International Journal of Coal Geology 154–155 (2016) 265–274

Contents lists available at ScienceDirect

International Journal of Coal Geology

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

Experimental study of CO2–brine–rock interaction during CO2

sequestration in deep coal seams
Kairan Wang, Tianfu Xu, Fugang Wang ⁎, Hailong Tian
Key Laboratory of Groundwater Resources and Environment, Ministry of Education, Jilin University, Changchun 130021, China

a r t i c l e i n f o a b s t r a c t

Article history: CO2 sequestration in deep coal seams is a potential option for reducing greenhouse gas emissions. Once CO2 is
Received 13 August 2015 injected into coal seams, sealing capability of the cap rock is critical. To investigate and quantify reactions over
Received in revised form 19 January 2016 time between CO2, cap rocks and brine, associated with selected cap rocks of the No. 3 coalbed of the Qinshui
Accepted 19 January 2016
Basin in China, batch experiments were conducted for reacting powdered rock samples (180–220 μm) with
Available online 20 January 2016
CO2 and brine, as well as CO2-free brine, at 160 °C and 15 MPa. The analysis of leachate chemistry indicated sig-
Keywords:
nificant mobilization of major elements from dissolution of carbonate and silicate minerals in the coal measure
CO2 storage strata. Analysis of reacted solids by XRD and SEM also revealed appreciable changes in mineralogical composi-
ECBM tions. For lithic sandstone after reaction with CO2–brine, the contents of quartz, plagioclase, illite and chlorite in-
Water–rock interaction creased considerably, whereas the contents of illite/smectite, biotite and kaolinite decreased more or less. The
Mineralogical changes calcareous mudstone reacting with CO2–brine and CO2-free brine all showed major mineralogical alteration
Caprock after 12 days of treatment. The modeling results identified key chemical processes, but they also showed that
the models are not capable of covering all possible contingencies. The precipitation of carbonate minerals
could also enhance the security of CO2 sequestration in deep coal seams.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Climate change has become a hot point involved in global environ-
mental issues. Controlling greenhouse gas emissions and protecting
global climate is a major issue at present. Of all types of greenhouse
gases blamed for climate change, emissions of CO2 from human activi-
ties has one of the largest impacts on climate change gases, accounting
for 63% of the temperature effect from all total greenhouse gases. Addi-
tionally, CO2 is retained in the atmosphere for more than 200 years
(Metz et al., 2005). The question of how to reduce the content of CO2
in the atmosphere is the current problem to be solved. It is well
known that geological CO2 storage (GCS) is undoubtedly the most real-
istic and effective disposal method. At present, storing CO2 by injection
into subsurface oil and gas reservoirs (Winter and Bergman, 1993;
Bachu and Shaw, 2003), deep saline aquifers (Xu et al., 2004; W.
Zhang et al., 2009; X. Zhang et al., 2009; Lei et al., 2015; Tian et al.,
2015) and deep unmineable coal beds (Massarotto et al., 2010;
Dawson et al., 2011) is the most valid and economic choice for reducing
CO2 emissions into the atmosphere. Of these methods, coal bed geolog-
ical disposal is one of the most favorable, as enhanced coal bed methane
recovery can be accomplished simultaneously with sequestration of
⁎ Corresponding author.
E-mail address: wkr8708206611@163.com (F. Wang).
CO2. This technique is known as CO2-ECBM (Gale and Freund, 2001;
White et al., 2005; Czerw, 2011; Baran et al., 2015).
Throughout the world, coal measure strata are important source
layers of oil and gas, and they are important reservoirs, especially for
natural gas resources. By the statistics, many large gas fields in the
world are associated with coal measure strata. Coal measure strata
include a large number of abandoned coal seams due to technical and
economic reasons, and these unmineable coal seams are potential geo-
logical structures that can be used for geological CO2 sequestration. Only
a handful of CO2-ECBM tests in the world have been implemented.
These tests showed great potential for both CO2 sequestration and
ECBM production. For instance, the United States built the first CO2-
ECBM pilot project in the San Juan basin, and more than 100,000 t of
CO2 has been injected into the Fruitland coal seam since 1996 (Weber
et al., 2012). Canada is in the process of a controlled trial of a CO2-
ECBM test in Alberta (Gentzis, 2000), and the evaluation of regional pro-
jects is widely being carried out throughout the world. In addition,
Australia, Japan, The Netherlands and other countries have implement-
ed CO2 injection to enhance CBM exploitation, and they have carried out
related researches (Li et al., 2004; Golding et al., 2013).
There are many coal-bearing rock series widely distributed in conti-
nental sedimentary basins (Qinshui Basin and Ordos Basin, etc.) in
China, which are more suitable for CO2 sequestration. Since 2002,
under the support of the governments of Canada and China, the China
United Coal Bed Methane Corporation carried out the theory and tech-
nological research of CO2 injection/burial, enhanced coal bed methane

