Applied Energy 227 (2018) 49–63

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

The influence of complicated fluid-rock interactions on the geothermal T

exploitation in the CO2 plume geothermal system☆
⁎⁎ ⁎⁎⁎ ⁎
Guodong Cuia,c, , Shaoran Rena, Zhenhua Ruib, , Justin Ezekielc, Liang Zhanga, ,
Hongsheng Wangd
a
School of Petroleum Engineering, China University of Petroleum (East China), Qingdao 266580, China
b
Department of Mechanical Engineering, Massachusetts Institute of Technology, Boston 02139, USA
c
Geothermal Energy and Geofuids Group, Department of Earth Sciences, ETH-Zurich, 8092 Zurich, Switzerland
d
College of Engineering & Mines, University of North Dakota, Grand Forks 58203, USA

H I G H L I G H T S

• Comprehensive fluid-rock interaction models were built for CPG system study.
• Back and down flow of water complicates fluid-rock interactions near injector.
• Salt precipitation can affect geochemical reaction during geothermal development.
• Geochemical reaction and salt precipitation reduce heat mining rate up to 2/5.
• Low salinity water injection can effectively reduce salt precipitation in CPG.

A R T I C L E I N F O A B S T R A C T

Keywords: The ubiquitous natural sedimentary reservoirs and their high permeability have made the CO2 plume geothermal
CO2-plume geothermal system increasingly attractive. However, the complicated fluid-rock interactions during the geothermal ex-
Back flow of formation water ploitation can cause severe reservoir damage, constraining the excellent heat mining performance of the CO2 and
Geochemical reactions decreasing the possible applications of the CO2 plume geothermal system. In order to analyze and solve this
Salt precipitation
energy issue affecting the geothermal exploitation, in this study, a comprehensive numerical simulation model
Heat mining rate
was established, which can consider formation water evaporation, salt precipitation, CO2-water-rock geo-
chemical reactions, and the changes in reservoir porosity and permeability in the CO2 plume geothermal (CPG)
system. Using this model, the geochemical reactions and salt precipitation and their effects on the geothermal
exploitation were analyzed, and some measures were proposed to reduce the influence of fluid-rock interactions
on the heat mining rate. The simulation results show that the gravity and the negative gas-liquid capillary
pressure gradient induced by evaporation can cause the formation water to flow toward the injector. The back
flow of the formation water results in salt precipitation accumulation in the injection well region, which can
cause severe reservoir damage and consequent reductions to the heat mining rate. The CO2-water-rock geo-
chemical reactions could result in the dissolution of certain minerals and precipitation of others, but its minimal
influence on the heat mining rate can be ignored. However, salt precipitation can affect the geochemical re-
actions by influencing the CO2 flow and distribution, which can reduce the heat mining rate up to 2/5 of the
original. Sensitivity studies show that the reservoir condition can affect the salt precipitation and heat mining
rate, so a sedimentary reservoir with high temperature, high porosity and permeability, and low salinity should
be selected for CPG application, with an appropriately high injection-production pressure difference. The in-
jection of low salinity water before CO2 injection and the combined injection of CO2 and water vapor can be
applied to reduce the salt precipitation and increase the heat mining rate in the CPG system.

☆
The short version of the paper was presented at ICAE2016 on Oct 8-11, Beijing, China. This paper is a substantial extension of the short version of the conference paper (Original
paper title: ‘‘Combined effects of geochemical reactions and salt precipitation on geothermal exploitation in the CPG system” and Paper No.:957).
⁎
Corresponding author.
⁎⁎
Corresponding author at: School of Petroleum Engineering, China University of Petroleum (East China), Qingdao 266580, China.
⁎⁎⁎
Corresponding author.
E-mail addresses: cgdcui@163.com (G. Cui), zhenhuarui@gmail.com (Z. Rui), zhangliangkb@163.com (L. Zhang).

