Petroleum 9 (2023) 274e284

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Petroleum
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Assessment of CO2 geological storage capacity based on adsorption

isothermal experiments at various temperatures: A case study of No. 3
coal in the Qinshui Basin
Sijie Han a, b, Shuxun Sang a, b, c, *, Jinchao Zhang c, Wenxin Xiang c, Ang Xu c
a
Jiangsu Key Laboratory of Coal-based Greenhouse Gas Control and Utilization, China University of Mining and Technology, Xuzhou, 221008, China
b
Carbon Neutrality Institute, China University of Mining and Technology, Xuzhou, 221008, China
c
School of Resources and Earth Sciences, China University of Mining and Technology, Xuzhou, 221116, China

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

Article history: Carbon dioxide (CO2) capture, utilization, and storage (CCUS) is an important pathway for China to
Received 16 September 2021 achieve its “2060 carbon neutrality” strategy. Geological sequestration of CO2 in deep coals is one of the
Received in revised form methods of CCUS. Here, the No. 3 anthracite in the Qinshui Basin was studied using the superposition of
29 October 2021
each CO2 geological storage category to construct models for theoretical CO2 geological storage capacity
Accepted 1 April 2022
(TCGSC) assessment, and CO2 adsorption capacity variation with depth. CO2 geological storage potential
of No. 3 anthracite coal was assessed by integrating the adsorption capacity with the static storage and
Keywords:
dissolution capacities. The results show that (1) CO2 adsorption capacities of XJ and SH coals initially
CO2 geological storage in coal
Theoretical geological storage capacity
increased with depth, peaked at 47.7 cm3/g and 41.5 cm3/g around 1000 m, and later decreased with
The abundance of CO2 geological storage depth. (2) four assessment areas and their geological model parameters were established based on CO2
capacity phase variation and spatial distribution of coal thickness, (3) the abundance of CO2 geological storage
Anthracite capacity (ACGSC), which averages 40 cm3/g, shows an analogous circularity-sharp distribution, with the
Qinshui basin high abundance area influenced by depth and coal rank, and (4) the TCGSC and the effective CO2
geological storage capacity (ECGSC) are 9.72 Gt and 6.54 Gt; the gas subcritical area accounted for 76.41%
of the total TCGSC. Although adsorption-related storage capacity accounted for more than 90% of total
TCGSC, its proportion, however, decreased with depth. Future CO2-ECBM project should focus on high-
rank coals in gas subcritical and gas-like supercritical areas. Such research will provide significant
reference for assessment of CO2 geological storage capacity in deep coals.
© 2022 Southwest Petroleum University. Publishing services by Elsevier B.V. on behalf of KeAi
Communications Co. Ltd. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction technology for carbon emissions reduction has attracted world-

wide attention [1,2]. CO2 geological sequestration in deep coal
In response to the growing environmental problems caused by seams is an important part of CCUS and an inevitable pathway to
greenhouse gas emissions, China is committed to reaching peak achieve carbon peak and carbon neutralization in the coal industry
carbon emissions by 2030 and carbon neutrality by 2060. Carbon [3]. Previous studies have proposed different techniques for
dioxide (CO2) capture, utilization, and storage (CCUS) as a key assessment of CO2 storage potential in coal: CSLF [4], DOE [5] and
coalbed methane resource conversion methods [6e8]. In China,
several studies have applied modified versions of these techniques
to storage evaluation in different coal-bearing basins and found
* Corresponding author. that great potential exists for CO2 geological storage in deep coal
E-mail address: shxsang@cumt.edu.cn (S. Sang).
[9e12]. The key influence factors of CO2 geological storage in coal
Peer review under responsibility of Southwest Petroleum University.
include geological background conditions (e.g. stratigraphy, struc-
ture and hydrodynamics), coal occurrence and reservoir conditions
(e.g. depth, thickness, temperature, pressure, coal quality and
Production and Hosting by Elsevier on behalf of KeAi permeability) and engineering conditions [13,14]. Adsorption, the

https://doi.org/10.1016/j.petlm.2022.04.001
2405-6561/© 2022 Southwest Petroleum University. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
S. Han, S. Sang, J. Zhang et al. Petroleum 9 (2023) 274e284