http://dx.doi.org/10.1016/j.coal.2016.01.010
0166-5162/© 2016 Elsevier B.V. All rights reserved.
266 K. Wang et al. / International Journal of Coal Geology 154–155 (2016) 265–274
recovery, and successful implementation of a single well CO2 injection
test in the southern Qinshui Basin of Shanxi Province in 2004, obtaining
a series of key parameters (Wong et al., 2007, 2010; Wei et al., 2007).
Under the support of the China Ministry of Science and Technology,
the China United Coal Bed Methane Corporation carried out a techno-
logical research on deep coal seam CO2 injection and coal bed methane
exploitation in 2007, to achieve the commercialization of this technolo-
gy. This is the first research project of deep coal bed CO2-ECBM in China,
and 234 t of CO2 was injected into the No. 3 coal seam.
In recent years, in allusion to the basic theory of CO2-ECBM, a series
of studies on multicomponent gas competitive adsorption on coal sur-
faces (Tang et al., 2004; Zhang et al., 2004; Zhou et al., 2013), coal matrix
expansion and contraction induced by adsorption (Karacan, 2003; Qin
et al., 2005; Pan and Luke, 2007), and numerical simulation (Sun,
2005; Wu and Zhang, 2007; Siriwardane et al., 2012; Vishal et al.,
2013) were carried out. However, long-term studies have ignored the
fact that, once CO2 is injected into coal seams, it will dissolve in forma-
tion water and form carbonic acid. Thus, the minerals in coal seams
and roof-floor rocks were dissolving and the components of coal were
changing. Secondary aluminosilicate and carbonate minerals could be
formed at the same time, so that CO2 can be safely sealed underground
for a long time (Li et al., 2013).
To reveal the physicochemical processes and evaluate the security of
CO2 sequestration in deep unmineable coal seams, it is necessary to
carry out the related experimental investigations on CO2–brine–rock re-
actions, to discuss the geochemical behavior and possible mechanism of
mineral traps in the long-term interaction between CO2 and coal mea-
sure strata, and to provide a natural analogy as a research object and
as a geological basis for CO2-ECBM projects.
Fig. 1. Burial depth contour map of the No. 3 coal seam of the Qinshui Basin and the stratigraphic section of coal-bearing strata.
Modified from Wei et al. (2007) and Cai et al. (2015).
2. Geological setting
The Qinshui Basin is a near longitudinal-trending tectonic basin be-
tween Taihang Mountain and Lvliang Mountain, located in the middle
of the North China Platform. The basin has experienced the tectonic
movements of the Indosinian Period (Late Permian to Triassic), the
Yanshan Period (Jurassic to Early Cretaceous) and the Himalayan Period
(Late Tertiary). The basin's fold and fault structures are well developed,
and most of the tectonic lines are in the NE-NNE direction. The study
area, in the north block of Shizhuang, is located in the southeast of the
Qinshui Basin. The main geological structure is folding. Faulting is not
well developed, and existing faults are no longer than 100 m. Collapse
columns occur occasionally. The overall structure of the study area is
a western-leaning monocline (Fig. 1). The block is divided by the
longitudinal-trending syncline structure into three tectonic units. The
east unit is a gentle monoclinal structure, with only a few small faults
and with dip angles generally less than 5°, and it slowly uplifts towards
the SE. The central unit is a severely squeezed anticline-syncline pair
with a range of 210 m, and the axis orientation is NNE. The west unit
is a complex groove structure, with several large faults, and the coal
seam has a discernible undulation (Huang et al., 2010; Ye et al., 2012).
The Upper Carboniferous Taiyuan Formation and the Lower Permian
Shanxi Formation are the main coal-bearing strata in the study area,
containing a total of 6–11 coal seams. Among them, the thicknesses of
the No. 3 coal seam of the Shanxi Group and the No. 15 coal seam of
the Taiyuan Group are larger and have a stable spatial distribution.
They are the main coal seams for coal bed methane exploration.
The burial depth of the No. 3 coal seam is from 830 m to more than
1600 m due to dipping strata, and the thickness is 4–6 m with an
 K. Wang et al. / International Journal of Coal Geology 154–155 (2016) 265–274 267

average of 5.82 m. The No. 3 coal is mainly bright coal with vitrain
bands, metallic luster, vertical joints, and endogenous fissure develop-
ment. Plant fossil fragments can be found in part of the boreholes, and
there is a sandy mudstone or shale interlayer with a thickness of 0.24–
0.7 m (average 0.44 m) in the coal seam. Its roof is mainly composed
of mudstone, siltstone and silty mudstone, which locally is fine and me-
dium grained sandstone. Its floor is mainly mudstone and siltstone,
which locally is silty mudstone (Lu et al., 2012). The No. 3 coal seam is
considered to be suitable for geological CO2 storage.
of the two samples, as determined by X-ray fluorescence (XRF), are
given in Table 2. The XRD analysis was conducted using a PANalytical
X'Pert PRO powder diffractometer with a Cu X-ray source at 45 kV and
40 mA. Powder X-ray diffractograms were recorded between 5° and
52° 2-Theta. XRF analysis was conducted using a Rigaku ZSX Primus II
automatic order scanning X-ray fluorescence spectrometer. EMP analy-
ses were conducted on a JEOL JXA-8230 at 15 kV and 15 nA. SEM-EDS
observations were made using a Hitachi JSM-6700F field-emission scan-
ning electron microscope equipped with an INCA ENERGY 350 EDS
microanalytical system.

3. Materials and methods

3.1. Materials
The roof rocks of the No. 3 coal seam used in the experiments were
taken from the north block of Shizhuang of the Qinshui Basin in Shanxi
Province. Microscopic observations in transmitted light were made on
polished thin sections with a standard thickness of 0.02 mm. These ex-
aminations were carried out using a Leica DM2500 polarizing micro-
scope. Two types of lithology samples were selected: lithic sandstone
and calcareous mudstone (Fig. 2).
X-ray diffraction (XRD) semi-quantitative analysis, Electron Micro-
probe (EMP) analysis and Scanning Electron Microscopy (SEM) incor-
porating the use of a quantitative energy dispersive spectrometer
(EDS) confirm that the main mineral composition in the lithic sand-
stone includes quartz, clay minerals, plagioclase (albite dominated),
and a small amount of chlorite, and the main mineral composition in
the calcareous mudstone includes clay minerals, quartz, and small
amounts of K-feldspar and calcite (Table 1). The chemical compositions
3.2. Experimental setup and methods
The experiments were conducted in several uniform high-
temperature and high-pressure airtight reaction kettles, with liners
made of Hastelloy C-276 (Fig. 3). The advantages of the kettles are
their resistance to acid and alkali corrosion. The volume of the reaction
kettles was 300 mL. Other instruments, such as the incubator chamber,
electronic scales, and pH meters, were also used. The crushed rock, with
a grain size between 180 and 220 μm, was rinsed with distilled water
and dried in an oven at 80 °C for 48 h prior to the experiments. Before
the experiments, a mixture of rock and brine solution (1 M NaCl,
Merck analytical grade) with a water/rock ratio of 20:1 was poured
into the reactor, and then the mixture was bubbled with (N2) to remove
O2 from the solution to imitate the conditions found in geological reser-
voirs. For easier observation of mineral morphology, a polished thin sec-
tion was also added in the reactor. The system was then heated to the
desired temperatures before pressurizing with CO2 from a commercially
supplied bottle (≥ 99.9 vol.%). In the experiments with CO2–brine, a

Fig. 2. Thin-section imaging of the roof rock samples with a polarizing microscope. (a and b) Lithic sandstone, 10× magnification: (a) with plane-polarized light and (b) with cross-
polarized light. These two images show quartz, sandstone fragments and feldspar phenocrysts. (c and d) Calcareous mudstone, 10× magnification: (c) with plane-polarized light and
(d) with cross-polarized light. These two images show mudstone fragments and clay minerals. Carbonate cement is present in the fractures.
268 K. Wang et al. / International Journal of Coal Geology 154–155 (2016) 265–274

Table 1
Mineralogical composition by XRD (wt.%) (semi-quantitative).

Sample Quartz Plagioclase K-feldspar Calcite I/S Kaolinite Chlorite Biotite

Lithic sandstone 48 13 N/D N/D 25 10 2 2

Calcareous mudstone 19 2 2 2 54 20 N/D 1

I/S: illite/smectite mixed-layer minerals.

N/D: not detected.

Table 2
Chemical composition by XRF (%).