https://doi.org/10.1016/j.apenergy.2017.10.114
Received 4 January 2017; Received in revised form 20 October 2017; Accepted 30 October 2017
Available online 06 December 2017
0306-2619/ © 2017 Elsevier Ltd. All rights reserved.
G. Cui et al.
Nomenclature
Symbols
a the dimensionless association coefficient of H2O, 2.6
A the reactive specific surface area for the reactant mineral
β, m2/m3
A0 the reactive specific surface area for the reactant mineral β
at the initial time, m2/m3
DCO2 the diffusion coefficient of CO2 in the formation water,
m2/s
Eβ the activation energy for mineral reaction β, J/mol
fCO2,g the fugacity of CO2 in the gas is phase, MPa
fCO2,w the fugacity of CO2 in the aqueous phase, MPa
fH2O,g the fugacity of H2O in the gas is phase, MPa
fH2O,w the fugacity of H2O in the aqueous phase, MPa
f Hs 2 O the fugacity of H2O at saturation pressure, MPa
fH2O the fugacity of pure H2O at any one pressure and tem-
perature, MPa
s
HCO 2
Henry’s constant of CO2 at the H2O saturation pressure
HCO2 Henry’s constant at pressure at zero salinity, MPa
Hsalt,CO2 Henry’s constant of CO2 in brine, MPa
ksalt,CO2 the salt-out coefficient for CO2, kg/mol
Keq,a the chemical equilibrium constant for the intra-aqueous
reaction a, dimensionless
Keq,β the chemical equilibrium constant for the mineral reaction
β, dimensionless
kβ the rate constant of mineral reaction β, mol/(s m2)
kβ∗ the rate constant of the mineral reaction β at 25 °C, m mol/
s K−i
k the current reservoir permeability, md
k0 the initial reservoir permeability, md
msalt the molality of the dissolved salt, mol/kg H2O
MH2O the molar mass of H2O, g/mol
naq the number of ions in the intra-aqueous reaction, a
Nβ the mole number of mineral β per unit rock volume at the
current time, mol/m3
Nβ0 the mole number of mineral β per unit rock volume at the
1. Introduction
Geothermal energy has several advantages, including large reserves,
wide distribution, and low carbon emissions and was considered to be
one of the promising supplements to fossil energy [1,2]. The current
surveys show that there are more than 14 × 1024 J and 25 × 1024 J of
geothermal reserves, respectively, in the U.S. and China [3,4]. How-
ever, the conventional geothermal reservoirs are usually located in the
tectonically or volcanologically active regions and have small reservoir
volumes, limiting wide developments and the utilization of the geo-
thermal resources [5]. Therefore, some new methods will have to be
developed to extract the abundant geothermal energy from the sub-
surface [6–8]. Meanwhile, the global warming induced by continuous
emissions of greenhouse gases can result in the melting of mountain
glaciers and the rise of the sea level [9,10]. CO2 is the primary green-
house gas, and some measures must be taken to control and decrease
the CO2 concentration in the atmosphere [10–12].
In recent years, with the development of technology [13–16], some
fluids were proposed as the working fluid to exploit geothermal energy
[17,18] and CO2 was also proposed as a heat transmission fluid this can
combine the geothermal exploitation and CO2 greenhouse gas emission
reduction effectively [19–27]. Compared to water as a conventional
heat transmission fluid, CO2 has many advantages for geothermal ex-
ploitation. At normal reservoir conditions, CO2 will be in its super-
critical state of low viscosity, high density, and high heat capacity,
50
Applied Energy 227 (2018) 49–63
initial time, mol/m3
Nsalt the mole number of precipitated salt per unit rock volume
at the current time, mol/m3
Nsalt0 the mole number of precipitated salt per unit rock volume
at the initial time, mol/m3
n an index, integer
p the reservoir pressure at the current time, MPa
pHs 2 O the saturation pressure of H2O, MPa
p0 the reference pressure at the initial time, MPa
Qa the activity product of the intra-aqueous reaction a, di-
mensionless
Qβ the activity product of the mineral reaction β, di-
mensionless
Raq the number of intra-aqueous reactions
rβ the rate of the mineral reaction β, mol/(s m3)
T′ the temperature in °F, °F
Tc,H2 O the critical temperature of CO2, K
T the temperature in K, K
Tc the temperature in °C, °C
vH2O the molar volume of H2O, cm3/mol
v CO2 the partial molar volume of CO2 at the boiling point, m3/
mol
v the stoichiometric coefficient, dimensionless
yH2O,w the mole fraction of H2O in the aqueous phase, di-
mensionless
Greek letters
ζi the coefficient for calculating the chemical equilibrium,
μ the viscosity of the formation water (Pa s)
ρβ the molar density of the mineral β, mol/m3
ρsalt the molar density of the solid salt, mol/m3
Φ the current reservoir porosity after considering salt dis-
solution, geochemical reaction, and pressure changes
Φ0 the initial reservoir porosity
∂k the activity of component k
which can increase the injectivity and heat mining rate [19,22,25].
Meanwhile, due to the large compressibility of CO2, the temperature
difference between injection and production wells can result in a sig-
nificant thermo-siphon effect, which can be fully utilized to decrease
the parasitic power consumption [20,21,26].
The concept of using supercritical CO2 as a heat transmission fluid
was first proposed in a geothermal exploitation from Hot Dry Rock by
Brown (CO2-EGS) [19]. Subsequently, Pruess et al. studied the flow
characteristics and heat mining rate in the CO2-EGS in detail [20,21].
However, the ultra-deep well fracturing used in the CO2-EGS may cause
seismicity, which makes the economic benefits and reservoir sealing
uncertain. To solve these questions, Randolph et al. proposed a concept
of using CO2 to exploit the geothermal from a natural high-permeability
reservoir that is overlain by a low-permeability cap rock and this con-
cept is called CO2-plume geothermal (CPG) system [22]. Natural high-
temperature reservoirs are ubiquitous throughout the world and have
larger pore volumes than the tight hot dry rocks [28], which means
more CO2 can be sequestrated [29] and more geothermal can be
exploited. Also, the CPG system can reduce or eliminate the need for
complex and expensive hydraulic fracturing that is typically required in
the EGS system [22,23,27]. These advantages make the CPG system
attract more and more attention all over the world [30,31].
However, there are still some issues with using CO2 to exploit
geothermal energy. Compared with the CO2-EGS, more formation water
is initially stored in the natural high-permeability reservoirs, which
G. Cui et al.
means there is a period for water production before CO2 production in
the CPG system. Some literature has indicated that the production of
formation water can decrease the heat mining rate because of the high
viscosity of the water [23,25]. Moreover, the formation water will react
with the injected CO2 and then change the reservoir porosity and per-
meability [32,33], which can affect the exploitation of geothermal
energy. Usually, three distinct zones can form and develop with the
continuous CO2 injection during geothermal exploitation [19,32]: a
single phase of dry CO2, two phases of CO2-water mixture, and a single
phase of water with some dissolved CO2. The injected CO2 and the
water will chemically react with the rock minerals in the zones of the
two-phase CO2-water mixture and the single-phase water with dis-
solved CO2, which results in mineral changes. Whereas in the zone of
the two-phase CO2-water mixture, the formation water, especially the
irreducible water, will evaporate into the CO2 phase and then increase
the dissolved Na+ and Cl− concentration; this can result in salt pre-
cipitation and damage the reservoir [32,34]. Meanwhile, the develop-
ment of the three zones can affect the geochemical reactions and salt
precipitation, which complicates the geochemical reactions and salt
precipitation and may intensify their influence on the heat mining rate.
Studies on CO2 storage in conventional aquifers and sedimentary
formations have demonstrated that the chemical equilibrium in the
formation water can be broken after CO2 injection, which can result in
different geochemical reactions involving mineral dissolution and pre-
cipitation [10,35–38]. Moreover, high reservoir temperature in the CPG
system can accelerate the reaction rate and induce simultaneous
changes to the reservoir porosity and permeability, which can sig-
nificantly affect the heat mining rate [32,39,40]. Some researchers have
performed the CO2-formation water-rock geochemical reactions. Ueda
et al. conducted laboratory experiments in a CO2-water-rock system,
which indicated that the presence of CO2 could promote the dissolution
of plagioclase and anorthite minerals and the precipitation of carbonate
substances [40]. Wan et al. proposed a two-dimension reactive trans-
port simulation model to study the geochemical reactions in a CO2-
water-rock system and assessed their impact on fluid flow [41]. Xu et al.
studied the influence of CO2-water-rock interactions on the heat mining
rate through a two-dimension reactive transport simulation model in a
CPG system [32]. All of these studies showed that the CO2-water-rock
geochemical reactions could change the reservoir porosity and a certain
amount of CO2 can be trapped or stored in the products of mineral
reactions.
For the salt precipitation, some experiments and simulation re-
search has been conducted. The core flooding experiments indicated
that the CO2 injection could result in salt precipitation, which can lead
to low permeability and decrease the CO2 injectivity [42–45]. Further,
some CT scans revealed that a locally higher salt precipitation could
occur in the area near the injection well [45,46]. Regarding the simu-
lation aspects, many multi-phase reactive flow simulations suggested
that the evaporation of formation water can result in salt precipitation,
which would damage the reservoir and reduce the heat mining rate
[29,31]. For example, the Spycher et al. [47] model of geothermal
exploitation from Hot Dry Rock showed that significant salt precipita-
tion clogging occurred in the production region for a low-salinity
system, while clogging in the injection area occurred for a high-salinity
system. Our previous research also indicated that local high salt pre-
cipitation could severely damage the reservoir due to a back flow of the
formation water under some conditions [25]. All of these research in-
dicated that salt precipitation could change the reservoir porosity and
permeability and affect the fluid flow in the geothermal exploitation
using CO2.
As the description above, although the geochemical reactions and
salt precipitation are just physical and chemical reactions from a geo-
physical perspective, they will become directly relevant to the energy
issues when these fluid-rock interactions occur in the geothermal ex-
ploitation in the CPG system. These fluid-rock interactions can damage
the reservoir, decreasing the permeability and CO2 flow rate, and
51
Applied Energy 227 (2018) 49–63
resulting in the heat mining rate decreasing eventually during geo-
thermal exploitation. In some cases, these fluid-rock interactions even
may totally clog local porosity and interrupt the continuity of geo-
thermal exploitation, which will seriously restrict the development of
geothermal energy. More importantly, the geochemical reactions and
salt precipitation affect each other in the CPG system, and these reac-
tions can affect the formation and development of seepage zones,
which, in turn, can also affect these reactions. Moreover, some studies
show that the formation water will flow back to the injection well under
the actions of evaporation and capillary pressure, which may intensify
the reservoir damage caused by the geochemical reactions and salt
precipitation. However, there is a lack of systemic research work on the
geochemical reaction and salt precipitation, particularly on their com-
bined effects on the reservoir properties and heat mining rate in the
CPG system. Therefore, it is essential and helpful to study their com-
bined effect on the reservoir properties and geothermal energy ex-
ploitation in the actual application of the CPG system.
Therefore, the primary objectives of this work are to study the
combined phenomenon of geochemical reactions and salt precipitation
and their effects on the heat mining rate in the CPG system and thereby
propose some measures to solve this energy issue affecting the geo-
thermal exploitation. In this study, a comprehensive model for geo-
thermal exploitation via CO2 recycling from a natural high-permeability
reservoir was established that considers various processes, including
the dissolution and diffusion of CO2 in formation water, the evaporation
of formation water, geochemical reactions, salt precipitation, and the
variations of porosity and permeability. The flow behavior of the CO2,
geochemical reactions, salt precipitation, and their combined effects on
the heat mining rate was analyzed, and the influences of reservoir
pressure and temperature, the porosity, the permeability, the salinity of
formation water, and the injection-production pressure difference were
studied. In the end, techniques for preventing and mitigating the for-
mation damage caused by these fluid-rock interactions are proposed
and evaluated to enhance the heat mining rate during the real appli-
cation of the CPG system.
2. Comprehensive model for the CO2 geothermal exploitation
system
2.1. Mathematical models
2.1.1. Evaporation and dissolution of water
The formation water will continuously evaporate into the CO2 phase
during CO2 injection, and a high temperature and continuous injection
can significantly accelerate the evaporation. It is reasonable to assume
the gaseous and aqueous phases are in thermodynamic equilibrium
during CO2 injection and the following equation of the equality of fu-
gacity was adopted for modeling the evaporation and dissolution of
H2O in the simulation:
fH2 O,g = fH2 O,w (1)
where fH2O,g is the fugacity of the H2O in the gas phase (MPa), which
can be calculated from an equation of state (EOS) [48]; and fH2O,w is the
fugacity of the H2O in the aqueous phase (MPa).
For calculating the fugacity of the saturated H2O ( f Hs 2 O ), the equa-
tions below were used [49]:
f Hs 2 O ⎧ 0.95958 + 9.66833 × 10−5T ′−6.175′ × 10−7T ′
2
= −10 ′ 3
′
−3.08333 × 10 T ,T > 90°F
PHs 2 O ⎨
1, otherwise (2)
⎩
where f Hs 2 O is the fugacity of the H2O at the saturation pressure and T′ is
the temperature in °F.
Then, the fugacity of the H2O at any pressure and temperature was
calculated based on the fugacity of the saturated H2O using:
G. Cui et al. Applied Energy 227 (2018) 49–63

p v H2 O ⎞ 30
fH2 O = f Hs 2 O exp ⎜⎛ Wilke model calculated
∫p dp⎟

Diffusion coefficients of CO2 in

s
⎝ H2 O RT ⎠ (3) Experiment results calculated [57]
24 Experiment results calculated [58]
where fH2O is the fugacity of the H2O at any one pressure and tem- Experiment results calculated [59]

water, 10-9m2/s
perature; p is the reservoir pressure; pHs 2 O is the saturation pressure of 18
H2O at any one temperature and was calculated using the method in
Ref. [50]; T is the temperature in K; and vH2O is the molar volume of the 12
H2O, which can be calculated by the method in Ref. [51].
Lastly, the fugacity of the H2O considering the solvent can be ac-
6
curately calculated using:
fH2 O,w = yH2 O,w ·fH2 O (4) 0
270 320 370 420 470 520
where yH2O,w is the mole fraction of the H2O in the aqueous phase. Temperature, K
Fig. 1. Diffusion coefficients of CO2 in the formation water under different temperature.
2.1.2. Evaporation and dissolution of CO2
Most of the injected CO2 will be in the gas phase, and a part of the
injected CO2 will dissolve into the aqueous phase during the geothermal formation water [55] using:
exploitation using supercritical CO2 as the heat transmission fluid. As
7.4 × 10−15 (aMH2 O)0.5T
was done with the H2O, the equality of fugacity equation was used to DCO2 = 0.6
μvCO (11)
model the evaporation and dissolution of CO2 during geothermal ex- 2