main mechanism of CO2 geological sequestration in coal, accounts the highly positive magnetic anomaly and magmatic hydrothermal
for most of the storage capacity. However, adsorption capacity is veins in the south and north Qinshui Basin demonstrated that the
known to decrease with burial depth after it reaches the maximum concealed intrusions played a significant role in promoting the
capacity [15]. Similar capacity change has been reported for coalification in these areas [24].
methane adsorption, indicating a synergistic control of tempera- No. 3 coal seam in Qinshui Basin has an annular shape and its
ture and pressure [16]. The high pressure contributes to improve depth increases progressively from the edge of the basin to the
CO2 storage capacity in coals but its control may be weak after CO2 hinterland. Depth ranges from less than 300 m at the edge to
becomes supercritical phase, which is resulted from the pressure greater than 2000 m at the center, near Qinxian County (Fig. 1a).
effect on CO2 adsorption [17e19]. However, the decrease in the Due to the control exerted by a group of parallel normal faults,
adsorption capacity is more significant at greater depth, suggesting depth increased rapidly to about 4500 m near Qi County in the
that supercritical CO2 adsorption is more sensitive to the negative northwest of the basin. No.3 coal in the Shanxi Formation is widely
effect of temperature [20]. As temperature and pressure interplays distributed across the basin with thickness ranging from 0.53 to
in the coal reservoir environment, the transformation of CO2 fluid 7.84 m. Generally, thickness increase gradually from north to south
properties influences its adsorption behavior on coal thereby with the southeast being the thickest (Fig. 1b). While coal thickness
resulting in storage capacity variation at different depths [21]. Due is greater than 6 m in the Anze-Panzhuang area, it is less than 2 m
to the high density of supercritical CO2 and the decease in in the middle and the northern part of the basin. The relatively
adsorption capacity under deep coal environment, free CO2 stored uniform and regular development of the No. 3 coal seam in the
in pores plays an increasing role on the total CO2 geological storage Qinshui Basin not only facilitates subsequent calculation of CO2
capacity [22,23]. Interestingly, the variation of CO2 geological geological storage capacity, but also reduces the impact of coal
storage capacity at different depths was not considered in previous seam heterogeneity on the accuracy of assessment results.
studies. In addition, the lack of CO2 adsorption isotherms at
different temperatures during assessment of storage capacity in 3. Samples and methods
coal often results in inaccurate determination of absolute adsorp-
tion capacity. 3.1. Samples
In this study, the high-pressure CO2 isotherm adsorption ex-
periments at varying temperatures were first conducted on two Two coal samples (XJ and SH coals) were collected from the
anthracites collected from the Qinshui Basin and then the super- Xinjing Coal Mine in Yangquan City and Sihe Coal Mine in Jincheng
critical DR adsorption model was used to fit the adsorption data. City which are in the north and south of the Qinshui Basin. Two
Second, a new method for calculating CO2 geological storage ca- samples, belong to No.3 coal in the Shanxi Formation, are anthracite
pacity based on adsorption isotherm was proposed, and it was with vitrinite and inertinite macerals and no chitinite. These two
applied for prediction of the CO2 adsorption capacities at different anthracites can represent major No.3 coal rank in the Qinshui Basin,
depths. Third, Based on the division of the Qinshui Basin and the which have a high affinity with gas adsorption capacity. Their
establishment of CO2 geological storage model parameters, the mineralogical composition is mainly quartz, calcite, pyrite, and
distribution of the abundance of CO2 geologic storage capacity minor clay minerals. Pore structures, especially the surface area
(ACGSC) in No.3 coal in the Qinshui Basin was presented. Finally, associated with gas adsorption, obtained from mercury intrusion
the theoretical CO2 geologic storage capacity (TCGSC) and the porosimetry of the coal sample sets are highly consistent. Basic
effective CO2 geologic storage capacity (ECGSC) in the different analysis of vitrinite reflectance, macerals and pore structure are
areas were calculated. The aim of this study is to develop an shown in Table 1.
improved method for assessment of CO2 geological storage po-
tential of coal. 3.2. High pressure CO2 adsorption isothermal experiments

