCO 3 ,  HCO 3-CO 3 Li and
Christov andDuan [34]
Moller [19]
CaCa
θ - H−, MgCa - Na Pabalan and Pitzer [49]
Christov and Moller [19]
ψOH −Cl − Na ,ψOH − HCO3 Ca - Mg− Na , ψCO3−Cl − Na , Pabalan and Pitzer [49]
ψCO3− HCO3− Na , ψCO3−Cl −Ca , ψOH −Cl −Ca , Li and Duan [34], Duan and Li [20]
 OH -Cl - Na ,  OH - HCO −COOH
3- Na−, Na
ψCO3 3-Cl - Na ,  CO 3- HCO 3- Na ,
Li and Duan [34], Duan and Li [20]
ψCl − Mg− ,ψ
CaCO Cl-−
3-Cl , 
CaNa −Ca , ψ Ca−, H−CO
OH -Cl -Cl Ca3-, Na
ψ-Cl
OH− H − Mg
Appelo [30]
 Cl - Mg -Ca ,  Cl - Na -Ca ,  Cl - H -Ca ,  Cl - H - Mg Appelo [30]
3.1. Mineral Solubility
3.1. Mineral Solubility
With the thermodynamic model discussed above, the solubility of carbonate minerals
(calcite,With the thermodynamic
magnesite and dolomite) modelcandiscussed above, in
be calculated theaqueous
solubilityphase
of carbonate minerals (calcite,
(with/without gases in
magnesite at
equilibrium) and dolomite)
various can be calculated
temperatures in aqueous
and pressures. phase (with/without
To validate gases in
the thermodynamic equilibrium)
model, at
the existing
various temperatures and pressures. To validate the thermodynamic model,
experimental data of carbonate mineral-gas-water equilibria should be reproduced. Predictions of the existing
experimental
mineral dataare
solubilities of also
carbonate
made mineral-gas-water
at various values of equilibria shouldpressure
temperature, be reproduced.
and NaClPredictions
molality. of
mineral solubilities are also made at various values of temperature, pressure and NaCl molality.
Calcite solubility experiments have usually been conducted with CO2 in equilibrium. A comparison
Calciteof solubility
of the values experiments
calcite solubility obtainedhave usually
from been conducted
experimental with calculated
data and those CO2 in equilibrium. A
by the proposed
comparison of the values of calcite solubility obtained from experimental data and those calculated
model at a CO2 partial pressure of 12 (bar) at different temperatures and NaCl molalities is shown
by the proposed model at a CO2 partial pressure of 12 (bar) at different temperatures and NaCl
in Figure 5. This model can well reproduce the experimental data of calcite solubility, as shown in
molalities is shown in Figure 5. This model can well reproduce the experimental data of calcite
the comparison.
solubility, as shown in the comparison.

Figure 5. Calcite solubility in aqueous solution with CO2 in equilibrium obtained from experimental
Figure 5. Calcite solubility in aqueous solution with CO2 in equilibrium obtained from experimental
data [51,52] and the calculated results using this model. (a) Calcite solubility varying with NaCl
data [51,52] and the calculated results using this model. (a) Calcite solubility varying with NaCl molality
molality at different temperatures. (b) Calcite solubility varying with temperature at different NaCl
at different temperatures. (b) Calcite solubility varying with temperature at different NaCl molalities.
molalities.

Calcite solubility in pure water and in NaCl solutions at various values of pressure,
temperature and NaCl salinity are shown in Figure 6. Calcite solubility in pure water increases with
pressure and decreases with temperature. At a given temperature and pressure, within the lower
NaCl molality range (0–1.5), calcite solubility increases with NaCl molality, but decreases in the
higher NaCl molality range (1.5–6).
Experimental data for magnesite solubility is rare. Bénézeth et al. [53] conducted synthetic
Energies 2018, 11, 2627 11 of 18