ploitation using supercritical CO2: where DCO2 is the diffusion coefficient of CO2 in the formation water;
fCO2,g = fCO2,w (5) MH2O is the molar mass of H2O, a is the dimensionless association
coefficient of the H2O (the value is 2.6); μ is the viscosity of the for-
where fCO2,g is the fugacity of the CO2 in the gas phase, which can be mation water and can be calculated using the method used in Ref. [56];
calculated from an equation of state (EOS) [48]; fCO2,w is the fugacity of and v CO2 is the partial molar volume of the CO2 at the boiling point and
the CO2 in the aqueous phase and was calculated using the procedure its value is 34 cm3/mol.
described below: Fig. 1 shows the diffusion coefficients of the CO2 in water calculated
First, Henry’s constant at the H2O saturation pressure was calcu- by the Wilke-Chang model and the experimental results [57–59]. It can
lated using the following equation [52]: be seen that there is good agreement between the diffusion coefficients
s calculated by the model and experimental results, especially in the
lnHCO = lnpHs 2 O −9.4234(T /Tc,H2 O )−1
2 temperature ranges of 270 K and 370 K, which means that the Wilke-
+ 4.0087(1−T / Tc,H2 O )0.355 (T / Tc,H2 O )−1 Chang model can be used in this study for calculating the diffusion
coefficients of CO2 in the formation water.
+ 10.3199[exp(1−T / Tc,H2 O )](T / Tc,H2 O )−0.41 (6)
s
where HCO 2
is Henry’s constant of CO2 at the H2O saturation pressure; 2.1.4. Geochemical reactions and salt precipitation
Tc,H2O is the critical temperature of CO2. 2.1.4.1. CO2-formation water-rock geochemical reactions. Compared to
Then, Henry’s constant at any pressure was calculated using the the conventional CO2 geological storage that can result in mineral
flowing equation: dissolution and precipitation in the long term, the geothermal
1 p reservoir’s high temperature will accelerate the geochemical reaction
s
lnHCO2 = lnHCO 2
+
RT
∫p s
H2 0
vCO2 dp
(7) rate, which may significantly affect the heat mining rate in a short span
of time. In this study, the geochemical reactions are divided into two
where HCO2 is Henry’s constant at a certain pressure at zero salinity; p is types of reactions: intra-aqueous reactions and mineral reactions.
the reservoir pressure; vCO2 is the partial molar volume of CO2 and was The intra-aqueous reactions are defined as the reactions that in-
calculated using the following equation [53]: volved H+ and OH and occurred in the aqueous phase after the CO2 was
vCO2 = 37.51−9.585 × 10−2T c + 8.74 × 10−4T c 2−5.044 × 10−7T c3 (8) dissolved in the water. Because the intra-aqueous reaction can be
considered a relatively fast process [60], it is reasonable to assume its
c
where T is the temperature in °C. equilibrium can be reached instantaneously and therefore there is no
Lastly, Henry’s constant considering the solvent was calculated need to consider its kinetics during simulation.
using: The chemical equilibrium in the simulator is modeled using the
following equations:
Hsalt ,CO2 ⎞
ln ⎛⎜ ⎟ = ksalt ,CO 2 msalt
Qa = K eq,a a = 1,2⋯Raq (12)
⎝ HCO2 ⎠ (9)
naq
where Hsalt,CO2 is Henry’s constant of the CO2 in brine; msalt is the
molality of the dissolved salt; and ksalt,CO2 is the salt-out coefficient for Qa = ∏ ∂kv
k=1 (13)
CO2 and was calculated using the following equation [54]:
where Keq,a is the chemical equilibrium constant for the intra-aqueous
ksalt ,CO2 = 0.11572−6.0293 × 10−4T c + 3.5817 × 10−6T c 2−3.7772 × 10−9T c3
reaction a; ∂k is the activity of component k; v is the stoichiometric
(10) coefficient; Qa is the activity product; Raq is the number of the intra-
aqueous reactions; and naq is the number of ions in reaction a.
2.1.3. Diffusion of CO2 in the aqueous phase Regarding the calculation of the chemical equilibrium constant, it is
The dissolved CO2 diffuses in the formation water, which can affect modeled as a fourth order polynomial function of temperature [61,62]:
the contact area between the CO2 and formation water; therefore, the logK eq,a = ζ 0 + ζ1 T c + ζ2 T c 2 + ζ3 T c3 + ζ 4 T c 4 (14)
CO2 diffusion is essential for accurately simulating CO2-water-rock
geochemical reactions. In this section, the Wilke-Chang molecular dif- where T is the current reservoir temperature in °C and the coefficient ζi
c

fusion model is used to calculate the diffusion coefficient in the is given in Table 4 for the related intra-aqueous reactions in this paper.

52
G. Cui et al. Applied Energy 227 (2018) 49–63

The mineral reactions are defined as the reactions involving various and CO2 geochemical reactions, the salt precipitation is still named as
aqueous and mineral components in the reservoir. Similar to the intra- salt precipitation, although its modeling method is the same as the CO2
aqueous reactions described above, the chemical equilibrium constant geochemical reactions.
of the mineral reactions can also be modeled using Eqs. (12)–(14) and
their coefficients are also given in Table 4 [62]. However, the rate of the 2.1.5. Variation of porosity and permeability
mineral reactions is much lower than that of the intra-aqueous reac- Salt precipitation, geochemical reactions, and reservoir pressure can
tions and the equilibrium of the reaction cannot be achieved in- affect the reservoir porosity, then result in a change in the reservoir
stantaneously. Therefore, a kinetics model was needed to calculate the permeability. Therefore, the relationship of porosity and permeability
reaction rate and time taken for the reaction to reach equilibrium [62]: must be considered. The variation of reservoir porosity can be modeled
using the following equation [66]:
Qβ ⎞
rβ = Akβ ⎛⎜1− ⎟ β = 1,2⋯Rm β R 0 0
⎝ K eq,β ⎠ (15) ⎡ ⎛ Nβ−N β Nsalt −Nsalt ⎞⎤
ϕ = ⎢ϕ0− ∑ ⎜ + 0
⎟ ⎥·[1 + CΦ (p−p )]
β ⎝
ρβ ρ salt (18)
where rβ is the reaction rate; A is the reactive surface area for the re- ⎣ ⎠⎦
actant mineral β; kβ is the rate constant of reaction β and it is tem- where Φ is the current reservoir porosity considering salt dissolution,
perature dependent; Keq,β is the chemical equilibrium constant for re- geochemical reaction, and pressure changes; Φ0 is the initial reservoir
action β that also can be calculated using Eq. (14); and Qβ is the activity porosity; Nsalt is the number of moles of precipitated salt per unit rock
product that can be calculated using Eqs. (12) and (13). volume at the current time; Nsalt0 is the number of moles of precipitated
The rate constant of the reaction under a different temperature can salt per unit rock volume at the initial time; ρβ is the molar density of
be modeled using the following equation: the mineral β; ρsalt is the molar density of the salt in its solid state; p is
Eβ 1 1 the current reservoir pressure; and p0 is the reference pressure at the
kβ = kβ∗exp ⎡− ⎛ − ⎞ ⎤
⎜ ⎟
initial time.
⎢ R ⎝ T T0 ⎠ ⎥ (16)
⎣ ⎦ The variation of permeability with the porosity change can be
where Eβ is the activation energy for mineral reaction β, and kβ∗ is the modeled using the following equations [67]:
rate constant of the reaction at 298.15 K (i.e., 25 °C). n 2
ϕ 1−ϕ0 ⎞
The reactive surface area of a specific mineral reactant changes with k = k 0 ⎛⎜ 0 ⎞⎟ ⎛⎜ ⎟

the dissolution/precipitation of the mineral components, which can be ⎝ ⎠ ⎝ 1−ϕ ⎠

correlated with the mole concentration of the mineral component:
Nβ
A= A0
N β0
where A is the reactive specific surface area at the initial time, m /m3;
0 2
Nβ0 is the number of moles of mineral β per unit rock volume at the
initial time; and Nβ is the number of moles of mineral β per unit rock
volume at a current time. All related parameters are given in Tables 3
and 4.
2.1.4.2. Precipitation and dissolution of NaCl. The CO2 injection will
result in continuous evaporation of H2O, which can increase the salinity
of the formation water and make the NaCl eventually precipitate. In the
previous simulation studies of salt precipitation, thermodynamic
models were adopted in the common software TOUGH2/ECO2N
[32,35,47,63,64]. In this study, the mineral reaction model described
above was adopted for simulating the salt precipitation and dissolution
[65]. However, the precipitation and dissolution rates of salt usually are
higher than that of rock minerals, so the related parameters in the
model are modified to simulate this process accurately. In addition, the
precipitation rate is assumed to be the same as the dissolution rate in
this study and the related parameters are given in Tables 3 and 4. At the
same time, to facilitate the distinction between the salt precipitation
ϕ (19)
where k is the current reservoir permeability after considering salt
dissolution, geochemical reaction, and pressure changes; k0 is the initial
reservoir permeability; and n is an index, whose value from previous
(17)
experimental results is 4 [25], but in this study its value was set to 5 to
model the effect of the precipitation-aggregation of minerals and salt in
the pore-throat.
2.2. Reservoir simulation model
Based on the above mathematical models, a comprehensive simu-
lation model, including formation water evaporation, CO2-formation
water-rock geochemical reactions, salt precipitation, and the changes of
reservoir porosity and permeability, was established using a commer-
cial reservoir simulation software: CMG GEM. The software can not
only simulate the multiphase flow, geochemical reactions, and salt
precipitation, it can also calculate the heat transfer between the fluids
and formation rocks [62,65,66]. The key parameters in the model can
be seen in Table 1, which were set according to the physical properties
of a target reservoir in the Songliao Basin, Northeastern China [68,69].
The volume of the high natural permeability geothermal reservoir is
600 m × 500 m × 100 m. All boundaries of the reservoir are enclosed
with no fluid exchange, but heat exchange can take place between the
reservoir and surrounding rock. The initial temperature of the

Table 1
Parameter setting of the comprehensive model for geothermal exploitation in the CO2 geothermal exploitation system.