2. Geological setting of Qinshui Basin The CO2 isothermal adsorption experiment used the DXF-II high-
pressure, high-temperature isothermal adsorption system designed
The Qinshui Basin is a simple NNE-trending synclinorium tra- by our group [19]. The device is designed based on the manometric
versed by sparse faults, with its fold axis located on the Yushe- method principle, and the excess adsorption amount was calculated
Qinxian-Qinshui line (Fig. 1). The basin has an incomplete strati- using the equation of state of real gas. In the experiments, 50 g al-
graphic sequence without Silurian, Devonian and Lower Carbonif- iquots of each coal sample, with particle size ranging from 60 to 80
erous and this sequence is consistent with those in North China. mesh (0.25e0.18 mm), were analyzed. The experiment was con-
Therein, Carboniferous-Permian (CeP) are the major coal-bearing ducted in accordance with Chinese National Standard (Experimental
strata. Controlled by syncline, CeP is only exposed at the margin method of high-pressure adsorption isothermal to coal-capacity
of the basin and the reverse dome-like structure of the basin in- method) and yielded a relative error of ±1%. Before CO2
dicates that the CeP coals are deeply buried at the center of basin. isothermal adsorption, the air tightness of the equipment was first
The degree of structural deformation in the basin is generally low assessed, and then equilibrium moisture treatment of coal samples
and the effect of tectonic damage on the CeP coal seam is minimal. and the determination of volume of adsorption cell was carried out.
The coal-bearing strata (CeP system), in the order of successive In order to ensure that no liquefaction of CO2 is under high pressure,
development are, Benxi Formation, Taiyuan Formation, Shanxi the isotherm was designed at 40
C, 50
C, 60
C, 70
C and 80
C.
Formation, Xiashihezi Formation, Shangshihezi Formation and Maximum adsorption equilibrium pressure was 16 MPa with excess
Shiqianfeng Formation, and their depositional environments range adsorbed volume recorded every 2 MPa.
from marine carbonate platform and barrier island-lagoon-tidal flat
to delta and meandering river sedimentary systems. Its overlying 3.3. Supercritical Dubinin-Radushkevich (DR) adsorption model
strata, Triassic, which are widely distributed in the basin, are
composed by tight clastic rock assemblages. They are considered as In this study, the supercritical gas adsorption model proposed
good cap rocks because of their low porosity and permeability and by Sakurovs et al. [25] was used to fit the experimental adsorption
form lithologic traps for CeP coal measure gas. Although the large- data under equilibrium moisture at different temperatures. Based
scale magmatic intrusions were undiscovered in the Qinshui Basin, on the micropore filling theory, this model can accurately fit the
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S. Han, S. Sang, J. Zhang et al. Petroleum 9 (2023) 274e284

Fig. 1. The tectonic characteristics of the Qinshui Basin and the distribution of 3# coal. (a) Depth of 3# coal; (b) Thickness of 3# coal.

Table 1
Basic properties of XJ and SH coals in the Qinshui Basin.

Sample Ro(%) Vitrinte (vol%) Inertinite (vol%) Pore volume (cm3/g) Special surface area (m2/g) Porosity (%) Apparent density (g/mL)

XJ 2.64 70.70 29.30 0.0346 18.50 4.30 1.24

SH 3.45 82.10 17.90 0.0325 18.49 4.22 1.30

CO2 adsorption curve from subcritical to supercritical conditions,

and reflect the adsorption characteristics of supercritical CO2 on Mt ¼ A  H  rcoal  V  rg (3)
coal. The equation has the following form.