Sample SiO2 Al2O3 TFe2O3 CaO MgO K2O Na2O TiO2 P2O5 MnO L.O.I SUM

Lithic sandstone 76.31 10.38 6.67 0.33 1.01 0.63 2.01 0.26 0.02 0.02 2.21 99.86
Calcareous mudstone 56.3 20.47 4.01 2.73 2.23 2.9 0.75 0.88 0.15 0.07 9.29 99.78

L.O.I: loss on ignition.

pressure of 15 MPa was achieved by adjusting the initial CO2 pressure
using the air compressor and booster pump after heating. The system
was closed for the duration of the experiment; therefore, no sampling
was carried out until the end of the experiment. In all experiments par-
ticles in the solution were kept in suspension by turbulent stirring at a
speed of 200 rpm. There was a ± 1 °C variation in temperature, and
the pressure stayed within ± 3 bar. Once stabilized, the temperature
stayed relatively stable throughout the experiments. A summary of
the experimental parameters is given in Table 3.
After the reaction, liquid and solid samples were collected after
quenching and releasing the pressure in the reactor. The solution
was filtered through a 0.45 μm filter to separate the solution from
the solids. The liquid samples for metal analysis were acidified to
pH 2 with pure HNO 3 to prevent the precipitation of metals. Dis-
solved SiO2 was determined using a Seal-AutoAnalyzer 3™. Basic
metals were determined with an inductively coupled plasma mass
spectrometry (ICP-MS) (Agilent 7500C), and dissolved anions were
determined by ion chromatography (IC) (Metrohm 861). All report-
ed pH and alkalinity measurements were taken 3 h after the samples
were equilibrated with atmospheric P CO2 at room temperature
(20 °C). Solid samples were washed with distilled water on a
0.45 μm filter and then oven dried at 80 °C for 48 h before they
were analyzed. The mineral compositions of powder samples were
analyzed by XRD and XRF, and mineral morphology observations
were made on polished thin sections with SEM-EDS.
4. Results and analyses
4.1. Reaction of solid phases
4.1.1. Lithic sandstone
The content of solid minerals in lithic sandstone changed extensively
at the end of the experiment after 12 days. The primary minerals
alterated appreciably under the effect of CO2 acid fluid during the

Fig. 3. Schematic diagram of the experimental device.

Table 3
List of experiments and experimental parameters.

Sample Experiment Starting fluid Temperature (°C) Pressure (MPa) Solids (g) Water/rock ratio Duration (days)

Lithic sandstone Ext. 1 B+C 160 15 12.5 20:1 3

Ext. 2 B+C 160 15 12.5 20:1 6
Ext. 3 B+C 160 15 12.5 20:1 9
Ext. 4 B+C 160 15 12.5 20:1 12
Calcareous mudstone Ext. 5 B+C 160 15 12.5 20:1 12
Ext. 6 B 160 0.62a 12.5 20:1 12

B + C: reacted with brine and CO2.

B: reacted with CO2-free brine.
a
Saturated vapor pressure of water at 160 °C (~0.62 MPa).
 K. Wang et al. / International Journal of Coal Geology 154–155 (2016) 265–274
Fig. 4. Bulk XRD plots of the lithic sandstone: unreacted and reacted for 3, 6, 9, 12 days
with CO2–brine. Qtz—quartz, Pl—plagioclase, Kao—kaolinite, Chl—chlorite.
reaction time, where ions leached from minerals into the solution and
then formed new minerals through geochemical reactions (Fig. 4).
From the SEM images of lithic sandstone after the experiment, we
can see that quartz exhibited overgrowth phenomena (Fig. 5a) and
Fig. 5. SEM images of the lithic sandstone after 12 days of reaction with CO2–brine. (a) authigenic quartz, (b) corroded albite, (c) kaolinite in the cement, (d) authigenic chlorite.
269
plagioclase was slightly corroded (Fig. 5b). During the lithic sandstone
experiment, the plagioclase composition as determined by EMPA did
not significantly change. The plagioclase composition for untreated
and CO2-treated samples was generally clustered about the albite end-
member (Table 5). In addition, kaolinite and chlorite were also precipitat-
ed (Fig. 5c and d). However, through the SEM observation, and combined
with XRD analyses of the solid phase after the experiments, there were no
discernable new mineral phases (especially secondary carbonate min-
erals) precipitated in the whole experimental process. Therefore, after
different reaction times, the content and morphological structure of the
initial minerals changed appreciably. The relative contents of quartz, illite
and chlorite clearly increased, whereas the contents of illite/smectite, bi-
otite and kaolinite decreased more or less. (Table 4).
4.1.2. Calcareous mudstone
The mineral composition of the calcareous mudstone alterated
severely after the reaction compared with the original material. The
peaks of plagioclase, siderite, and dolomite were not clearly discernible
in the unreacted material, but they all increased after reaction with
CO2–brine and brine only, and they exhibited an analogical trend
(Fig. 6). This was due to the presence of large amounts of clay minerals
in the calcareous mudstone. The dissolution of K-feldspar and clay
minerals can release K, Al, Fe, Mg and other metal ions, and the dissolu-
tion of a small amount of calcite could supply HCO− 3 , which can generate
secondary carbonate minerals when combined with the metal ions
(Fig. 7d). As in the experiments of lithic sandstone, illite and chlorite
were all generated in large quantities (Fig. 7b and c). However, plagio-
clase experienced slight growth under the experimental conditions
(Fig. 7a). In this process, CO2 could not be a decisive factor in the forma-
tion of secondary carbonate minerals, although it may be at longer reac-
tion times.
270 K. Wang et al. / International Journal of Coal Geology 154–155 (2016) 265–274

Table 4 Table 6
Mineral composition by XRD after reaction (semi-quantitative). Saturation index of minerals involved in geochemical reactions.