Parameters Value Parameters Value

Depth, m 3500 Initial water saturation, % 100

Pressure, MPa 35 Gas-liquid relative permeability curve Corey (1954)a
Temperature, C 150 Aqueous phase irreducible saturation 0.3
Porosity, % 10 Gaseous phase irreducible saturation 0.05
Horizontal permeability, md 100 Solubility of CO2 in water, % 2.7
Heat capacity of rock, J·(kg K)−1 840 Solubility of water in CO2, % 10.45
Thermal conductivity of rock,·J·(m s K)−1 2 Diffusion coefficient of CO2 in water, 10−9 m2 s−1 11
Heat capacity of formation water, J kg−1 K−1 4111.6 Salinity, ppm 51,526
Thermal conductivity of water, J·(m s K)−1 0.7 Salinity of NaCl, mg/L 50,000
Heat capacity of CO2, J·(kg K)−1 1744.8 Temperature of injected CO2, °C 40
Thermal conductivity of CO2, J·(m s K)−1 0.07 Displace pressure, MPa 2

a
Parameters used in the Corey model, Swn = 0.3, Sgn = 0.05.

53
G. Cui et al.
surrounding rock is 150 °C and the heat capacity and thermal con-
ductivity of the surrounding rock are the same as those of the reservoir
rock. The burial depth of the reservoir is 3500 m and the initial pressure
and temperature at the top of the reservoir are assumed to be 35 MPa
and 150 °C, respectively. The initial reservoir porosity is 0.1, and the
horizontal and vertical permeability is 100 md and 50 md, respectively.
The injection and production wells are located on opposite ends in the
x-direction of the reservoir and their pressure difference is 2 MPa. In
addition, the effect of the thermal expansion on the reservoir porosity is
not considered in this model because it is not the focus of the research
and it has a small effect. A gas-liquid capillary pressure curve was
adopted in the simulation, as shown in Fig. 2, and its drainage and
imbibition capillary pressure curves are assumed to be the same for
simplicity.
The ionic composition of the formation water and mineral compo-
sition of the rock adopted in this study can be seen in Table 2, which
were set based on a reservoir in the Jilin oilfield in the Songliao Basin,
Northeastern China. However, it should be noted that only three mi-
nerals were analyzed in this study because of their representativeness
and their related chemical reaction equations and related parameters
can be seen in Tables 3 and 4. To compare and analyze the related
effects, other cases based on the base model described in Table 1 were
established, as shown in Table 5. The first three cases were established
to mainly analyze the fluid flow; the fourth case was developed to
analyze the effect of the CO2 geochemical reactions. Case 5 was then
developed to analyze the effect of salt precipitation.
3. One-dimension simulation results and analysis
During the geothermal exploitation in the CPG system, in order to
clearly understand the fluid flow, geochemical reactions, and salt pre-
cipitation, it is useful to first analyze these processes with a one-di-
mension model. In the one-dimension model, the reservoir described in
Table 1 is discretized by non-uniform meshes of 80 × 1 × 1 and small
grids are used in the area near the injection well, starting with 0.1 m
then increasing to 10 m. The injection well is located at the end of the
reservoir where the grids are small; the production well is located at the
end of the reservoir where the grids are big.
3.1. Analysis of fluid flow
Fig. 3 shows the one-dimension distributions of the formation water
saturation in Cases 1, 2, and 3 under different time. As seen in Fig. 3,
the water saturation in Case 2 is always lower than in Case 1 at various
time while the water saturation in Case 3 is always higher than in Case
1, which means the formation water evaporation and gas-liquid capil-
lary pressure play opposite roles in the water flow. To more clearly
understand the influences of the capillary pressure and the water eva-
poration on the water flow, the changes in the formation water sa-
turation in the block where the injection well is located were analyzed.
It can be seen from Fig. 4 that the existence of capillary pressure makes
the decrease rate of the water saturation in Case 1 slower than that in
Case 2, which means the capillary pressure is not conducive to water
flow to the production well. However, the decrease rate of the water
saturation in Case 1 is higher than that in Case 3, meaning the eva-
poration can accelerate the decrease rate of the water saturation and is
conducive to water flow toward the production well.
Fig. 5 shows the one-dimension distribution of formation water flow
velocity in Cases 1, 2, and 3 at different times. As shown, the values in
Cases 2 and 3 are always positive, which means the water always flows
to the production well. However, sometimes the values in the area
about 20 m from the injection well in Case 1 are negative, meaning that
the water can flow back to the injection well. Fig. 6 illustrates the water
flow velocity changes over time in the block where the injection well is
located; as shown, the water can flow back to the injection well in the
early stage of geothermal exploitation. The back flow of formation
54
Applied Energy 227 (2018) 49–63
water is controlled by the evaporation and gas-liquid capillary. During
the geothermal exploitation using CO2, both the high reservoir tem-
perature and continuous CO2 injection intensify the water evaporation
and then result in a high negative water saturation gradient in the area
near the injection well, which increases the gas-liquid capillary pressure
gradient. When the gas-liquid capillary pressure gradient is higher than
the displacement pressure difference in the area near the injection well,
the formation water flows back to the injection well. For the areas away
from the injection well, the CO2 phase has been saturated with the
vapor coming from the irreducible water, which stops the water eva-
poration and the induced back flow. Therefore, not only does the dis-
placement pressure difference affect the water flow, the gas-liquid ca-
pillary and water evaporation also can affect the water flow, especially
in the area near the injection well. It should be noted that the back flow
of formation water may occur only when the water saturation is higher
than the irreducible water saturation; if the water saturation is lower
than the irreducible water saturation, only evaporation occurs.
3.2. Geochemical reactions and salt precipitation
Fig. 7 illustrates the one-dimension distributions of minerals change
and the reservoir porosity after 30 years of geothermal exploitation in
Case 4. It can be seen that the anorthite, especially in the area near the
injection well, dissolves into the formation water, but the calcite and
kaolinite mainly precipitate into the area near the production well,
which results in some CO2 sequestration in the reservoir as calcite. The
reason for the serious anorthite dissolution in the area near the injec-
tion well may be caused by the back flow of the formation water [5].
Under the action of the back flow, the supply of the formation water
delays the water from disappearing in the injection well area, which
prolongs the geochemical reaction time and then increases the mineral
change. Moreover, the continuous evaporation increases the con-
centration of the Na+ and Cl− and subsequently decreases the H2O
fraction, which decreases the activity product of anorthite reaction and
finally makes the anorthite more easily dissolve into the water. Mean-
while, the high temperature in the area near the production well ex-
acerbates the geochemical reactions and then increases the mineral
change. Fig. 8 illustrates the one-dimension distributions of the mi-
nerals and reservoir porosity after 30 years of geothermal exploitation
in Case 5. It can be seen that a severe salt precipitation occurs in the
area near the injection well because a lot of NaCl carried by the back
flow of formation water precipitates under the action of continuous
evaporation. Under the combined actions of the salt precipitation and
the geochemical reactions, the porosity near the injection well de-
creases from 0.1 to 0.09 after 30 years of CO2 injection.
4. Two-dimension simulation results and analysis
Gravity also affects the fluid flow during geothermal exploitation in
the CPG system [71]. Under the action of gravity, the injected CO2 will
Fig. 2. Gas-liquid capillary pressure curve.
G. Cui et al. Applied Energy 227 (2018) 49–63

Table 2
Composition of the formation water and rock minerals.

Ionic composition of the formation water Ion Na+ Al3+ H+ SiO2 Cl− HCO3− CO32− OH−
Concentration/mol L−1 1 2.3 × 10−11 1.0 × 10−6 9.12 × 10−5 1 2.5 × 10−2 1.2 × 10−5 5.5 × 10−6

Mineral composition of the rock Mineral Anorthite Calcite Kaolinite

Fraction/% 0.036 0.153 0.00135

Table 3 Table 5
Kinetic parameters of the mineral reactions and salt precipitation. Simulation cases for sensitivity analysis.

Mineral logk25 °C/ Activation energy/ Initial specific reactive Case Capillary Evaporation of CO2-water-rock Salt precipitation
mol m−2 s−1 J mol−1 surface/m2 m−3 pressure water reaction

Calcite −8.8 41870 88 1 Yes Yes No No

Anorthite −13 67,830 88 2 No Yes No No
Kaolinite −13 62,760 1760 3 Yes No No No
Solid Sal −5 2000 176 4 Yes Yes Yes No
5 Yes Yes Yes Yes
Note: logk25 °C is the logarithm of the rate constant of a reaction at 25 °C; for the salt
precipitation, it is set to −5 and the activation energy of salt precipitation is set to
2000 J mol−1 [65,70].

gradually rise because of the density difference between the CO2 and
water, which can change the shape of the seepage zones. The changes in
these seepage zones will affect the geochemical reactions and salt
precipitation, which can have a great effect on the heat mining rate in
the CPG system. Therefore, gravity must be considered for accurate
modeling of the geothermal exploitation in the CPG system. In this
section, based on the grid in the one-dimension model, the reservoir is
divided into 10 layers in the z-direction to create an 80 × 1 × 10 grid
in the two-dimension model. The injection well is perforated at the
lower 5 layers; the production well is perforated at the upper 5 layers.
As with the analysis of the one-dimension simulation, the five cases
described in Table 5 were also used to analyze the fluid flow, geo-
chemical reactions, salt precipitation, and their influence on the geo- Fig. 3. One-dimension distribution of formation water saturation under different time.

thermal exploitation in the two-dimension simulation.