 where Mt is the TCGSC, t; A is the area for CO2 geological storage,
rg D½lnðra =rg Þ2 m2, H is the height of coal, m; rcoal is the apparent density of coal, g/
Vexc ¼ V0 1  e þ krg (1)
ra cm3; V is the CO2 storage capacity in 1 g of coal, cm3/g.
Due to the long mineraleH2OeCO2 mineralization reaction time
where Vexc is the excess adsorption amount, cm3/g, V0 is the and the small number of raw materials, the CO2 mineralization
maximum adsorption capacity, cm3/g; D is a constant, indicating storage capacity is negligible. CO2 storage capacity, as defined in
the interaction between gas and coal; rg is the density of CO2 under this study, is composed of adsorption capacity, static storage ca-
standard conditions, g/cm3; ra is the adsorbed density of CO2 (1.0 g/ pacity and dissolution capacity. Since V is the CO2 storage capacity
cm3; cited by Day et al. [26]); k is the correction parameter for the in 1 g of coal, by using the concept of CBM resources abundance, we
expansion caused by gas adsorption. Free CO2 density at a given define this capacity as ACGSC. The equation has the following form:
pressure and temperature can be accurately calculated by NIST
REFPROP software. V ¼ Vad þ Vv0 þVs (4)
According to the definition of excess adsorption, the difference
between absolute and excess adsorption is equal to the volume that where Vv0 is the CO2 static capacity in 1 g of coal, which is defined as
has the same density as free gas in the adsorption space. Therefore, CO2 capacity in non-adsorptive space, cm3/g; Vs is the CO2 disso-
the absolute adsorption volume can be calculated as follows: lution storage capacity in 1 g of coal, cm3/g.
Adsorption capacity was obtained by combining Equations (1)
Vexc
Vab ¼    (2) and (2); static storage capacity, from the equation of real gas; and
1  rg ra dissolution derived from CO2 solubility equation proposed by Duan
and Sun [27]. Equation (4) is the complete CO2 storage capacity
where Vab is the CO2 absolute adsorption capacity, cm3/g; formula, which can give the ACGSC at different pressures and
temperatures.
3.4. Method for calculations of CO2 geological storage capacity in
coal 4ð1  SW ÞPVM 4Sw SCO2 VM
V ¼ Vab ðT; PÞ þ þ (5)
ZRT rcoal rcoal
The method used to calculate CO2 geological storage capacity is
based on the one used for CBM geological resources. TCGSC was Where VM is the molar volume of CO2, 22.4 L/mol, Vab (T, P) is the
obtained from the total CO2 storage capacity in 1 g of coal. The absolute adsorption capacity at a given temperature and pressure,
equation has the following form: cm3/g; 4 is the porosity of coal obtained by mercury intrusion
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porosimetry, %; Sw is the water saturation, %; P is the pressure, MPa, volume vs. pressure, and pressure vs. free CO2 density, the excess
Z is the compressibility factor at a given temperature and pressure; adsorption curves of XJ and SH coals at different CO2 densities were
R is the molar gas constant, 8.314 Pa$m3$mol1$K1; T is the tem- plotted (Fig. 3). It was evidenced from the curves that excess
perature, K; SCO2 is the solubility of CO2 in pure water in this study adsorption initially increased rapidly with CO2 density from 0 to
(The ionic concentration is negligible for CO2 dissolution calcula- 0.15 g/cm3, reached maximum values around 0.15e0.2 g/cm3, and
tion because of the low salinity in coal-bed water in the Qinshui later decreased showing negative correlation with free CO2 density.
Basin), mmol/cm3. In contrast to the excess adsorption curves generated on the graph
According to the classic pyramid model of CO2 geological storage with pressure as abscissa, the excess adsorption volume at each
capacity, ECGSC is a subset of TCGSC. In theory, TCGSC is the density point decreased with temperature, and no crossover of the
maximum under prevailing geological and engineering conditions curves was observed.
after delineating the assessment range [28]. Although CO2/CH4 Fitted results of supercritical DR adsorption model indicated
replacement reaction can occur in coals and improve CH4 recovery, that the fitted curves match the adsorption data with a high cor-
the CH4 is not completely released and the stored CO2 only occupies relation coefficient (r2 > 0.95) (see Table 3). Interestingly, the fit at
the space created post-CH4 extraction. The formula for calculating low temperature is better compared with high temperature, which
ECGSC is as follows: may be related to the transformation of supercritical CO2 adsorp-
tion behavior from micropore filling to surface coverage at high
Me ¼ Mt  RF (6) temperature. XJ coal decreasing V0 range of 45.81 to 31.43 cm3/g is
lower than that of SH coal, 53.41 to 33.86 cm3/g. The D values of the
where Me is the ECGSC, t; RF is the recovery factor of coalbed two coals (0.058e0.09 for XJ and 0.059e0.071 for SH) are similar,
methane enhanced by CO2 injection, %. and their k values are negative, suggesting that adsorption-induced
swelling reduced adsorption capacity. The effect of temperature is
4. Results negative on maximum adsorption capacity (V0) and constant k, but
positive on D value. On the whole, the adsorption parameters show
4.1. Results of isothermal experiments a regular relationship with temperature, and this forms the basis
for predicting CO2 adsorption capacity at varying temperatures.
CO2 excess adsorption curves showed maximum adsorption
volume between 6 and 9 MPa, and gradually moved to the right
5. Discussion
with increasing temperature (Fig. 2). The maximum excess
adsorption capacity of each coal sample, 32.27 cm3/g (XJ) and
5.1. Prediction of CO2 adsorption capacity with depth in the Qinshui
37.53 cm3/g (SH), were recorded at 40
C. After crossing the
Basin
maximum values, the curves show some irregular descents, but the
descents had different sharps at different temperatures. At low
Various subcritical and supercritical CO2 adsorption experi-
pressure (<6 MPa), excess adsorption decreased with temperature.
ments showed that CO2 adsorption capacity on coal changes
However, a reversal occurs at high pressure, the higher the tem-
significantly under the influence of temperature and pressure.
perature, the greater the excess adsorption is. This indicated that
Hence, when predicting the CO2 adsorption capacity at different
high temperature only had a negative effect on excess adsorption
depths, temperature and pressure variation should be considered
volume at low pressure. The curves crossed at various points and
simultaneously to avoid the deviation caused by fixed adsorption
the intersection position shifted rightwards. Excess adsorption
capacity on the assessment of CO2 geological storage. The super-
volume also revealed a stronger change near the critical pressure at
critical DR adsorption model, based on the adsorption potential
low temperature. Overall, temperature is a strong influence on
theory, is independent of temperature. However, the influence of
excess adsorption curve inflections.
temperature on adsorption parameters should be considered when
using supercritical DR adsorption model to predict CO2 adsorption
4.2. Fitted results capacity at different depths.
V0 represents CO2 adsorption capacity on coal, and correlates
In order to match the definition of density variables in super- negatively with temperature (T). D is a constant that reflects the
critical DR adsorption model, NIST REFPROP software was used to interaction between CO2 and coal, and its value is positively
calculate free CO2 densities at various pressures and temperatures correlated with the square of temperature. In contrast, k value is
(Table 2). Based on the relationship between excess adsorption negatively correlated with temperature as high-temperature