Calcite solubility in pure water and in NaCl solutions at various values of pressure, temperature
and NaCl salinity are shown in Figure 6. Calcite solubility in pure water increases with pressure and
decreases with temperature. At a given temperature and pressure, within the lower NaCl molality
range (0–1.5), calcite solubility increases with NaCl molality, but decreases in the higher NaCl molality
range (1.5–6).
Energies 2018, 11, x 11 of 18
Experimental data for magnesite solubility is rare. Bénézeth et al. [53] conducted synthetic magnesite
solubility product measurements at temperatures ranging from 50 to 200 (◦ C) with 0.1 (molal) NaCl
(molal) NaCl
Energies 2018,solutions,
11, x and with CO2 partial pressure under 30 (bars). A comparison of18Mg2+
11 of
solutions, and with CO2 partial pressure under 30 (bars). A comparison of Mg2+ molality of the
molality of the solution in equilibrium with magnesite between the experimental data and calculated
solution in equilibrium
(molal) NaCl in with and
solutions, magnesite
with CO between
2 partialthe experimental
pressure data
under and
30 and calculated
(bars). A comparison results
of Mgis shown
2+
results is shown Figure 7. Generally, the calculated values measurements are comparable
in Figure 7. Generally,
molality the calculated
of the solution in equilibriumvalues
withand measurements
magnesite areexperimental
between the comparable data
withand
calculated
calculated values
with calculated values a little bit higher than the measurements. Magnesite solubility in pure water
a littleresults is shown
bit higher than intheFigure 7. Generally,
measurements. the calculated
Magnesite values
solubility and measurements
in pure water or NaCl are comparable
solutions at various
or NaCl solutions at various temperatures, pressures and NaCl molalities of the solutions are shown
with calculated
temperatures, valuesand
pressures a little
NaCl bit molalities
higher thanof thethe
measurements.
solutions areMagnesite
shown insolubility
Figure 8.in pure water
The magnesite
in Figure
or NaCl8. solutions
The magnesiteat varioussolubility in pure
temperatures, waterand
pressures increases with pressure
NaCl molalities and decreases
of the solutions are shown with
solubility in pure water increases with pressure and decreases with temperature. In NaCl solutions,
temperature. In NaCl solutions, magnesite solubility increases with NaCl
in Figure 8. The magnesite solubility in pure water increases with pressure and decreases with molality in the lower
magnesite solubility increases with NaCl molality in the lower salinity range (0–1.5) but decreases in
salinity range (0–1.5)
temperature. but decreases
In NaCl solutions, in the higher
magnesite salinityincreases
solubility range (1.5–6).
with NaCl molality in the lower
the higher salinity range (1.5–6).
salinity range (0–1.5) but decreases in the higher salinity range (1.5–6).

Figure 6. Calcite solubility in pure water or NaCl solutions calculated by this model at different
Calcitesolubility
Figure 6. Calcite solubility in
in pure
pure water
water oror NaCl
NaCl solutions
solutions calculated
calculated by
by this
this model
model at
at different
different
temperature, pressure and NaCl molality. (a) Calcite solubility in pure water varying with pressure
temperature, pressure andand NaCl
NaCl molality.
molality.(a)
(a)Calcite
Calcitesolubility
solubilityininpure
purewater
watervarying with
varying withpressure at
pressure
at different temperatures. (b) Calcite solubility in NaCl solutions varying with NaCl molality at
different temperatures.
at different (b)
temperatures. Calcite solubility in NaCl solutions varying with NaCl molality at
(b) Calcite solubility in NaCl solutions varying with NaCl molality at 343.15 (K)
343.15 (K) and various pressures.
and various
343.15 pressures.
(K) and various pressures.

Figure 7. Magnesite solubility calculated by this model (lines) and obtained from the experimental
work of Benezeth et al. [53] (dots).