Minerals Lithic sandstone Calcareous mudstone Minerals Lithic sandstone Calcareous mudstone

Initial B+C B+C B+C B+C Initial B+C B B+C B+C B+C B+C B+C B (12d)
(3d) (6d) (9d) (12d) (12d) (12d) (3d) (6d) (9d) (12d) (12d)

Quartz 48 57 42 52 57 19 44 46 Temperature 160 °C 160 °C 160 °C 160 °C 160 °C 160 °C

Plagioclase 13 17 25 18 11 2 4 5
SI SI SI SI SI SI
K-feldspar N/D N/D N/D N/D N/D 2 2 2
Chlorite 2 12 15 17 14 N/D 6 6 Albite 0.156 0.375 0.425 0.504 0.934 1.501
I/S 25 N/D N/D N/D N/D 54 N/D N/D Ankerite −0.580 0.211 0.638 0.726 −6.515 −4.823
Illite N/D 8 9 11 9 N/D 26 24 Calcite −1.137 −0.499 0.000 0.002 0.000 0.000
Kaolinite 10 6 9 8 9 20 8 8 Chlorite −0.024 −0.060 −0.062 −0.065 −35.822 −6.980
Calcite N/D N/D N/D N/D N/D 2 N/D N/D Dolomite 1.623 1.426 1.152 1.932 10.208 6.509
Biotite 2 N/D N/D N/D N/D 1 N/D N/D Dawsonite −1.259 −1.030 −0.938 −0.829 −1.207 −3.166
Siderite N/D N/D N/D N/D N/D N/D 4 2 Illite −0.008 0.009 0.005 0.002 −0.236 −0.011
Dolomite N/D N/D N/D N/D N/D N/D 6 7 Kaolinite 1.261 1.310 1.286 1.281 1.445 −0.476
K-feldspar −3.010 −2.868 −2.842 −2.836 −0.439 −0.555
B + C: reacted with brine and CO2.
Quartz 0.123 0.120 0.101 0.096 0.360 −0.136
B: reacted with CO2-free brine.
Siderite 0.980 1.388 1.411 1.413 −5.813 −5.038
All values are percentages of total dry weight.
Smectite 1.340 1.354 1.349 1.347 0.188 −0.016
I/S: illite/smectite mixed-layer minerals.
pHm 5.72 5.67 5.86 5.93 6.52 6.97
N/D: not detected.
pH 4.791 4.988 5.124 5.174 5.003 7.516

B + C: reacted with CO2–brine. B: reacted with brine only.

m: measured.
4.2. Fluid chemistry
SI: log (IAP/K), where IAP = ion activity product and K = equilibrium constant.

4.2.1. Reaction with lithic sandstone

Because the composition of the reaction liquid is 1 M NaCl solution,
some ions (K, Ca, Mg, Fe and Si) did not exist in the initial solution. For
the four experiments at 3, 6, 9 and 12 days, all of these ions were detect-
ed, indicating dissolution of reacting solids. A large amount of CO2
quickly dissolved into the water under high temperature and high pres-
sure, generating a large amount of HCO− 3 , and pH also decreased rapidly.
After 6 days of reaction, the concentration of HCO− 3 increased to
11.41 mmol/L, and pH was reduced to 5.67. Then, the concentration of
HCO− 3 began to decline, and pH began to rise (Fig. 8).
Because CO2 dissolved into the solution in this process, forming an
acidic environment, mineral dissolution occurred and then precipita-
tion. This mainly involved the dissolution of aluminosilicate minerals.
The calcium concentration in solution continued to increase. After
Table 5
Representative plagioclase compositions before and after CO2 treatment, as determined by
EMP analysis.
6 days, it was increasing faster, and reached 2.02 mmol/L at the end of
the experiments. Magnesium and SiO2 had the same trend: increasing
at the beginning, then decreasing gradually until they reached their
lowest values after 6 days, and then increasing. Fe concentrations in-
creased almost five-fold after 6 days of reaction, and then it declined
sharply (Fig. 9).
4.2.2. Reaction with calcareous mudstone
The release of major ions into solution varied, mainly depending on
the reacting fluids. To evaluate the effects of CO2 in the reaction process,
two experiments were conducted: Ext. 5 CO2–brine and Ext. 6 CO2-free
brine with calcareous mudstone. As shown in Fig. 10, in solutions from
reactions with CO2–brine, the concentration of Ca was almost double,
whereas concentrations of K, Fe, Si were higher by 54, 94 and 27%, re-
spectively, compared to their corresponding cases of brine only. The
concentration of Mg in the CO2–brine experiment was 65 times higher
than that in the brine-only experiment.

Untreated CO2 treated CO2 treated

for 3 days for 12 days

SiO2 67.29 67.77 66.89

Al2O3 20.69 20.19 20.15
MgO 0.01 0.02 0.01
FeO 0.15 0.11 0.21
TiO2 0.01 0.02 0.01
MnO 0.02 0.01 0.01
CaO 0.29 0.18 0.51
Na2O 10.42 10.67 10.24
K2O 0.18 0.23 0.07
∑ 99.06 99.20 98.10

Normalized to 8 oxygen
Si 3.14 3.16 3.12
Al 1.10 1.07 1.07
∑ 4.24 4.23 4.19
K 0.01 0.02 0.01
Ca 0.02 0.01 0.04
Na 0.77 0.79 0.76
Ti 0.00 0.00 0.00
Mg 0.00 0.00 0.00
Fe 0.01 0.01 0.02
Mn 0.00 0.00 0.00
∑ 0.81 0.83 0.83
xkfs 0.01 0.03 0.01
xan 0.03 0.01 0.05
Fig. 6. Bulk XRD plots of the calcareous mudstone: unreacted, reacted with CO2–brine, and
xab 0.96 0.96 0.94
reacted with brine only.
 K. Wang et al. / International Journal of Coal Geology 154–155 (2016) 265–274 271

Fig. 7. SEM images of the calcareous mudstone after 12 days of reaction with CO2–brine. (a) albite secondary enlargement boundary, (b) authigenic chlorite, (c) illite, and (d) carbonate
minerals.

4.3. Geochemical modeling
Based on a mass balance, the saturation index (SI) of the primary and
secondary minerals can reflect the mineral dissolution and precipitation
to a certain extent. The saturation index of minerals can be calculated
by geochemical modeling. The simulation was done with the non-
isothermal multiphase reactive transport code TOUGHREACT, which
was developed by US Lawrence Berkeley National Laboratory (Xu et al.,
2006). A broad range of subsurface thermal–physical–chemical processes
are considered under various thermohydrological and geochemical
conditions of temperatures (0–300 °C), pressures (1 to hundreds bars),
water saturation, ionic strength (up to 6 mol/kg H2O), and pH. The pro-
gram can be applied to the related numerical simulation study for pore
media and fractured rock for one, two, and three-dimensional domain.
On the basis of the measured final solution composition of fluids,
equilibrium speciation calculations were made for all experiments for
the two rock samples. In addition, a predictive kinetic calculation was
also run for the lithic sandstone that was reacted with CO2–brine for 3,
6, 9, and 12 days at 160 °C and 15 MPa. Saturation indices are given in
Table 6.