Fig. 2. Results of high-pressure CO2 adsorption experiments under equilibrium moisture condition at different temperatures. (a) XJ coal; (b) SH coal.

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S. Han, S. Sang, J. Zhang et al. Petroleum 9 (2023) 274e284

Table 2
CO2 free density corresponding to each equilibrium pressure at different temperatures.

Sample 40
C 50
C 60
C 70
C 80
C

Pressure(MPa) Density(g/ Pressure(MPa) Density (g/cm3) Pressure (MPa) Density (g/cm3) Pressure (MPa) Density (g/cm3) Pressure (MPa) Density (g/cm3)
cm3)

XJ 2.8 0.05 2.3 0.04 2.6 0.05 2.2 0.04 2.8 0.05
4.9 0.11 4.7 0.10 4.9 0.10 4.9 0.09 4.9 0.09
6.4 0.17 6.4 0.15 6.2 0.13 6.1 0.12 6.4 0.12
8.6 0.38 8.2 0.23 8.6 0.22 8.6 0.19 8.6 0.18
10.1 0.64 10.3 0.42 10.2 0.30 10.3 0.26 10.1 0.23
12.5 0.73 12.5 0.61 12.2 0.45 12.5 0.37 12.5 0.32
14.2 0.77 14.1 0.68 14.2 0.57 14 0.46 14.2 0.39
16.7 0.80 16.4 0.73 16.5 0.65 16.7 0.57 16.7 0.50
SH 2.4 0.05 2.5 0.05 2.3 0.04 2.2 0.04 2.7 0.04
4.5 0.10 4.3 0.09 4.1 0.08 4.5 0.08 4.1 0.07
5.8 0.14 5.3 0.11 5.2 0.10 5.2 0.10 5.7 0.10
8.6 0.38 8.2 0.23 8.1 0.20 8.4 0.19 8.6 0.18
10.2 0.64 10.2 0.41 10.4 0.32 10.3 0.26 10.3 0.23
12.2 0.72 12.5 0.61 12.7 0.49 12.4 0.37 12.7 0.33
14.6 0.77 14.2 0.68 14.3 0.58 14.6 0.49 14.7 0.41
16.8 0.81 16 0.72 16.2 0.64 16.3 0.56 16.7 0.50

Fig. 3. Fitted results of CO2 adsorption data using supercritical DR adsorption model. (a) XJ coal; (b) SH coal.

Table 3
Fitted adsorption parameters obtained by supercritical DR adsorption model.