Figure
Figure 7.
7. Magnesite
Magnesite solubility
solubility calculated
calculated by
by this
this model
model (lines)
(lines) and
and obtained
obtained from
from the experimental
the experimental
work
work of
of Benezeth
Benezeth et
et al. [53] (dots).
al. [53] (dots).
Energies 2018, 11, 2627
x 12 of 18
Energies 2018, 11, x 12 of 18

Figure 8. Magnesite solubility in pure water or NaCl solutions calculated by this work at various
Figure 8. Magnesite solubility in pure water or NaCl solutions calculated by this work at various
8. Magnesite
Figure of
values solubility in pure
pressure, temperature and water or NaCl solutions
NaCl molality calculated
of the solution. (a) by this worksolubility
Magnesite at variousinvalues
pure
values of pressure, temperature and NaCl molality of the solution. (a) Magnesite solubility in pure
of pressure,
water temperature and NaCl molality of the solution. (a) Magnesite solubility in
varying with pressure at different temperature. (b) Magnesite solubility in NaCl solutions pure water
water varying with pressure at different temperature. (b) Magnesite solubility in NaCl solutions
varying with
varying with pressure
NaCl at different temperature.
molality (b) Magnesite solubility in NaCl solutions varying with
varying with NaCl molalityatat343.15
343.15(K)
(K)and
and various pressures.
various pressures.
NaCl molality at 343.15 (K) and various pressures.
ToToaddress
address thetheso-called
so-called“dolomite
“dolomite problem”,
problem”, Bénézeth
Bénézeth et et al.
al.[54]
[54]measured
measurednatural
naturaldolomite
dolomite
To
(CaMg(CO address the so-called
3)23))2solubility
“dolomite problem”, Bénézeth et al. [54] measured natural dolomite
(CaMg(CO ) solubilitywith
withaatemperature
temperature range
range of 50 to
of 50 to 253
253 (°C)
(°C)withwith0.1
0.1(molal)
(molal)NaCl NaCl solutions
solutions
(CaMg(CO
using 3 )2 ) solubility
a hydrogen electrode with a temperature rangelogarithmic (◦ C) with 0.1 (molal)
of 50 to 253concentrations NaCl solutions
using a hydrogen electrodeconcentration
concentrationcell.
cell. The
The logarithmic concentrations ofofMg
Mg , Ca
2+,2+Ca 2+ and
2+ and H+Hin+ in
2+ , Ca2+ and H+
using
thethe a hydrogen
solution at at electrode
equilibrium concentration cell. The logarithmic concentrations of Mg
solution equilibriumwith withdolomite
dolomiteare
are provided
provided inin the
the literature
literature[54].
[54].AAcomparison
comparison between
between
in the
thethe solution
experimental at equilibrium
experimentalresults resultsfrom with dolomite
fromBénézeth
Bénézeth et are
et al. provided
al. [54] in
[54] and the the literature
the results [54].
results calculated A
calculatedusingcomparison
usingthis thismodelbetween
model is is
the experimental
shown
shown in in Figure
Figure results
9.9.The from
Thetrends Bénézeth
trendsofofthe et al. [54]
themeasurements and the
measurements varying results
varying with calculated
withtemperature using
temperatureare this
arealso model
alsoobtained is
obtainedshown
byby
in Figure
this
this 9. The trends of the measurements varying with temperature are also obtained by this model.
model.
model.

Figure 9. Aqueous species concentration in equilibrium with dolomite obtained from experimental
results
9. [54] and the calculated results by this model at various
Figure
Figure 9. Aqueous
Aqueous species
species concentration
concentration in
in equilibrium
equilibrium with temperatures.
with dolomite obtained from
dolomite obtained from experimental
experimental
results [54] and the calculated results by this model at various temperatures.
results [54] and the calculated results by this model at various temperatures.
The presented model is used for the calculation of dolomite solubility at various values of
temperature,
The presentedpressure
presented model
modelandisNaCl
usedmolality,
for the as shown in of
calculation Figure 10. From
dolomite the figure,
solubility it is shown
at various that of
values
dolomite
temperature, solubility
temperature, pressure in
pressure and water
and NaCl increases
NaCl molality, with pressure and decreases
molality, as shown in Figure 10. From with
From the temperature. In NaCl
the figure, it is shown that
solutions,
dolomite dolomiteinsolubility
solubility water increases with
increases with NaCl molality
pressure and in the lowerwith
decreases salinity range (0–1.5)
temperature. In but
NaCl
solubility in water increases with pressure and decreases with temperature. In NaCl solutions,
decreases in the higher salinity range (1.5–6).
solutions, dolomite solubility increases with NaCl molality in the lower salinity range (0–1.5) but
dolomite solubility increases with NaCl molality in the lower salinity range (0–1.5) but decreases in
decreases
the higherin the higher
salinity rangesalinity
(1.5–6).range (1.5–6).
Energies 2018,
Energies 2018, 11,
11, 2627
x 13 of
13 of 18
18