4.1. Analysis of fluid flow

Fig. 9 illustrates the two-dimension distributions of the CO2 sa-

turation in Cases 1, 2 and 3 under different time. It can be seen that the
injected CO2 flows toward the production under the action of the dis-
placement pressure difference while simultaneously migrating upward
over time under the action of gravity. Under the actions of the dis-
placement pressure difference and gravity, the injected CO2 first forms
a funnel-shaped plume. Then, with continuous CO2 injection, the
formed CO2 plume constantly moves toward the production well and
eventually causes a CO2 breakthrough in the production. Before CO2
breakthrough in the production well, the production fluid is a single
phase (water) because the reservoir is initially full of formation water.
In this situation, there is only the two-phase zone and the single-phase
zone CO2 dissolved in the reservoir, and the CO2 has not yet played a Fig. 4. One-dimension change of formation water saturation in the block where the in-
jection well is located over time.
role in geothermal exploitation. After the CO2 breakthrough in the
production well, the CO2 single-phase zone begins to form in the

Table 4
Chemical reaction and salt precipitation equations and reaction equilibrium coefficients.

Reaction equation ζ0 ζ1 ζ2 ζ3 ζ4

H+ + OH− = H2O 14.9282 −0.0419 1.97 × 10−4 −5.55 × 10−7 7.58 × 10−10
CO2 + H2O = HCO3− + OH− −6.5492 0.0090 −1.02 × 10−4 2.76 × 10−7 −3.56 × 10−10
HCO3− = CO32− + H+ 10.6080 −0.0128 1.20 × 10−4 −3.02 × 10−7 2.69 × 10−10
Calcite + H+ = Ca2+ + HCO3− 2.0689 −1.4267 −6.06 × 10−6 1.46 × 10−7 −4.19 × 10−10
Anorthite + 8H+ = 4H2O + Ca2+ + 2Al3+ + 2SiO2(aq) 3.1746 −0.2012 5.96 × 10−4 −9.04 × 10−7 9.15 × 10−11
Kaolinite + 6H+ = 5H2O + 2Al3+ + 2SiO2(aq) 9.2954 −0.0980 2.92 × 10−4 −3.27 × 10−7 −3.31 × 10−10
Salt = Na+ + Cl− 1.5686 0.0004 5.00 × 10−6 −3.00 × 10−9 −5.00 × 10−12

Note: the coefficient ζI of salt precipitation is calculated by the solubility of NaCl under different temperature.

55
G. Cui et al. Applied Energy 227 (2018) 49–63

Fig. 5. One-dimension distribution of formation water flow velocity under different time.
Fig. 6. One-dimension change of formation water flow velocity in the block where in-
jection well is located over time.
reservoir and this CO2 acts as a heat transmission fluid for geothermal
exploitation. However, it should be noted that there is still a lot of
formation water in the reservoir after 30 years in two-dimension si-
mulation because the water below the production well cannot be dis-
placed by the CO2.
As can be seen in Fig. 9, the CO2 distribution area in Case 1 is
slightly smaller than that in Case 2, but is slightly larger than that in
Case 3. This indicates that the capillary pressure is adverse to CO2 flow
to the production well, but water evaporation is conducive to CO2 flow
to the production well (as with the results of the one-dimension simu-
lation). However, it should be noted that the CO2 saturation distribu-
tions in the area near the injection well in different cases differ. In Case
1, the CO2 saturation in the area near the injection well perforations is
lower than that in other areas. This is because not only can the back
flow of formation water affect the fluid flow, but the gravity can also
result in the formation water above the perforation flowing down to the
injection well in Case 1. As shown in Fig. 10a, under the combined
actions of the back flow and gravity-caused down flow, all water near
the injection well, including the upper areas to the right, flows to the
perforation, resulting in a high water saturation in the injection well
area. In Case 2, only the CO2 saturation in the area of upper perforation
is lower than that in other areas. This is because only the water above
the perforation caused by the gravity flows down to the injection well
due to water evaporation (as shown in Fig. 10b). As for Case 3, the
water saturation is always higher than the irreducible water saturation
and the change in the water saturation is slow due to the inexistence of
water evaporation, which makes the water down flow caused by gravity
different from that in Case 2 and eventually results in the CO2 satura-
tion being evenly distributed. Therefore, gravity not only affects the
shape of the CO2 plume and seepage zones, but also has an effect on the
water flow in the area near the injection well during the geothermal
exploitation in the CPG system.

4.2. Geochemical reactions and salt precipitation

Fig. 11 shows the two-dimension distributions of the CO2 saturation,

minerals change, porosity, and permeability after 30 years of CO2 in-
jection in Case 4. It can be seen that almost all formation water in the
reservoir has been completely evaporated because of the continuous
injection of the dry CO2, and the CO2 distribution area in Case 4 is
almost the same as that in Case 1. As shown in Fig. 11, the region of
anorthite dissolution and calcite and kaolinite precipitation is almost
same as the CO2 saturation distribution. However, compared to the
mineral changes in the one-dimension simulation, the minerals change
in the area near the injection well is small. This is because the CO2
injection rate in the single grid near the injection well in the two-di-
mension model is higher than that in the one-dimension model, which
accelerates the water evaporation and then weakens the effect of the
Fig. 7. One-dimension distributions of minerals change and porosity after 30 years in back flow on the geochemical reactions. Meanwhile, it can be seen that,
Case 4.
at the bottom of the production well in two-dimension simulation, there
is the largest mineral change because there are a lot of formation water
in there that can react with the injected CO2 for a long time. In general,
the mineral change caused by the geochemical reactions has little effect
on the reservoir porosity and permeability, as only the porosity and
permeability in the bottom of the production well decrease to 0.096 and
79 md, respectively, due to the serious mineral change.
Fig. 12 shows the two-dimension distributions of the CO2 saturation,
minerals change, porosity, and permeability after 30 years of CO2 in-
jection in Case 5. Apparently, it can be seen that the CO2 distribution
area in Case 5 is smaller than that in Case 4 and there is a large area at
the bottom of the reservoir in Case 5 where the injected CO2 cannot
spread. Because a lot of NaCl is carried to the injection well area under
the combined actions of back flow and gravity-caused down flow, it
then precipitates, which results in a substantial decrease to the porosity
Fig. 8. One-dimension distributions of minerals change and porosity after 30 years in and permeability, as shown in Fig. 12. The low permeability of the
Case 5.
injection well area decreases the CO2 injection rate and then results in a

56
G. Cui et al. Applied Energy 227 (2018) 49–63

a-1 CO2 saturation after 6 months in Case 1 a-2 CO2 saturation after 1 year in Case 1 a-3 CO2 saturation after 30 years in Case 1

b-1 CO2 saturation after 6 months in Case 2 b-2 CO2 saturation after 1 year in Case 2 b-3 CO2 saturation after 30 years in Case 2

c-1 CO2 saturation after 6 months in Case 3 c-2 CO2 saturation after 1 year in Case 3 c-3 CO2 saturation after 30 years in Case 3
Fig. 9. Two-dimension distribution of CO2 saturation under different time for Cases 1, 2 and 3.

change to the CO2 plume path. As shown, the change of the CO2 plume
path causes a large region at the bottom of the production well to not be
displaced by the CO2 in Fig. 12a compared to the CO2 saturation in
Fig. 11a. Due to the influence of the CO2 distribution area, the mineral
change in Case 5 is lower than that in Case 4, although both mineral
change distributions are similar. Therefore, the direct influence of salt
precipitation on the geochemical reactions is not significant, and its
effect on geochemical reactions mainly occurs through the indirect in-
fluence on the CO2 distribution area. Corresponding with the salt pre-
cipitation and geochemical reactions, the injection well area is severely
damaged by the salt precipitation and results in the porosity and per-
meability decreasing to 0.018 and 2 md, respectively, which means the
salt precipitation, especially in the injection well area, is the primary
factor preventing geothermal exploitation in the CPG system. However,
it should be noted that the reservoir damage (i.e., permeability) may be
exaggerated in this example because the precipitated salt in the injec-
tion well area can be moved by the injected CO2, which is not con-
sidered in this study.
4.3. Influence on heat mining rate
Fig. 13 illustrates the production rates of the fluids under the dif-
ferent cases. As shown, the water is first produced from the production
well because the reservoir is initially full of formation water. After a
while, the breakthrough of the injected CO2 at the production occurs
and, subsequently, the water production rate rapidly decreases while
the CO2 production rate increases with the continuous injection of CO2.
As shown in Fig. 14, the existence of the formation water affects the
heat mining rate in the early stage of geothermal exploitation due to the
multiphase flow. Under the action of multiphase flow, the heat mining
rate first decreases and then increases over time after CO2 breakthrough
occurs at the production well. Therefore, the production of formation
water really can affect the heat mining rate, especially in the early stage
of geothermal exploitation. Meanwhile, it can be seen from Fig. 14 that
the heat mining rate begins to decline after 25 years of geothermal
exploitation as the heat front has moved to the production well, as
shown in Fig. 15. However, the average reservoir temperature in Case 1
only reduces from 150 °C to about 90 °C after 30 years, meaning there is
still a lot of heat that can be mined in the reservoir.
As shown in Figs. 13 and 14, it can be seen from the first three cases
that the gas-liquid capillary has little effect on the CO2 production and
heat mining rates, but evaporation can significantly affect the CO2 pro-
duction and heat mining rate. This is because the evaporation of formation
water can significantly increase the pore space of the CO2 migration,
which then results in a CO2 flow rate increase. By comparing Case 1 and
Case 4, it can be seen that the geochemical reactions have little effect on
the CO2 production and heat mining rates, especially in the early stage of
geothermal exploitation. After about 15 years of exploitation, the influence
of the geochemical reactions on the CO2 production begins to increase,
which then results in a slight decrease of the heat mining rate because of
the severe geochemical reactions at the bottom of the production well (as
shown in Fig. 13). By comparing Case 1 and Case 5, it can be seen that the
CO2 production rate decreases from 30 kg/s to 13 kg/s and the heat
mining rate decreases from 15 MW to about 6 MW under the combined
actions of the geochemical reactions and the salt precipitation. This is
because severe salt precipitation that occurred in the injection well area
can substantially reduce the porosity and permeability, which can result in
the CO2 production and heat mining rates decreasing in the early stage of
geothermal exploitation. Therefore, the effect of the salt precipitation on
the heat mining rate is greater than the effect of the geochemical reactions
on the heat mining rate in the CPG system. These simulation results in-
dicate that the reservoir damage caused by the salt precipitation must be
considered and should be reduced or avoided when practically applying
CO2 for geothermal exploitation.