Fig. 8. Changes in pH and HCO−

3 concentration during the reaction time for the lithic Fig. 9. Changes of ion concentrations during the reaction time for the lithic sandstone
sandstone experiments. experiments.
272 K. Wang et al. / International Journal of Coal Geology 154–155 (2016) 265–274
Fig. 10. Leachate chemistry of the calcareous mudstone reacted with CO2–brine and brine-
only for 12 days at 160 °C.
From the simulation results, it can be seen that, for the lithic sand-
stone reacted with CO2–brine at 160 °C, the solution gradually became
saturated with respect to ankerite and illite over time. Dawsonite and
K-feldspar in all four experiments at different reaction times were not
saturated. Calcite was unsaturated in the early stage of the reaction,
then it reached a saturated state after 12 days of reaction. The solution
was saturated with respect to kaolinite, quartz, siderite and smectite
in all four experiments. For the calcareous mudstone, the main change
was the emergence of plagioclase and dolomite, which were detected
by XRD and SEM. This was consistent with the positive saturation indi-
ces. The solution was saturated with respect to kaolinite, quartz and
smectite under the CO2–brine condition, whereas it was unsaturated
with respect to these minerals under the CO2-free condition. For both
lithic sandstone and calcareous mudstone, the solution was unsaturated
with respect to chlorite in all six experiments, indicating that its disso-
lution would continue if the experiment was been allowed to run for
longer periods.
5. Discussion
5.1. Dissolution and precipitation of minerals induced by injected CO2
To speed up the rate of reactions, and to overcome the kinetic barrier
of mineral dissolution and precipitation, the experiments were run at
higher temperature (160 °C) than the current reservoir temperature
(40 °C). This is because the rate of silicate mineral reactions increases
with increased temperature (Gunter et al., 1997; Gislason and Oelkers,
2003; Credoz et al., 2009). In addition, the reactive surface area of the
caprock material was increased by crushing it to 180–220 μm grain
size to increase the reactivity. A brine solution of 1 M NaCl was used
as a substitute for formation water to encourage the dissolution process,
as the presence of more ions in the initial brine solution, especially diva-
lent cations, has a pH-buffering effect and decreases the acid-induced
reactions. The water rock ratio was also increased for reactivity com-
pared to practical geological storage conditions. Further enhancement
of dissolution was guaranteed by continuous stirring. Results of the
six experiments provided data that contribute to the qualitative under-
standing of fluid rock interactions under geochemical settings of CO2 se-
questration in deep coal seams. From X-ray diffraction analysis and SEM
images, dissolution and precipitation of minerals due to reaction of
acidic fluid with formation rock after CO2 injection could be clearly
observed. However, secondary carbonate minerals were found in the in-
tergranular pore space only in the experiment of calcareous mudstone
reacted with CO2 and brine for 12 days. The generation of secondary car-
bonate minerals was not found in any of the other experiments. The
main reason may be because the reaction time was shorter. The exper-
iments of other studies lasted for longer times, e.g., several weeks,
months or more than 1 year (Alemu et al., 2011; Tarkowski and
Wdowin, 2011; Fischer et al., 2013; Wdowin et al., 2014). With the
progress of the experiments, various elements released into the reaction
liquid from primary materials, resulting in dramatic changes in ion con-
centrations in the aqueous phase, which can be used as an effective
monitoring tool of CO2 leakages from underground reservoirs to shal-
low aquifers, This makes it valuable and necessary to obtain the chemi-
cal background characteristics of aquifers.
Geochemical simulation can reflect the results of the experiments to
some extent, but there were also some differences between the simula-
tion and experimental results (Gaus, 2010). This is because a number of
parameters were used in the simulation, and the actual formation con-
dition is very complex. There are many factors involved in geochemical
reactions, and the differences between simulation and experimental re-
sults are larger when an actual field situation is considered. Therefore,
the fitting of experimental and simulation results is very challenging.
However, if considering the thermal dynamic parameters of actual min-
erals, geochemical modeling is also very necessary (Fischer et al., 2013).
In view of these reasons, the geochemical modeling needs a more com-
prehensive database that includes various minerals, particularly for clay
minerals with unique qualities.
Under the condition of geologic sequestration, CO2 injected into the
target reservoir will tend to migrate upwards towards the cap rock, be-
cause the density of the CO2 is lower than that of the formation water.
Because of the overlying cap rock with a lower permeability, much of
the supercritical CO2 will accumulate at the bottom of the cap rock
and migrate slowly with the flow of the formation water (Bachu and
Shaw, 2003; Xu et al., 2010). The accumulated CO2 under the cap rock
will gradually dissolve into brine, lowers the pH and change the aque-
ous complexation, thereby inducing mineral alteration. In turn, the min-
eralogical composition could impose significant effects on the evolution
of the solution, and on the CO2 storage. The sealing ability of the cap rock
is always the key in the study of the safety of GCS, and it is also an impor-
tant security index in the evaluation of GCS (W. Zhang et al., 2009;
X. Zhang et al., 2009). A large number of experiments (Kaszuba et al.,
2005; Wigand et al., 2008; Busch et al., 2009; Gaus, 2010; Yalcinkaya
et al., 2011; Liu et al., 2012) and numerical simulations (Gaus et al.,
2005; Gherardi et al., 2007; Fischer et al., 2013, 2014; Tian et al., 2014)
were carried out to study the effects of CO2–brine–rock geochemical
reactions on the self-sealing of cap rock. The results show that the influ-
ence mainly depends on mineral composition, pH conditions and reac-
tion time, etc. Secondary precipitation of minerals could block pore
channels, further reducing the rate of CO2 diffusion and restricting the
process of interaction between fluid and rock.