Energies 2018, 11, x 13 of 18

Figure 10. Dolomite solubility in pure water or NaCl solution calculated by this work at various
Figure10.10.Dolomite
Dolomitesolubility
solubility in
in pure
pure water
water or NaCl solution calculated bybythis
thiswork at at
various
Figure
temperatures, pressures and NaCl molalities.or(a)
NaCl solutionsolubility
Dolomite calculatedvarying work
with various
pressure at
temperatures, pressures and NaCl molalities. (a) Dolomite solubility varying with pressure at
temperatures, pressures and NaCl molalities. (a) Dolomite solubility varying with pressure
different pressures. (b) Dolomite solubility varying with NaCl molality at 343.15 (K) and various at different
different pressures. (b) Dolomite solubility varying with NaCl molality at 343.15 (K) and various
pressures.
pressures. (b) Dolomite solubility varying with NaCl molality at 343.15 (K) and various pressures.
pressures.
3.2. Mutual Effects of Dissolutions of Gases and Minerals
3.2.3.2.
Mutual
Mutual Effects
EffectsofofDissolutions
DissolutionsofofGases
Gases and
and Minerals
Minerals
When CO2 is injected into a carbonate aquifer, CO2 and carbonate mineral solubility in water
WhenWhenCO CO2 is injected into a carbonate aquifer, CO2 and carbonate mineral solubility in water
2 is injected into a carbonate aquifer, CO2 and carbonate mineral solubility in water
are affected by each other. It has been observed in subsurface hot water recovery projects that
areareaffected
affected byeach
by other.
other. ItIt has
has been
been observed in subsurface
subsurfacehot hotwater
waterrecovery
recoveryprojects
projects that
carbonate mineraleach deposition usually observed in
triggers a decrease in permeability, and the subsurface that
fluid
carbonate
carbonate mineral
mineraldeposition
depositionusually
usually triggers
triggers a decrease in
a decrease in permeability,
permeability,and andthe
thesubsurface
subsurface fluid
fluid
can be blocked [2]. CO2 injection into water can re-dissolve the carbonate minerals. The geochemical
cancanbebe blocked [2]. CO injection into
blocked [2]. CO2 injection into water
2 water can re-dissolve the carbonate minerals. The geochemical
re-dissolve the carbonate minerals. The geochemical
model constructed in the previous sections can be used to evaluate the solubility effects of CO2 and
model
model constructed
constructedininthe theprevious
previoussections
sections can be used
used to
to evaluate
evaluatethethesolubility
solubilityeffects
effects
of of
COCO 2 and
2 and
carbonated minerals. The CO2 solubility in pure water and carbonate mineral (calcite and magnesite)
carbonated
carbonated minerals.
minerals.The TheCO CO2 2solubility
solubility in
in pure water
water and
andcarbonate
carbonatemineral
mineral(calcite
(calcite and
and magnesite)
magnesite)
saturated solutions at various values of temperature and pressure is shown in Figure 11. The results
saturated
saturated solutionsatatvarious
solutions variousvalues
values ofof temperature
temperature andand pressure
pressureisisshown
shownininFigure
Figure11.11.
TheTheresults
results
show
show that thethe
that dissolved
dissolved mineral
mineral effects on the
effects on CO
the solubility
2 CO in water
solubility in are insignificant.
water are This isThis
insignificant. because
is is
show that the dissolved mineral effects on CO2 solubility in water are insignificant. This
2
thebecause
solubilitythe of carbonate minerals
solubilityofofcarbonate is
carbonateminerals not significant to change
minerals is not significant the solution properties.
because the solubility significantto tochange
changethethesolution
solutionproperties.
properties.