57
G. Cui et al.
a-1 2D distribution of water flow velocity after 6 months in Case 1
b-1 2D distribution of water flow velocity after 6 months in Case 2
c-1 2D distribution of water flow velocity after 6 months in Case 3
Fig. 10. Two-dimension distribution of the water flow velocity under different time for Cases 1, 2 and 3.
5. Sensitivity study on the heat mining rate
The reservoir changes and injection-production pressure difference
can affect the fluid flow and induced geochemical reactions and salt
precipitation, which can then affect the heat mining rate. In this sec-
tion, based on Case 5 in the two-dimension, sensitivity studies were
performed to analyze the influences of the initial reservoir temperature,
pressure, porosity, permeability, salinity, and injection-production
pressure difference, which can provide some guidance on screening
reservoirs for geothermal exploitation.
As seen from Fig. 16, the increase of the initial reservoir tempera-
ture can increase the heat mining rate because of the enthalpy of CO2
increases with the temperature increase. However, the increase of the
initial reservoir pressure would decrease the heat mining rate because
the enthalpy of CO2 decreases with the increasing pressure. All in-
creases in the initial reservoir porosity, permeability, and injection-
production pressure difference can increase the heat mining rate, but
the high permeability would result in the heat mining rate decreasing in
the latter stage of geothermal exploitation due to the heat breakthrough
at the production well. The salinity of the formation water has the
greatest impact on the heat mining rate, and the heat mining rate de-
creases rapidly with the salinity increase. When the molarity of the CO2
58
Applied Energy 227 (2018) 49–63
a-2 2D distribution of water flow velocity after 1 year in Case 1
b-2 2D distribution of water flow velocity after 1 year in Case 2
c-2 2D distribution of water flow velocity after 1 year in Case 3
in the water is 2 mol/L, the heat mining rate eventually drops to 0 MW
after 15 years of exploitation because severe salt precipitation com-
pletely blocks the injection well area.
All simulation results show that the fluid-rock interactions can affect
the heat mining rate, but the reservoir condition determines their in-
fluence. Notably, the back flow caused by the evaporation and gas-li-
quid capillary can result in a complex fluid-rock interaction, which even
can control the heat mining rate in some particular situation. Therefore,
the reservoir conditions and injection-production pressure difference
should be comprehensively considered when selecting a reservoir to
exploit geothermal energy using CO2. The above simulation results
indicate that a reservoir with high reservoir temperature, porosity,
permeability, and low salinity should be selected first to exploit geo-
thermal using an appropriate high injection-production pressure dif-
ference.
In addition, it should be noted that different reservoirs have dif-
ferent ionic and mineral compositions, which can significantly affect
the geochemical reactions and salt precipitation, so the geochemical
reactions and salt precipitation, combined with the real reservoir con-
ditions, should be carefully studied. In addition, the gas-liquid capillary
will also affect the salt precipitation by changing the back flow in the
injection well area and its influence will be studied in future research.
G. Cui et al. Applied Energy 227 (2018) 49–63

a CO2 saturation distribution b Anorthite change distribution c Calcite change distribution

d Kaolinite change distribution e Porosity distribution f Permeability distribution

Fig. 11. Two-dimension distribution of the related reservoir physical properties after 30 years in Case 4 (positive means precipitation and negative means precipitation for the mineral
change).

a CO2 saturation distribution b Salt precipitation distribution c Anorthite change distribution

d Calcite change distribution e Kaolinite change distribution f Porosity distribution

g Permeability distribution
Fig. 12. Two-dimension distribution of the related reservoir physical properties after 30 years for Case 5 (positive means precipitation and negative means precipitation for the mineral
change).