5.2. Potential mobilization of organic compounds due to the presence of CO2
Supercritical CO2 is a good solvent for organic compounds such as
benzene, toluene, ethyl-benzene, and xylene (BTEX), phenols, and poly-
cyclic aromatic hydrocarbons (PAHs) (Anitescu and Tavlarides, 2006;
Kolak and Burruss, 2006). Monitoring results from GCS field tests have
shown that organic compounds are mobilized following CO2 injection
(Monin et al., 1988; Olukcu et al., 1999; Okamoto et al., 2005; Kharaka
et al., 2009, 2011; Scherf et al., 2011). Such results have raised concerns
regarding the potential for groundwater contamination by toxic organic
compounds mobilized during GCS. Knowledge of the mobilization
mechanism of organic compounds and their transport and fate in the
subsurface is essential for assessing risks associated with GCS. Especially
for coal measure strata, which contain large amounts of organic matter,
once CO2 is injected into the coal seams for long term sequestration, it
will inevitably extract the organic matter from the coal and typical cap
rock such as shale or mudstone.
 K. Wang et al. / International Journal of Coal Geology 154–155 (2016) 265–274
There is still very little study devoted specifically to organic material
migration caused by CO2 sequestration in deep coal seams or aban-
doned oil and gas field formations. Kolak and Burruss (2006) conducted
laboratory experiments to evaluate the potential for mobilizing non-
methane hydrocarbons during CO2 storage or enhanced coal bed meth-
ane recovery from deep coal beds, where coal samples of different rank
were extracted with supercritical CO2 (40 °C; 10 MPa). The experimen-
tal results showed that supercritical CO2 is capable of mobilizing hydro-
carbons from the coal matrix. The amount and type of hydrocarbons
mobilized varied in response to coal rank. The hydrocarbon distribu-
tions in samples extracted indicate that this influence of coal rank is
likely derived from the chemical changes associated with bitumen gen-
eration and cracking during increasing degrees of coalification and ther-
mal maturation. The coal samples continued to yield hydrocarbons
during consecutive supercritical CO2 extractions, indicating that the ex-
tent of hydrocarbon mobilization is not controlled solely by the solubil-
ity of hydrocarbons in supercritical CO2, but it may also be affected by
other factors, including hydrocarbon partitioning between bitumen-
supercritical CO2 phases. Zhong et al. (2014) conducted column exper-
iments using a water-wetted sandstone core installed in a tri-axial
core holder to study the potential impact on groundwater of toxic
organic compounds mobilized from coal by supercritical CO2 under
simulated GCS conditions. Their results indicated that the mobility
though the core sample was much higher for BTEX compounds than
for naphthalene. Retention of organic compounds from the vapor
phase to the core appeared to be primarily controlled by partitioning
from the vapor phase to the aqueous phase. Adsorption to the surfaces
of the wetted sandstone was also significant for naphthalene. Reduced
temperature and elevated pressure resulted in greater partitioning of
the mobilized organic contaminants into the pore water.
In this study, we focused on inorganic minerals, rather than organic
matter, in coal seams, despite the lack of theoretical or experimental
studies regarding the transport of organic compounds mobilized by
CO2 from a coal seam to the shallow aquifer or ground surface. There-
fore, the mobilization of organic compounds and its effects on the
physic-chemical properties of coal and rock should be considered in
future studies.
6. Conclusions
Experimental study indicated that, in the process of CO2 storage in
deep coal seams, the cap rock actively participated in chemical reactions
and played an important role in geological CO2 sequestration. The
chemical composition of the fluid and minerals alteration reflected the
process of CO2–brine–rock interaction. The change of mineral compo-
nents was clearly observed, mainly including dissolution of silicate min-
erals in lithic sandstone experiments, and precipitation of carbonate
minerals in calcareous mudstone experiments. Overall, the calcareous
mudstone was more reactive than the lithic sandstone, as documented
by the dissolution of calcite and illite/smectite and the formation of do-
lomite, siderite, illite and chlorite. CO2 was also permanently trapped as
dolomite and siderite. The lithic sandstone showed significant dissolu-
tion of silicate minerals (illite/smectite, kaolinite and biotite) and the
formation of chlorite and illite. Formation of clay minerals could cause
intergranular and intragranular pore blockage, reducing the porosity
of cap rock and thereby preventing permeation of CO2 through the
cap rock into the shallow aquifer, which would otherwise lead to
groundwater pollution. Thus, the formation of clay minerals would
increase the security of geological CO2 sequestration.
Geochemical simulation can reflect the dissolution and precipitation
state of minerals to some extent, but it does not entirely coincide with
the experimental results. Therefore, to guarantee the reliability of the
results, simulation requires many of the physical properties of the actual
formation and the thermal dynamic parameters of the rocks.
Finally, these types of water-rock interaction studies should be ap-
plied to the real project sites with 3-D models. As much as possible,
273
consideration should be given to the effects of relevant factors, includ-
ing fluid flow, geochemical reactions and geomechanics. The conjunc-
tion of these methods can yield more comprehensive prediction of the
physico-chemical changes due to mineral dissolution and precipitation
of caprock in geological CO2 storage.
Acknowledgments
This work was supported by the China Geological Survey working
project (Grant No. 12120113006300). We would like to thank the editor
Dr. Karacan, and three anonymous reviewers for their constructive
comments and suggestions for improving the quality of this paper.
References
Alemu, B.L., Aagaard, P., Munz, I.A., Skurtveit, E., 2011. Caprock interaction with CO2: a
laboratory study of reactivity of shale with supercritical CO2 and brine. Appl.
Geochem. 26 (12), 1975–1989.
Anitescu, G., Tavlarides, L.L., 2006. Supercritical extraction of contaminants from soils and
sediments. J. Supercrit. Fluids 38, 167–180.