Figure 11. CO2 solubility in pure water or carbonate mineral saturated solutions at different
temperatures
Figure 11. CO and pressures. Solid lines are CO 2 solubility in puresaturated
water. Dashed lines atrepresent
Figure 11. CO22 solubility
solubility in
in pure
pure water
water or
or carbonate
carbonate mineral
mineral saturated solutions different
solutions at different
calcite saturated
temperatures and solutions.
pressures.Dash-dot
Solid linesare
lines represent
CO magnesiteinsaturated
2 solubility pure solutions.
water. Dashed lines represent
temperatures and pressures. Solid lines are CO2 solubility in pure water. Dashed lines represent
calcite saturated
calcite saturated solutions.
solutions. Dash-dot
Dash-dot lines represent magnesite
lines represent magnesite saturated
saturated solutions.
solutions.
To evaluate the effects of CO2 on solubilities of carbonate mineral influenced by CO2, carbonate
mineral (calcite,the
To evaluate
evaluate magnesite
theeffects and
of
effects ofdolomite)
CO on solubilities
on2solubilities
2CO
in pure
of carbonate
solubilities water andmineral
mineral
of carbonate CO2 saturated
influenced solutions
by CO by are
2, carbonate
influenced CO2 ,
calculated using
mineral (calcite, the presented model at various values of temperature and pressure (Figure 12). It isare
carbonate mineralmagnesite and dolomite)
(calcite, magnesite solubilities
and dolomite) in pureinwater
solubilities and CO
pure water and2 saturated solutions
CO2 saturated solutions
evident from
calculated usingthe
the comparison that the
presented model solubility
at various of all
values of three carbonate
temperature andminerals
pressurein(Figure
water 12).
withIt is
are calculated using the presented model at various values of temperature and pressure (Figure 12). It is
fromthe
evident from thecomparison
comparison
thatthat
the the solubility
solubility of all of all carbonate
three three carbonate
mineralsminerals
in water in water
with with
dissolved
Energies 2018, 11, 2627 14 of 18

Energies 2018, 11, x 14 of 18

CO2 is significantly increased. The increase is higher at the lower temperature (25 ◦ C) than at the higher
dissolved CO2 is significantly increased. The increase is higher at the lower temperature (25 °C) than
temperature (150 ◦ C).
at the higher temperature (150 °C).

Figure 12. Carbonate mineral solubility in pure water or in CO2 saturated solutions. (a) Calcite
Figure 12. Carbonate mineral solubility in pure water or in CO2 saturated solutions. (a) Calcite solubility.
solubility. (b) Magnesite solubility. (c) Dolomite solubility.
(b) Magnesite solubility. (c) Dolomite solubility.

3.3.
3.3. Impurity
Impurity Effects
Effects on
on Gas-Water-Mineral
Gas-Water-Mineral Equilibria
Equilibria
In
In CO
CO22 geologic
geologicprojects,
projects,the
theevaluation
evaluationof ofthe
theeffects
effectsof
of impurities
impurities (such
(such as
as NN22,, O
O22)) in
in terms
terms of
of
water properties(density,
water properties (density, viscosity,
viscosity, pH),pH), gas-water-mineral
gas-water-mineral equilibria,
equilibria, and reservoir
and reservoir property property
change
change
(porosity(porosity and permeability)
and permeability) is an important
is an important topic, sincetopic, since decreasing
decreasing CO2 purity CO 2 purityreduces
efficiently efficiently
the
reduces
cost of COthe2 cost of CO
capture. 2 capture.to
Compared Compared to CO2-water-mineral
CO2 -water-mineral systems, N2systems, N2 orthe
or O2 affects O2CO affects
2
the CO
dissolution 2

dissolution and solute concentration in water. At the same temperature and pressure,
and solute concentration in water. At the same temperature and pressure, the presence of N2 or O2 the presence
of
in N 2 or
gas O2 inchanges
phase gas phase changes of
the fugacity theCOfugacity of CO2, and the CO2 solubility in water (Figure 13).
2 , and the CO2 solubility in water (Figure 13). The carbonate
The carbonate
dissolution dissolution isaffected
is significantly significantly
by COaffected by CO2 concentration in water as shown from the
2 concentration in water as shown from the calculations in
calculations in the
the previous section. previous section.
Energies 2018, 11, 2627 15 of 18
Energies 2018, 11, x 15 of 18