59
G. Cui et al.
Fig. 13. Production rates of the fluids over time for the different cases.
Fig. 14. Heat mining rate and average reservoir temperature for the different cases.
6. Methods for solving this energy issue
It can be seen from the above simulations that the existence of the
formation water can seriously affect the heat mining rate in the early
stage of geothermal exploitation, especially the salt precipitation
caused by the back flow of the formation water can intensify this in-
fluence. Therefore, the production time of the water should be shor-
tened through some measures, like improving the injection-production
pressure difference in the early stage. For enhancing the heat utilization
efficiency, the produced high-temperature water also can be used.
a Temperature distribution in Case 1 b Temperature distribution in Case 2
d Temperature distribution in Case 4
Fig. 15. Two-dimension temperature distribution after 30 years for the different cases.
60
Applied Energy 227 (2018) 49–63
Meanwhile, some gas-liquid separators or high-pressure drying devices
should be used to separate the water vapor in the produced CO2.
The influence of the salt precipitation on the heat mining rate is
greater than that of the geochemical reactions, so salt precipitation
should be avoided or mitigated. However, the natural high-perme-
ability reservoir usually has a high salinity, which may result in a severe
salt precipitation. Therefore, some methods should be developed to
solve this energy issue mainly caused by the salt precipitation and
thereby further promote the actual application of the CPG system. Some
studies show that low salinity water injection before CO2 injection can
prevent salt precipitation because the low salinity injected water can
separate the direct contact of the high salinity formation water and the
subsequently injected CO2 [25,33]. Also, the method of co-injecting
CO2 and water vapor [25,33] can prevent salt precipitation because the
dissolved water in CO2 can decrease or even stop the water evaporation
and induced salt precipitation.
Based on the two-dimension Case 5, two simulation schemes were
established to evaluate the effectiveness of these methods, (Table 6).
The ratio of water vapor to CO2 for the second scheme was selected
based on trial and error simulation, in which the heat mining rate is the
highest. It can be seen that both these schemes can increase the heat
mining rate, as shown in Figs. 17 and 18. Compared with co-injecting
the CO2 and water vapor, the low salinity water injection prior to CO2
injection has a better effect on increasing the heat mining rate as it can
increase the production rate from 13 kg/s to about 30 kg/s and the heat
mining rate from 6 MW to 14 MW after 30 years of development. Con-
sidering that implementing the first method will not interrupt the
production after CO2 has been injected to exploit geothermal, low
salinity water injection prior CO2 injection is recommended when the
formation water salinity in the reservoir is high.
7. Conclusions
In geothermal exploitation from natural high-permeability reservoirs
via CO2 recycling, the water evaporation, gas-liquid capillary, geochemical
reactions, and salt precipitation can significantly affect the fluid flow and
development of seepage zones, becoming an energy issue affecting the
geothermal energy exploitation. In this paper, a comprehensive simulation
model that considers formation water evaporation, CO2-formation water-
rock geochemical reactions, salt precipitation, and the changes of reservoir
porosity and permeability was established to analyze the effects of the
complicated fluid-rock interactions on the geothermal exploitation.
c Temperature distribution in Case 3
e Temperature distribution in Case 5
G. Cui et al.
a Heat mining rates at different initial reservoir temperature
c Heat mining rates at different injection-production pressure difference
e Heat mining rates at different initial reservoir permeability
Fig. 16. Results of the heat mining rate in sensitivity simulations.
Table 6
Different schemes for enhancing the heat mining rate.
Scheme Description Injected fluid
0 2D case 5 × ×
1 Early low salinity water injection H2O/CO2
2 Co-injection of CO2 and water vapor 0.007H2O + 0.993CO2
Note: × means no corresponding measure.
(1). During the geothermal exploitation in a CO2 plume geothermal
system, the continuous CO2 injection can make the water rapidly
evaporate into the CO2 phase and result in a high water saturation
gradient in the area near the injection well as well as a high gas-
liquid capillary, which causes the formation water flow back to the
injection well. This back flow can affect the geochemical reactions
and the salt precipitation near the injection well and complicate
the fluid-rock interactions.
(2). The simulation results indicate that the decrease of het mining rate
61
Applied Energy 227 (2018) 49–63
b Heat mining rates at different initial reservoir pressure
d Heat mining rates at different initial reservoir porosity
f Heat mining rates at different initial salinity
Injection timing Injection duration Mechanisms
× ×
At the beginning One month Lower salinity
Along with CO2 injection × Reduce vaporization
caused by salt precipitation is much greater than that from geo-
chemical reactions. Although the CO2-water-rock geochemical re-
actions can lead to the dissolution of certain minerals and pre-
cipitation of others, its influence on the heat mining rate is
negligible. However, severe salt precipitation due to capillary-
caused back flow and gravity-caused down flow in the injector
region can substantially decrease the porosity and permeability,
which can result in a substantial decline in the heat mining rate up
to 2/5 of its original.
G. Cui et al.
Fig. 17. Production rates of the fluids for the different methods for enhancing the heat
mining rate.
Fig. 18. Heat mining rate of the different methods for enhancing the heat mining rate.
(3). Sensitivity studies show that the effect of salt precipitation on the
heat mining rate is reservoir specific. Salt precipitation can se-
verely damage the reservoir and even completely block the re-
servoir when the salinity is very high. When a low injection-pro-
duction pressure difference cannot overcome the capillary pressure
gradient, it can enhance the back flow of formation water and
intensify the salt precipitation. Geothermal reservoirs with a high
temperature, high porosity and permeability, and low salinity
should be selected first for the application of a CO2 plume geo-
thermal system, and an appropriately high injection-production
pressure difference should be adopted.
(4). In order to solve the energy issue affecting the heat mining rate
mainly caused by the salt precipitation, both the injection of low
salinity water before CO2 injection and the co-injection of CO2 and
water vapor can be used during geothermal exploitation in the CPG
system. The low salinity water injection prior to CO2 injection is
firstly recommended due to its conveniences and high efficiency.
Acknowledgements
This research was supported by the National Natural Science
Foundation of China (No. 51674282), the Fundamental Research Funds
for the Central Universities (No. 17CX06006), the graduate innovation
funding project from China University of Petroleum (East China)
(YCX2017022) the National Oil and Gas Major Projects (No.
2016ZX05056004-003), and the Changjiang Scholars and Innovative
Research (IRT 1294 and 1086/14R58).
References
[1] Ali Sayigh. Renewable energy—the way forward. Appl Energy 1999;64(1):15–30.
< https://doi.org/10.1016/s0306-2619(99)00117-8 > .
62
Applied Energy 227 (2018) 49–63
[2] Gupta H, Roy S. Geothermal energy: an alternative resource for the 21st century.
Amsterdam: Elsevier; 2007.
[3] Tester JW, Anderson BJ, Batchelor AS, Blackwell DD, DiPippo R, Drake EM, et al.
The future of geothermal energy. Massachusetts Institute of Technology; 2006.
[4] Wang GL, Li KW, Lin WJ, Lin LJ, Liu ZM, Zhang W, et al. Assessment of geothermal
resources in China. In: 38th Workshop on Geotherm Reserv Eng Stanford, CA:
Stanford Univ.; 2013
[5] Blackwell DD, Richards M. Geothermal map of North America. American Assoc.
Petroleum Geologist (AAPG); 2004. 1 sheet, scale 1:6,500,000.
[6] IPCC, Climate Change 2013: The physical science basis, contribution of working
group I to the fifth assessment report of the intergovernmental panel on climate
change. In: Stocker TF, Qin D, Plattner G-K, Tignor M, Allen SK, Boschung J, et al.
(editors), Cambridge United Kingdom and New York, USA: Cambridge University
Press; 2013. p. 1535.
[7] Procesi M, Cantucci B, Buttinelli M, Armezzani G, Quattrocchi F, Boschi E. Strategic
use of the underground in an energy mix plan: synergies among CO2, CH4 geological
storage and geothermal energy, Latium region case study (Central Italy). Appl
Energy 2013;110:104–31. http://dx.doi.org/10.1016/j.apenergy.2013.03.071.
[8] Ghasemi H, Sheu E, Tizzanini A, Paci M, Mitsos A. Hybird solar-geothermal power
generation: optimal retrofitting. Appl Energy 2014;131:158–70. http://dx.doi.org/
10.1016/j.apenergy.2014.06.010.
[9] Shengjun Z, Huaixin W, Tao G. Performance comparison and parametric optimi-
zation of subcritical Organic Rankine Cycle (ORC) and transcritical power cycle
system for low-temperature geothermal power generation. Appl Energy
2011;88:2740–54. http://dx.doi.org/10.1016/j.apenergy.2011.02.034.
[10] De Silva GPD, Ranjith PG, Perera MSA. Geochemical aspects of CO2 sequestration in
deep saline aquifers: a review. Fuel 2015;155:128–43.
[11] Bachu S, Adams J. Sequestration of CO2 in geological media in response to climate
change: capacity of deep saline aquifers to sequester CO2 in solution. Energy
Convers Manage 2003;44:3151–75.
[12] Luo F, Xu RN, Jiang PX. Numerical investigation of the influence of vertical per-
meability heterogeneity in stratified formation and of injection/production well
perforation placement on CO2 geological storage with enhanced CH4 recovery. Appl
Energy 2013;102:1314–23. http://dx.doi.org/10.1016/j.apenergy.2012.07.008.
[13] Wang JL, Zhao L, Wang XD. An experimental study on the recuperative low tem-
perature solar Rankine cycle using R245fa. Appl Energy 2012;94:34–40. http://dx.
doi.org/10.1016/j.apenergy.2012.01.019.
[14] Yin H, Sabau AS, Conklin JC, McFarlane J, Qualls AL. Mixtures of SF6-CO2 as
working fluids for geothermal power plants. Appl Energy 2013;106:243–53. http://
dx.doi.org/10.1016/j.apenergy.2013.01.060.
[15] Maraver D, Royo J, Lemort V, Quoilin S. Systematic optimization of subcritical and
transcritical organic rankine cycles (ORCs) constrained by technical parameters in
multiple applications. Appl Energy 2014;117:11–29. http://dx.doi.org/10.1016/j.
apenergy.2013.11.076.
[16] Sauret E, Gu Y. Three-dimensional off-design numerical analysis of an organic
rankine cycle radial-inflow turbine. Appl Energy 2014;135:202–11. http://dx.doi.
org/10.1016/j.apenergy.2014.08.076.
[17] Chen H, Goswami DY, Rahman MM, Stefanakos EK. Energetic and exergetic analysis
of CO2-and R32-based transcritical Rankine cycles for low-grade heat conversion.
Appl Energy 2011;88:2802–8. http://dx.doi.org/10.1016/j.apenergy.2011.01.029.
[18] Toffolo A, Lazzaretto A, Manente G, Paci M. A multi-criteria approach for the op-
timal selection of working fluid and design parameters in organic rankine cycle
systems. Appl Energy 2014;121:219–32. http://dx.doi.org/10.1016/j.apenergy.
2014.01.089.
[19] Brown DW. A hot dry rock geothermal energy concept utilizing supercritical CO2