Coal Fitted parameter 40
C 50
C 60
C 70
C 80
C

0:0111T 2
V0(cm3/g)
D ðXJ Þ ¼  0:051 (8)
XJ 45.81 42.40 37.57 35.29 31.43 10000
D 0.058 0.068 0.069 0.078 0.090
k 1.46 2.26 3.56 5.81 7.19
R2 0.99 0.98 0.96 0.95 0.96
SH V0(cm3/g) 53.41 47.55 41.28 37.29 33.86
D 0.058 0.063 0.068 0.070 0.073 kðXJÞ ¼  0:15T þ 45:95 (9)
k 1.09 1.14 1.60 3.39 3.56
R2 0.99 0.99 0.97 0.95 0.95

reduces the swelling caused by gas adsorption. Hence, the graphs 1

V0 ðSHÞ ¼ 54:78  1000  122:06 (10)
showing the relationship between adsorption parameters (V0, D T
and k) and temperature were established (Fig. 4). The relationships
are linear with very high correlation coefficients (r > 0.9) that
shows the reliability of the modified equation of supercritical CO2
adsorption model. 0:0046T 2
D ðSH Þ ¼ þ 0:015 (11)
According to the linear fitted results, the relationship between 10000
temperature and the three adsorption parameters for XJ and SH
coals can be expressed as:

kðSHÞ ¼  0:072T þ 21:8 (12)

By integrating the above expressions with the supercritical DR
1
V0 ðXJÞ ¼ 39:69  1000  80:86 (7) adsorption model, the calculation model of CO2 excess adsorption
T capacity for XJ and SH coals at different temperatures and pressures
(free phase density) can be obtained:
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S. Han, S. Sang, J. Zhang et al. Petroleum 9 (2023) 274e284

Fig. 4. Relationship between temperature and adsorption parameters. (a) XJ coal; (b) SH coal. (T means temperature).

!



 0:0111T 2 ra
1 rg  10000
0:051 ln2 rg
VXJ ¼ 39:69  1000 80:86 1 e
T ra
þ ð  0:15T þ 45:95Þrg
(13)


1
VSH ¼ 54:78  1000  122:06
T
!


 2 ra
rg  10000 þ0:015 ln rg
0:0046T 2

 1 e þ ð  0:072T þ 21:8Þrg
ra
(14)
Previous reports on the temperature and pressure of coal seams
in the Qinshui Basin showed geothermal gradient of 28.2
C/km
Fig. 5. Variation of CO2 densities and adsorption amounts of XJ and SH coals at
[29] and the pressure coefficient of 0.71 MPa/100 m [30]. Based on
different temperatures and pressures in Qinshui Basin (a) Density of CO2; (b) CO2
these data, CO2 density curve at depth interval between 0 and adsorption amount.
3000 m was generated using NIST REFPROP software, see fig. 5(a).
The CO2 density curve increased monotonically, but the increment
rate is significantly higher between 0 and 1500 m than between like phases [31,32]. Unlike gas-like supercritical CO2 that has low
1500 and 3000 m. After temperature and pressure reached critical density and high compressibility, liquid-like supercritical CO2 has
points, CO2 entered the supercritical phase. The transition from high density and low compressibility. The density boundary be-
subcritical to supercritical phase occurred around 1000 m (36.64
C, tween the two states is approximately equal to the critical density
7.1 MPa), and CO2 low increment rate between 1500 m and 3000 m of CO2 (0.448 g/cm3). CO2 shows rapid density increase and high
suggests that there is a change in density in the supercritical phase. compressibility before 1500 m, but beyond this depth, density
Previous studies suggest that although supercritical CO2 has some increment rate reduced significantly. This suggests that, for deeply
characteristics of both gas and liquid, there are two supercritical buried coals, CO2 static storage capacity will almost remain un-
phases with large differences in properties; the gas-like and liquid- changed or even decrease due to pore-space compressibility.