Figure 13. Phase equilibria of CO2-brine-calcite and CO2-N2-brine-calcite at 100 (°C) and 300 (bar). (a)
Figure 13. Phase equilibria of CO2 -brine-calcite and CO2 -N2 -brine-calcite at 100 (◦ C) and 300 (bar). (a)
CO2 molality varying with NaCl molality. (b) Ca2+ 2+ molality and pH varying with NaCl molality; solid
CO2 molality varying with NaCl molality. (b) Ca molality and pH varying with NaCl molality; solid
lines are Ca molality, and dashed lines are pH.
2+
lines are Ca2+ molality, and dashed lines are pH.
4. Conclusions
4. Conclusions
COCO 2 geologic storage with impurities (such as N 2 and O2) is an important choice for reducing
2 geologic storage with impurities (such as N2 and O2 ) is an important choice for reducing the
the cost of the full chain of CCS. However, the phase behavior of CO2-impurities-mineral systems is
cost of the full chain of CCS. However, the phase behavior of CO2 -impurities-mineral systems is key to
key to understanding the migration, storage capacity and safety when CO2 and impurities are
understanding the migration, storage capacity and safety when CO2 and impurities are injected into
injected into subsurface porous media. Rodrigues et al. [55] analyzed the CO2 utilization and storage
subsurface porous media. Rodrigues et al. [55] analyzed the CO2 utilization and storage mechanisms
mechanisms of different technologies (such as CO2 enhanced coal seam recovery and shale gas
of different technologies (such as CO2 enhanced coal seam recovery and shale gas recovery).
recovery). From the analysis in their work, fluid-mineral interactions and CO2 storage capacities are
From the analysis in their work, fluid-mineral interactions and CO2 storage
dramatically different in CO2 utilization and storage projects with
capacities are dramatically
different technologies. Fluid
different in CO2modeling
equilibrium utilizationisand a storage
basis for projects with different
the analysis. In this technologies. Fluid equilibrium
work, a thermodynamic modeling
model of
is aCO
basis for the analysis. In this work, a thermodynamic
2-N2-O2-brine system equilibria is established with a temperature
model of CO 2 -N -O
2 range
2 -brinefrom 0–250 (°C), a is
system equilibria
established with afrom
pressure range temperature
1–1000 (bar)rangeand from a NaCl (◦ C), a pressure
0–250molality range from range 0 tofrom
more 1–1000
than (bar) and aThe
6 (molal). NaCl
molality
model range from 0with
is validated to more thanexperimental
existing 6 (molal). The model
data fromissubsystems,
validated with suchexisting
as CO 2experimental
-brine, N2-brine,data
from subsystems, such as CO -brine, N -brine,
O2-brine, and CO2-N2-brine,2 in terms 2of gas solubility O 2 -brine, and CO
in brine and 2 -N 2H 2O solubility in gas phase. The in
-brine, in terms of gas solubility
brine and H2 Oshows
comparison solubility in gas
that the phase. Thedata
experimental comparison
can be well shows that theby
reproduced experimental
the presented data can be well
model.
reproduced WhenbyCO the presented
2 is dissolvedmodel.in an aquifer, water properties are changed in terms of pH, alkalinity,
cation
When andCO anion concentrations.
2 is dissolved Mineral water
in an aquifer, dissolution and precipitation
properties are changedare in affected
terms ofby thealkalinity,
pH, water
property change. In this work, the thermodynamic model of CO
cation and anion concentrations. Mineral dissolution and precipitation are affected by the water 2-N 2 -O 2-brine system is extended to
CO2-N2change.
property -O2-brine-carbonate
In this work, (mainly calcite, magnesite
the thermodynamic model and
of COdolomite) systems. With the new
2 -N2 -O2 -brine system is extended
to gas-water-mineral
CO2 -N2 -O2 -brine-carbonategeochemical(mainly model, the following
calcite, calculations
magnesite can be performed:
and dolomite) systems. With the new
The mineral solubility can be calculated with CO
gas-water-mineral geochemical model, the following calculations can be performed: 2 and/or other impurity gas components (N 2