instead of water. In: Proceedings of the twenty-fifth workshop on geothermal re-
servoir engineering, Stanford University, Stanford, California, January 24–26;
2000.
[20] Pruess K. Enhanced geothermal systems (EGS) using CO2 as working fluid – a novel
approach for generating renewable energy with simultaneous sequestration of
Carbon. Geothermics 2006;35(4):351–67. http://dx.doi.org/10.1016/j.
geothermics.2006.08.002.
[21] Pruess K. On production behavior of enhanced geothermal systems with CO2 as
working fluid. Energy Convers Manage 2008;49(6):1446–54. http://dx.doi.org/10.
1016/j.enconman.2007.12.029.
[22] Randolph JB, Saar MO. Coupling carbon dioxide sequestration with geothermal
energy capture in naturally permeable, porous geologic formations: implications for
CO2 sequestration. Energy Proc 2011;4:2206–13. http://dx.doi.org/10.1016/j.
egypro.2011.02.108.
[23] Zhang L, Ezekiel J, Li D, et al. Potential assessment of CO2 injection for heat mining
and geological storage in geothermal reservoirs of China. Appl Energy
2014;122:237–46. http://dx.doi.org/10.1016/j.egypro.2014.11.799.
[24] Shaoran Ren, Guodong Cui, Dexiang Li, et al. Development of geothermal energy
from depleted high temperature gas reservoir via supercritical CO2 injection. J
China Univ Petrol (Ed Nat Sci) 2016;40(2):91–8. http://dx.doi.org/10.3969/j.
ISSN. 1673-5005. 2016. 02. 011 [in Chinese].
[25] Cui G, Zhang L, Ren B, et al. Geothermal exploitation from depleted high tem-
perature gas reservoirs via recycling supercritical CO2: heat mining rate and salt
precipitation effects. Appl Energy 2016;183:837–52. http://dx.doi.org/10.1016/j.
apenergy.2016.09.029.
[26] Benjamin M. Adams, Thomas H. Kuehn, Jeffrey M. Bielicki, Jimmy B. Randolph,
Martin O. Saar. On the importance of the thermosiphon effect in CPG (CO2 plume
geothermal) power systems. Energy 2014;69:409-18. < https://doi.org/10.1016/j.
energy.2014.03.032 > .
[27] Salimi H, Wolf KH. Integration of heat-energy recovery and carbon sequestration.
Int J Greenhouse Gas Control 2012;6:56–68. http://dx.doi.org/10.1016/j.ijggc.
G. Cui et al.
2011.11.010.
[28] Eccles JK, Pratson L. A “carbonshed” assessment of small-vs. large-scale CCS de-
ployment in the continental US. Appl Energy 2014;113:352–61. http://dx.doi.org/
10.1016/j.apenergy.2013.07.002.
[29] Meng Q, Jiang X. Numerical analyses of the solubility trapping of CO2 storage in
geological formations. Appl Energy 2014;130:581–91. http://dx.doi.org/10.1016/j.
apenergy.2014.01.037.
[30] Quattrocchi F, Boschi E, Spena A, et al. Synergic and conflicting issues in planning
underground use to produce energy in densely populated countries, as Italy: geo-
logical storage of CO2, natural gas, geothermics and nuclear waste disposal. Appl
Energy 2013;101:393–412. http://dx.doi.org/10.1016/j.apenergy.2012.04.028.
[31] Adams BM, Kuehn TH, Bielicki JM, et al. A comparison of electric power output of
CO2 Plume Geothermal (CPG) and brine geothermal systems for varying reservoir
conditions. Appl Energy 2015;140:365–77. http://dx.doi.org/10.1016/j.apenergy.
2014.11.043.
[32] Xu T, Feng G, Shi Y. On fluid–rock chemical interaction in CO2-based geothermal
systems. J Geochem Explor 2014;144:179–93. http://dx.doi.org/10.1016/j.gexplo.
2014.02.002.
[33] Zhang L, Cui G, Zhang Y, et al. Influence of pore water on the heat mining per-
formance of supercritical CO2 injected for geothermal development. J CO2 Util
2016;16:287–300. < https://doi.org/10.1016/j.jcou.2016.08.008 > .
[34] Borgia A, Pruess K, Kneafsey TJ, et al. Numerical simulation of salt precipitation in
the fractures of a CO2-enhanced geothermal system. Geothermics 2012;44:13–22.
http://dx.doi.org/10.1016/j.geothermics.2012.06.002.
[35] Gaus I. Role and impact of CO2–rock interactions during CO2 storage in sedimentary
rocks. Int J Greenhouse Gas Control 2010;4(1):73–89. http://dx.doi.org/10.1016/j.
ijggc.2009.09.015.
[36] Palandri JL, Kharaka YK. Ferric iron-bearing sediments as a mineral trap for CO2
sequestration: iron reduction using sulfur-bearing waste gas. Chem Geol
2005;217(3):351–64. http://dx.doi.org/10.1016/j.chemgeo.2004.12.018.
[37] André L, Audigane P, Azaroual M, et al. Numerical modeling of fluid–rock chemical
interactions at the supercritical CO2–liquid interface during CO2 injection into a
carbonate reservoir, the Dogger aquifer (Paris Basin, France). Energy Convers
Manage 2007;48(6):1782–97. http://dx.doi.org/10.1016/j.enconman.2007.01.
006.
[38] Guo T, Li Y, Ding Y, Qu Z, Gai N, Rui Z. Evaluation of acid fracturing treatments in
shale formation. Energy Fuel 2017;31(10):10479–89. http://dx.doi.org/10.1021/
acs.energyfuels.7b01398.
[39] Ito H, Kaieda H, Ueda A, et al. Preliminary results of CO2 sequestration into Ogachi
geothermal reservoir, Northeast Japan. Proceedings world geothermal congress
Antalya, Turkey, 24–29 April; 2005.
[40] Ueda A, Kato K, Ohsumi T, et al. Experimental studies of CO2-rock interaction at
elevated temperatures under hydrothermal conditions. Geochem J
2005;39(5):417–25. http://dx.doi.org/10.2343/geochemj.39.417.
[41] Wan Y, Xu T, Pruess K. Impact of fluid-rock interactions on enhanced geothermal
systems with CO2 as heat transmission fluid. Proceedings of thirty-sixth workshop
on geothermal reservoir engineering, Stanford, California, Jan 1–Feb 2; 2011.
[42] Golghanddashti H, Saadat M, Abbasi S, Shahrabadi A. Experimental investigation of
salt precipitation during gas injection into a depleted gas reservoir. International
petroleum technology conference. Bangkok, Thailand; 7–9 February; 2012.
< https://doi.org/10.2523/15179-ms > .
[43] Ott H, De Kloe K, Taberner C, Marcelis F, Makurat A. Injection of super-critical CO2
in brine saturated sandstone. EGU general assembly conference. EGU general as-
sembly conference abstracts; 2010:4425–32.
[44] Ott H, de Kloe K, Marcelis F, Makurat A. Injection of supercritical CO2 in brine
saturated sandstone: pattern formation during salt precipitation. Energy Proc
2011;4:4425–32. http://dx.doi.org/10.1016/j.egypro.2011.02.396.
[45] Zeidouni M, Pooladi-Darvish M, Keith D. Sensitivity analysis of salt precipitation
and CO2-brine displacement in saline aquifers. SPE international conference on
CO2 capture, storage, and utilization. San Diego, USA; 2–4 November, 2009.
< https://doi.org/10.2118/126690-ms > .
[46] Ott H, Roels SM, Kloe KD. Salt precipitation due to supercritical gas injection: I.
Capillary-driven flow in unimodal sandstone. Int J Greenhouse Gas Control
2015;22(31):186–91. http://dx.doi.org/10.1016/j.ijggc.2015.01.005.
[47] Spycher N, Pruess K. A phase-partitioning model for CO2–brine mixtures at elevated
temperatures and pressures: application to CO2-enhanced geothermal systems.
Transp Porous Media 2009;82(1):173–96. http://dx.doi.org/10.1007/s11242-009-
9425-y.
63
Applied Energy 227 (2018) 49–63
[48] Peng DY, Robinson DB. A new two-constant equation of state. Ind Eng Chem
Fundam 1976;15(1):59–64. http://dx.doi.org/10.1021/i160057a011.
[49] Canjar LN, Manning FS. Thermodynamic properties and reduced correlations for
gases. Gulf Publishing Co., Houston, Texas; 1967. < https://doi.org/10.1002/aic.
690140603 > .
[50] Saul A, Wagner W. International equations for the saturation properties of ordinary
water substance. J Phys Chem Ref Data 1987;16(4):893–901. http://dx.doi.org/10.
1063/1.555787.
[51] Rowe AM, Chou JCS. Pressure-volume-temperature-concentration relation of aqu-
eous sodium chloride solution. J Chem Eng Data 1970;15(1):61–6. http://dx.doi.
org/10.1021/je60044a016.
[52] Harvey AH. Semiempirical correlation for Henry’s constants over large temperature
ranges. AIChE J 1996;42(5):1491–4. http://dx.doi.org/10.1002/aic.690420531.
[53] Garcia JE. Density of aqueous solutions of CO2. Lawrence Berkeley National
Laboratory; October 2001. < https://doi.org/10.2172/790022 > .
[54] Bakker RJ. Package FLUIDS 1. Computer programs for analysis of fluid inclusion
data and for modelling bulk fluid properties. Chem Geol 2003;194(1):3–23. http://
dx.doi.org/10.1016/s0009-2541(02)00268-1.
[55] Wilke CR, Chang P. Correlation of diffusion coefficients in dilute solutions. AIChE J
1955;1(2):264–70. http://dx.doi.org/10.1002/aic.690010222.
[56] Reid RC, Prausnitz JM, Sherwood TK. The properties of gases and liquids 3rd
ed.New York: McGraw-Hill; 1977. http://dx.doi.org/10.1002/aic.690240634.
[57] Li Lanlan. Determination of diffusion coefficients of CO2 and CH4 in NaCl aqueous
solutions under wide temperature-pressure conditions by in situ Micro-Raman
spectroscopy. China Univ Geosci. Wuhan; 2013 [in Chinese].
[58] Tamimi A, Rinker EB, Sandall OC. Diffusion coefficients for hydrogen sulfide,
carbon dioxide, and nitrous oxide in water over the temperature range 293–368 K. J
Chem Eng Data 1994;39(2):330–2. http://dx.doi.org/10.1021/je00014a031.
[59] Guo B, Hou JR, Chun-Lei YU, et al. Determination of diffusion coefficient for carbon
dioxide in the porous media. J Petrochem Univ 2009;22(4):38–40. [in Chinese].
[60] Nghiem L. Compositional simulator for carbon dioxide sequestration. Calgary,
Canada: Computer Modeling Group Ltd.; 2002.
[61] Stumm W, Morgan JJ. Aquatic chemistry: chemical equilibria and rates in natural
waters. Cram101 textbook outlines to accompany 1996;179(11):A277. < https://
doi.org/10.5860/choice.33-6312 > .
[62] Kumar A, Datta-Gupta A, Shekhar R, et al. Modeling time lapse seismic monitoring
of CO2 sequestration in hydrocarbon reservoirs including compositional and geo-
chemical effects. Pet Sci Technol 2008;26(7):887–911. http://dx.doi.org/10.1080/
10916460701825505.
[63] Borgia A, Pruess K, Kneafsey TJ, Oldenburg CM, Pan L. Simulation of CO2-EGS in a
fractured reservoir with salt precipitation. Energy Proc 2013;37:6617–24. http://
dx.doi.org/10.1016/j.egypro.2013.06.594.
[64] Hurter S, Berge J, Labregere D. Simulations for CO2 injection projects with com-
positional simulator. Offshore Europe, Aberdeen, Scotland, UK; 3–7 September
2007. < https://doi.org/10.2523/108540-ms > .
[65] Jin M, Ribeiro A, Mackay E. Geochemical modelling of formation damage risk
during CO2 injection in saline aquifers. J Nat Gas Sci Eng 2016;35:703–19. http://
dx.doi.org/10.1016/j.jngse.2016.08.030.
[66] Nghiem L, Sammon P, Grabenstetter J, et al. Modeling CO2 storage in aquifers with
a fully-coupled geochemical EOS compositional simulator. SPE 89474, SPE/DOE
fourteenth symposium on improved oil recovery, Tulsa, Oklahoma, 17–21 April;
2004. < https://doi.org/10.2523/89474-ms > .
[67] Lzgec O, Demiral B, Bertin H, et al. Experimental and numerical modeling of direct
injection of CO2 into carbonate formations. SPE 100809, 2006 SPE annual technical
conference and exhibition, San Antonio, Texas, 24–27 Sep; 2006. < https://doi.
org/10.2523/100809-ms > .
[68] Qijun Hou, Zhiqiang Feng, Zihun Feng. Continental petroleum geology of Songliao
basin. Beijing: Petroleum Industry Press; 2009.
[69] Zhanli Ren, Deming Xiao, Yuanlin Chi. Restoration of the palaeogeotherm in
Songliao Basin. Petrol Geol Oilfield Dev Daqing 2001;20(1):13–4. http://dx.doi.
org/10.3969/j.issn.1000-3754.2001.01.004. [in Chinese].
[70] Alkattan M, Oelkers EH, Dandurand JL, et al. Experimental studies of halite dis-
solution kinetics, 1. The effect of saturation state and the presence of trace metals.
Chem Geol 1997;137(3–4):201–19. http://dx.doi.org/10.1016/s0009-2541(96)
00164-7.
[71] Rui Z, Lu J, Zhang Z, Guo R, Ling K, Zhang R, Patil S. A quantitative oil and gas
reservoir evaluation system for development. J Nat Gas Sci Eng 2017;42:31–9.
http://dx.doi.org/10.1016/j.jngse.2017.02.026.