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Therefore, adsorption storage capacity is always dominant in the storage capacity assessment results. The gas subcritical area can be
total CO2 geological storage capacity. Based on CO2 density char- divided into north and south, and the depth to the thickest coal in
acteristics, the monotonically increasing curve can be divide into the southern area is less than 1000 m. This division also coincides
three segments with boundary depths of 1000 m and 1500 m be- with the distribution of coal ranks in the northern and southern
tween them. They are gas subcritical, gas-like supercritical, and basins. Consequently, based on depth, coal rank and thickness
liquid-like supercritical CO2 segments. distribution of No.3 coal, the Qinshui Basin can be divided into four
After obtaining the CO2 density curve, Equations (13) and (14) assessment areas: gas subcritical north, gas subcritical south, gas-
were used to calculate the curves of absolute adsorption capacity of like supercritical. and liquid-like supercritical areas, see fig. 6(a).
XJ and SH coals under reservoir conditions in the Qinshui Basin, see
fig. 5(b). CO2 adsorption capacities of the two coals show similar 5.2.2. CO2 geological storage parameter model
trends as they increased linearly and peaked around 1000 m. CO2 Qinshui basin is 29,400 km2 in areal extent, and the size of in-
adsorption capacity increased at a lower rate beyond the 1000 m, dividual divisions are: gas subcritical south, 10,785 km2; gas
indicating that pressure has a positive effect, but its control be- subcritical north area, 3625 km2; gas-like supercritical area,
comes increasingly weak with depth. At intervals between 1000 6350 km2; liquid-like supercritical area, 8650 km2. The tempera-
and 1500 m, the rate of CO2 adsorption capacity reduction is ture and pressure of No. 3 coal in Qinshui Basin are vertically
significantly reinforced due to the negative effect of increasing continuous. Previously reported geothermal gradient and pressure
temperature. Below 1500 m, the monotonous linear decrease coefficient were used to determine the temperature and pressure at
suggests that temperature is the governing factor in this segment. different depth intervals [29,30]. Therefore, the temperature and
The observed changes in adsorption capacity are highly consistent pressure ranges for the four subareas are gas subcritical north and
with CO2 phase change. Subcritical and gas-like supercritical CO2 south areas, 22.54e36.64
C and 3.55e7.1 MPa; gas-like supercrit-
have large compressibility. As density increases rapidly with depth, ical area, 36.64e50.74
C and 7.1e10.65 MPa; liquid-like supercrit-
more free CO2 molecules will approach the surface of coal. This will ical area, 50.74e64.84
C and 10.65e14.2 MPa according to their
increase the chance for the molecule to be captured onto the sur- depths. Coal thicknesses vary across the subareas and the average
face, thus contributing to an increase in adsorption capacity. values are 5 m, 2 m, 2 m and 1.5 m. Porosity of No. 3 coal as
However, CO2 density has a low increment rate in the liquid-like determined statistically is low (<5%) and only changed minimally
supercritical segment, which is not enough to offset the weak- with depth. This porosity is comparable to that of coals in the
ening of the attraction between CO2 molecules and coal caused by Qinshui Basin, which is generally less than 6% (average 4%).
rising temperature. Therefore, CO2 adsorption capacity is signifi- Therefore, average porosity of 4.26% obtained from mercury
cantly reduced in this segment. These results showed that CO2 intrusion porosimetry was applied to all subareas. Because of the
adsorption capacity has a strong link with CO2 density, suggesting single porosity value adopted for the coals, constant apparent
that supercritical adsorption behavior on coals may be related to density (1.25 g/cm3) was also assigned to them. The coals in Qinshui
density variation. Basin have varying water contents. It was assumed that shallow
coal at depths above 1000 m has 50% water saturation, and deep
5.2. Divisions of the Qinshui Basin and their geological model coal, 80%. After temperature and pressure were determined, the
parameters CO2 solubility calculation model proposed by Duan and Sun [27]
was used to obtain the solubility at each depth range, and their
5.2.1. Divisions of the Qinshui Basin based on No.3 coal distribution average values are 1.08 mol/L, 0.96 mol/L and 1.07 mol/L. At a given
and occurrence temperature and pressure, CO2 adsorption capacity is determined
No.3 coal of Shanxi Formation in the Qinshui Basin shows a using coal rank. Notably, coal rank is less than 1.5% in the basin and
regular distribution and its depth increases progressively from the its range is low and negligible. Due to the influence of magma
edge of the basin to more than 3000 m at the center (Fig. 1a). In intrusion, the coals in gas subcritical south area show high vitrinite
order to improve the reliability of CO2 geological storage capacity reflectance with an average of 3.5%. Coals preserved below 1500 m
assessment, considering the significant change of CO2 adsorption in the synclinal axis of the basin, which correspond to liquid-like
capacity at different depths, the Qinshui Basin was divided based on supercritical area, also have high coal rank (>3.0%). Vitrinite
the depth range of the different CO2 phases (division boundaries reflectance in other areas in the Qinshui Basin is about 2.5%. Based
are 1000 m and 1500 m). On the other hand, it is considered that on coal rank similarity, coals in gas subcritical north and gas-like
the CO2 leakage can easily occur at depths less than 500 m due to supercritical areas can be designated as XJ coal, and those in gas
poor storage conditions caused by methane weathering and faults. subcritical south and liquid-like supercritical areas, SH coal. While
In addition, coal mines are mostly located in this depth range. Thus, Equations (7)e(12) were used to calculate CO2 adsorption param-
CO2 cannot be effectively preserved due to significant destruction eters in different areas. Equations (13) and (14) were used at
of coal seams. Because CO2 adsorption capacity and coals perme- different depth ranges. In addition, CO2 density and compression
abilities are significantly reduced at depths greater than 2000 m, factor at different depths were calculated using NIST REFPROP
CO2 injection project faces a higher risk of failure and greater software. Ultimately, the geological model parameters for CO2
economic cost. Hence, coal seams shallower than 500 m and deeper storage in No. 3 coals in the Qinshui Basin were established (see
than 2000 m are not considered in the calculation of the TCGSC. Table 4).
Qinshui Basin can, thus, be divided by the depth of coal into three
assessment ranges: 500 me1000 m, 1000 me1500 m and 5.3. A preliminary assessment of CO2 geological storage capacity in
1500 me2000 m. CO2 adsorption capacity shows minimal changes No. 3 coal in the Qinshui Basin
in the first two depth ranges, but decreases linearly in the third.
During the assessment of TCGSC, the effect of coal seam hetero- 5.3.1. ACGSC distribution in the Qinshui Basin
geneity on CO2 storage capacity can be reduced by dividing the Although No. 3 coal in the Qinshui Basin is dominated by
depths. It should also be noted that the thickness of No.3 coal seam anthracite, its occurrence and physical properties show significant
ranges from an average of 2e3 m in the north central to 5 m in the heterogeneity that has implication for accurate assessment of CO2
south.(Fig. 1b). Clearly, even if other parameters are constant, the geological storage capacity. In order to reduce the influence of coal
thickness variation will still result in 2e3 times difference in heterogeneity on assessment results, ACGSC distribution can be
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Fig. 6. Divisions of Qinshui Basin and distribution of CO2 storage capacity. (a) Regional division of Qinshui Basin based on different CO2 phases; (b) Map showing the abundance of
CO2 geological storage capacity of Qinshui Basin No.3 coal.