Bachu, S., Shaw, J., 2003. Evaluation of the CO2 sequestration capacity in Alberta's oil and
gas reservoirs at depletion and the effect of underlying aquifers. Pet. Technol. 42 (9),
51–61.
Baran, P., Zarębska, K., Bukowska, M., 2015. Expansion of hard coal accompanying the
sorption of methane and carbon dioxide in isothermal and non-isothermal processes.
Energy Fuel 29 (3), 1899–1904.
Busch, A., Alles, S., Krooss, B.M., Stanjek, H., Dewhurst, D., 2009. Effects of physical sorp-
tion and chemical reactions of CO2 in shaly caprocks. Energy Procedia 1, 3229–3235.
Cai, Y., Liu, D., Pan, Z., Yao, Y., Li, C., 2015. Mineral occurrence and its impact on fracture
generation in selected Qinshui Basin coals: an experimental perspective. Int. J. Coal
Geol. 150, 35–50.
Credoz, A., Bildstein, O., Jullien, M., Raynal, J., Pétronin, J., Lillo, M., Pozo, C., Geniaut, G.,
2009. Experimental and modeling study of geochemical reactivity between clayey
caprocks and CO2 in geological storage conditions. Energy Procedia 1, 3445–3452.
Czerw, K., 2011. Methane and carbon dioxide sorption/desorption on bituminous
coal—experiments on cubicoid sample cut from the primal coal lump. Int. J. Coal
Geol. 85 (1), 72–77.
Dawson, G.K.W., Golding, S.D., Massarotto, P., Esterle, J.S., 2011. Experimental supercritical
CO2 and water interactions with coal under simulated in situ conditions. Energy
Procedia 4, 3139–3146.
Fischer, S., De Lucia, M., Liebscher, A., 2014. Kinetic modeling of laboratory CO2-exposure
experiments performed on whole rock reservoir samples. Greenh. Gases Sci. Technol.
4 (2), 244–256.
Fischer, S., Liebscher, A., De Lucia, M., Hecht, L., 2013. Reactivity of sandstone and siltstone
samples from the Ketzin pilot CO2 storage site—laboratory experiments and reactive
geochemical modeling. Environ. Earth Sci. 70 (8), 3687–3708.
Gale, J., Freund, P., 2001. Coal-bed methane enhancement with CO2 sequestration world-
wide potential. Environ. Geosci. 8 (3), 210–217.
Gaus, I., 2010. Role and impact of CO2–rock interactions during CO2 storage in sedimenta-
ry rocks. Int. J. Greenh. Gas Control 4 (1), 73–89.
Gaus, I., Azaroual, M., Czernichowski-Lauriol, I., 2005. Reactive transport modeling of the
impact of CO2 injection on the clayey cap rock at Sleipner (North Sea). Chem. Geol.
217 (3), 319–337.
Gentzis, T., 2000. Subsurface sequestration of carbon dioxide—an overview from an Alberta
(Canada) perspective. Int. J. Coal Geol. 43 (1), 287–305.
Gherardi, F., Xu, T.F., Pruess, K., 2007. Numerical modeling of selflimiting and self-
enhancing caprock alteration induced by CO2 storage in a depleted gas reservoir.
Chem. Geol. 244 (1), 103–129.
Gislason, S.R., Oelkers, E.H., 2003. Mechanism, rates, and consequences of basaltic glass
dissolution: II. An experimental study of the dissolution rates of basaltic glass as a
function of pH and temperature. Geochim. Cosmochim. Acta 67 (20), 3817–3832.
Golding, S.D., Uysal, I.T., Bolhar, R., Boreham, C.J., Dawson, G.K.W., Baublys, K.A., Esterle,
J.S., 2013. Carbon dioxide-rich coals of the Oaky Creek area, central Bowen Basin: a
natural analogue for carbon sequestration in coal systems. Aust. J. Earth Sci. 60 (1),
125–140.
Gunter, W.D., Wiwchar, B., Perkins, E.H., 1997. Aquifer disposal of CO2-rich greenhouse
gases: extension of the time scale of experiment for CO2 sequestering reactions by
geochemical modelling. Mineral. Petrol. 59 (1–2), 121–140.
Huang, X., Sun, Q., Yan, B., Xiong, D., Wang, W., 2010. Coalbed methane potential of
Shizhuang North Block in Qinshui Basin, Shanxi. China Coalbed Methane 7 (5), 3–9.
Karacan, C.Ö., 2003. Heterogeneous sorption and swelling in a confined and stressed coal
during CO2 injection. Energy Fuel 17 (6), 1595–1608.
Kaszuba, J.P., Janecky, D.R., Snow, M.G., 2005. Experimental evaluation of mixed fluid re-
actions between supercritical carbon dioxide and NaCl brine: relevance to the integ-
rity of a geologic carbon repository. Chem. Geol. 217 (3), 277–293.
Kharaka, Y.K., Campbell, P., Thomas, R.B., 2011. Environmental impacts of geologic se-
questration of CO2: mobilized toxic organic compounds. International Symposium
on Isotopes in Hydrology, Marine Ecosystems, and Climate Change Studies. IAEA,
Monaco (March 29, 2011).
Kharaka, Y.K., Thordsen, J.J., Hovorka, S.D., Nance, H.S., Cole, D.R., Phelps, T.J., Knauss, K.G.,
2009. Potential environmental issues of CO2 storage in deep saline aquifers:
274 K. Wang et al. / International Journal of Coal Geology 154–155 (2016) 265–274
geochemical results from the Frio-I Brine Pilot test, Texas, USA. Appl. Geochem. 24,
1106–1112.
Kolak, J.J., Burruss, R.C., 2006. Geochemical investigation of the potential for mobilizing
non-methane hydrocarbons during carbon dioxide storage in deep coal beds. Energy
Fuel 20, 566–574.
Lei, H., Xu, T., Jin, G., 2015. TOUGH2Biot—a simulator for coupled thermal–hydrodynam-
ic–mechanical processes in subsurface flow systems: application to CO2 geological
storage and geothermal development. Comput. Geosci. 77, 8–19.
Li, H., Shimada, S., Zhang, M., 2004. Anisotropy of gas permeability associated with cleat
pattern in a coal seam of the Kushiro coalfield in Japan. Environ. Geol. 47 (1), 45–50.
Li, W., Cheng, Y.P., Wang, L., Zhou, H.X., Wang, H.F., Wang, L.G., 2013. Evaluating the secu-
rity of geological coalbed sequestration of supercritical CO2 reservoirs: The Haishiwan
coalfield, China as a natural analogue. Int. J. Greenh. Gas Control 13, 102–111.
Liu, F., Lu, P., Griffith, C., Hedges, S.W., Soong, Y., Hellevang, H., Zhu, C., 2012. CO2–brine–
caprock interaction: reactivity experiments on Eau Claire shale and a review of rele-
vant literature. Int. J. Greenh. Gas Control 7, 153–167.
Lu, X., Huang, W., Tang, X., Ao, W., Zhang, S., Liu, S., Jia, Y., Liu, H., 2012. Impact of lime-
stone of no. 15 coal seam roof on the coal bed methane exploitation, Southern
Qinshui Basin. Geoscience 26 (3), 518–526.
Massarotto, P., Golding, S.D., Bae, J.S., Iyer, R., Rudolph, V., 2010. Changes in reservoir
properties from injection of supercritical CO2 into coal seams—a laboratory study.
Int. J. Coal Geol. 82 (3), 269–279.
Metz, B., Davidson, O., De Coninck, H.C., Loos, M., Meyer, L.A., 2005. IPCC special report on
carbon dioxide capture and storage. Prepared by Working Group III of the Intergov-
ernmental Panel on Climate Change. Cambridge University Press, New York.
Monin, J.C., Barth, D., Perrut, M., Espitalie, M., Durand, B., 1988. Extraction of hydrocarbons