andThe O2)mineral
dissolved. The comparisons
solubility with existing
can be calculated withexperimental
CO2 and/ordata show
other that carbonate
impurity (calcite,
gas components
magnesite and dolomite) solubility can be reproduced well by the presented model. It is also shown
(N2 and O2 ) dissolved. The comparisons with existing experimental data show that carbonate
by the calculations at various values of temperature and pressure that carbonate solubilities raise
(calcite, magnesite and dolomite) solubility can be reproduced well by the presented model. It is
considerably with CO2 dissolved in brine.
also shown by the calculations at various values of temperature and pressure that carbonate solubilities
Gas solubility in brine affected by carbonate dissolution in water is evaluated by the model.
raise considerably with CO2 dissolved in brine.
The effects of carbonate dissolution are not significant, because there is a lower level of mineral
Gas solubility in brine affected by carbonate dissolution in water is evaluated by the model.
solubility in water.
The effectsIon of carbonate dissolution
concentrations and pH can are benotcalculated
significant,bybecause
the model thereatisvarious
a lowertemperatures,
level of mineral solubility
pressures
in water.
and salinities. The effects of gas impurities on pH and Ca2+ concentration are evaluated in this work.
Ion concentrations
When CO2 is mixed with and N2pH or O can be calculated by the model at various temperatures, pressures
2, less mineral dissolution, lower Ca2+ concentration and higher pH
and salinities.
can be observedThe fromeffectstheofcalculation.
gas impurities on pH and
The change Ca2+ because
is mainly concentration of the CO are2 evaluated in this work.
fugacity reduction in
When CO2 iswith
gas phase mixed thewith N2 orofON22, or
presence less
O2mineral
, and thedissolution,
effect of N2 or lower Ca2+ concentration
O2 dissolution and higher pH
is not significant.
can be observed
To address fromthe the validation
calculation.ofThethe change
model, is mainly
futurebecause
work of the COsupply
should 2 fugacity reduction in
experimental
gasmeasurements
phase with the of presence of N2 orofOmore
phase behaviors 2 , and the effect
complex of N2 at
systems orvarious
O2 dissolution
temperatures is notand
significant.
pressures,
such as phasethe
To address equilibrium
validationofofCO the2-O 2-brinefuture
model, and CO 2-N2should
work -O2-brine, and experimental
supply carbonate dissolved water
measurements
of properties (i.e., different
phase behaviors of more ion concentrations,
complex systems pH and/or
at variousalkalinity) with different
temperatures levels of CO
and pressures, 2, N2 as
such
Energies 2018, 11, 2627 16 of 18

phase equilibrium of CO2 -O2 -brine and CO2 -N2 -O2 -brine, and carbonate dissolved water properties
(i.e., different ion concentrations, pH and/or alkalinity) with different levels of CO2 , N2 and/or O2 in the
system. In real geologic systems, geochemical reactions are much more complicated. More work is still
needed to assess the impurity effects on gas-water-mineral geochemical behaviors, especially when there
are redox reactions in the systems. In future work, minerals with different chemical valences such as
sulfides and sulfates will be considered to evaluate influences of oxygen.

Author Contributions: J.L. conducted the modeling work, wrote and revised the manuscript. R.A. worked on
part of the coding and reviewed the manuscript. X.L. reviewed and revised the manuscript.
Funding: This research was funded by National Natural Science Foundation of China (Grant No. 41502246) and
National Key R&D Program of China (Grant No. 2016YFE0102500).
Acknowledgments: Thanks to two anonymous reviewers for constructive suggestions.
Conflicts of Interest: The authors declare no conflict of interest.

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