from sedimentary rocks by supercritical carbon dioxide. Org. Geochem. 13, 1079–1086.
Okamoto, I., Li, X., Ohsumi, T., 2005. Effect of supercritical CO2 as the organic solvent on
cap rock sealing performance for underground storage. Energy 30, 2344–2351.
Olukcu, N., Yanik, J., Saglam, M., Yuksel, M., Karaduman, M., 1999. Solvent effect on the
extraction of Beypazari oil shale. Energy Fuel 13, 895–902.
Pan, Z., Luke, C., 2007. Effects of coal matrix shrinkage/swelling on enhanced CBM recov-
ery through CO2 sequestration. China Coalbed Methane 4 (1), 7–10.
Qin, Y., Fu, X.H., Wu, C.F., 2005. Self-adjusted elastic action and its CBM pool-forming
effect of the high rank coal reservoir. Chin. Sci. Bull. 50 (B10), 99–103.
Scherf, A.K., Zetzl, C., Smirnova, I., Zettlitzer, M., Vieth-Hillebrand, A., 2011. CO2SINK-
group mobilisation of organic compounds from reservoir rocks through the injection
of CO2—comparison of baseline characterization and laboratory experiments. Energy
Procedia 4, 4524–4531.
Siriwardane, H.J., Bowes, B.D., Bromhal, G.S., Gondle, R.K., Wells, A.W., Strazisar, B.R., 2012.
Modeling of CBM production, CO2 injection, and tracer movement at a field CO2
sequestration site. Int. J. Coal Geol. 96, 120–136.
Sun, K., 2005. Model and numerical simulation about multispecies fluid diffusion and
seepage in exploitation coalbed methane by gas injection. J. Liaoning Tech. Univ. 24
(3), 305–308.
Tang, S., Tang, D., Yang, Q., 2004. Variation regularity of gas component concentration in
binary-component gas adsorption–desorption isotherm experiments. J. China Univ.
Min. Technol. 33 (4), 448–452.
Tarkowski, R., Wdowin, M., 2011. Petrophysical and mineralogical research on the influ-
ence of CO2 injection on Mesozoic reservoir and caprocks from the Polish lowlands.
Oil Gas Sci. Technol. Rev. IFP Energies Nouvelles 66 (1), 137–150.
Tian, H., Pan, F., Xu, T., McPherson, B.J., Yue, G., Mandalaparty, P., 2014. Impacts of hydro-
logical heterogeneities on caprock mineral alteration and containment of CO2 in geo-
logical storage sites. Int. J. Greenh. Gas Control 24, 30–42.
Tian, H., Xu, T., Li, Y., Yang, Z., Wang, F., 2015. Evolution of sealing efficiency for CO2 geo-
logical storage due to mineral alteration within a hydrogeologically heterogeneous
caprock. Appl. Geochem. 63, 380–397.
Vishal, V., Singh, L., Pradhan, S.P., Singh, T.N., Ranjith, P.G., 2013. Numerical modeling of
Gondwana coal seams in India as coalbed methane reservoirs substituted for carbon
dioxide sequestration. Energy 49, 384–394.
Wdowin, M., Tarkowski, R., Franus, W., 2014. Supplementary studies of textural and min-
eralogical changes in reservoir and caprocks from selected potential sites suitable for
underground CO2 storage. Arab. J. Sci. Eng. 39 (1), 295–309.
Weber, M., Wilson, T.H., Akwari, B., Wells, A.W., Koperna, G., 2012. Impact of
geological complexity of the Fruitland formation on combined CO2 enhanced
recovery/sequestration at San Juan Basin pilot site. Int. J. Coal Geol. 104, 46–58.
Wei, C., Qin, Y., Wang, G.G., Fu, X., Jiang, B., Zhang, Z., 2007. Simulation study on
evolution of coalbed methane reservoir in Qinshui basin, China. Int. J. Coal Geol. 72
(1), 53–69.
White, C.M., Smith, D.H., Jones, K.L., Goodman, A.L., Jikich, S.A., LaCount, R.B., DuBose, S.B.,
Ozdemir, E., Morsi, B.I., Schroeder, K.T., 2005. Sequestration of carbon dioxide in coal
with enhanced coalbed methane recovery — a review. Energy Fuel 19 (3), 659–724.
Wigand, M., Carey, J.W., Schütt, H., Spangenberg, E., Erzinger, J., 2008. Geochemical effects
of CO2 sequestration in sandstones under simulated in situ conditions of deep saline
aquifers. Appl. Geochem. 23 (9), 2735–2745.
Winter, E.M., Bergman, P.D., 1993. Availability of depleted oil and gas reservoirs for
disposal of carbon dioxide in the United States. Energy Convers. Manag. 34 (9),
1177–1187.
Wong, S., Law, D., Deng, X., Robinson, J., Kadatz, B., Gunter, W.D., Zhiqiang, F., 2007.
Enhanced coalbed methane and CO2 storage in anthracitic coals—micro-pilot test at
South Qinshui, Shanxi, China. Int. J. Greenh. Gas Control 1 (2), 215–222.
Wong, S., Macdonald, D., Andrei, S., Gunter, W.D., Deng, X., Law, D., Ho, P., 2010. Concep-
tual economics of full scale enhanced coalbed methane production and CO2 storage
in anthracitic coals at South Qinshui basin, Shanxi, China. Int. J. Coal Geol. 82 (3),
280–286.
Wu, S., Zhang, A., 2007. A three-dimension multicomponent flow model of enhanced
coalbed methane recovery by gas injection. Nat. Gas Geosci. 18 (4), 580–583.
Xu, T., Apps, J.A., Pruess, K., 2004. Numerical simulation of CO2 disposal by mineral trap-
ping in deep aquifers. Appl. Geochem. 19 (6), 917–936.
Xu, T., Kharaka, Y.K., Doughty, C., Freifeld, B.M., Daley, T.M., 2010. Reactive transport
modeling to study changes in water chemistry induced by CO2 injection at the
Frio-I Brine Pilot. Chem. Geol. 271 (3), 153–164.
Xu, T., Sonnenthal, E., Spycher, N., Pruess, K., 2006. TOUGHREACT—a simulation program
for non-isothermal multiphase reactive geochemical transport in variably saturated
geologic media: applications to geothermal injectivity and CO2 geological sequestra-
tion. Comput. Geosci. 32, 145–165.
Yalcinkaya, T., Radonjic, M., Willson, C.S., Bachu, S., 2011. Experimental study on a single
cement-fracture using CO2 rich brine. Energy Procedia 4, 5335–5342.
Ye, J., Zhang, B., Wong, S., 2012. Test of and evaluation on elevation of coalbed methane
recovery ratio by injecting and burying CO2 for 3# coal seam of north section of
Shizhuang, Qingshui Basin, Shanxi. Chin. Eng. Sci. 14 (2), 38–44.
Zhang, W., Li, Y., Xu, T., Cheng, H., Zheng, Y., Xiong, P., 2009a. Long-term variations of CO2
trapped in different mechanisms in deep saline formations: a case study of the
Songliao Basin, China. Int. J. Greenh. Gas Control 3 (2), 161–180.
Zhang, X., Lu, X., Liu, Q., 2009b. The effect of the characteristics of cap on the escaping
velocity of CO2. Soil Eng. Found. 23 (3), 67–70.
Zhang, X., Qian, C., Peng, J., 2004. Adsorption and desorption characteristics of coal. Well
Test. Prod. Technol. 25 (3), 23–24.
Zhong, L., Cantrell, K.J., Bacon, D.H., Shewell, J., 2014. Transport of organic contaminants
mobilized from coal through sandstone overlying a geological carbon sequestration
reservoir. Int. J. Greenh. Gas Control 21, 158–164.
Zhou, F., Hussain, F., Cinar, Y., 2013. Injecting pure N2 and CO2 to coal for enhanced
coalbed methane: experimental observations and numerical simulation. Int. J. Coal
Geol. 116, 53–62.