Table 4
Geological parameters for CO2 storage in No.3 coal in different areas of the Qinshui Basin.

Parameters Gas subcritical area Gas-like supercritical area Liquid-like supercritical area

South North

Area/km2 10785 3625 6350 8650

Depth/m 500e1000 1000e1500 1500e2000
Temperature/
C 22.54e36.64 36.64e50.74 50.74e64.84
Pressure/MPa 3.55e7.1 7.1e10.65 10.65e14.2
Thickness/m 5.0 2.0 2.0 1.5
Coal rank/% 3.5 2.5 2.5 3.5
Apparent density/g$cm3 1.25 1.25 1.25
Porosity/% 4.57 4.57 4.57
Water saturation/% 50% 80% 80%
Solubility/mol$L1 1.08 0.96 1.07
Adsorption parameter (V0/cm3$g1) Eq. 10 Eq. 7 Eq. 7 Eq. 10
Adsorption parameter (D) Eq. 11 Eq. 8 Eq. 8 Eq. 11
Adsorption parameter (k) Eq. 12 Eq. 9 Eq. 9 Eq. 12

calculated prior to the combination of thickness and area to obtain No. 3 coal ACGSC distribution shows a ring band generally
TCGSC. Because adsorption storage is the main storage category in greater than 36 cm3/g (average 40 cm3/g). Abundance gradient
coals, factors like temperature, pressure, coal rank and thickness, shows positive correlation with coal depth. Unlike the monotonous
which control CO2 adsorption capacity, have key effect on the ac- distribution of depth, ACGSC initially increased, and later decreased
curacy of the assessment results. Temperature and pressure have from the edge to the center of the basin. The high ACGSC areas are
high affinities with depth, and they are also continuously distrib- distributed in the center of the syncline axis at a depth interval
uted. The effect of temperature and pressure on heterogeneity in between 1000 m and 1500 m (gas-like supercritical area), and the
coal reservoir can be reduced by taking the mean value. Coal rank Zhengzhuang-Fanzhuang area in the south of the basin. Clearly, the
and thickness are not only normally developed but are also locally observed variation in the level of abundance across these areas is
distributed in the Qinshui Basin. Coal reservoir heterogeneity in a due to different factors. In the gas-like supercritical area, pressure,
basin can be reduced by area division because the distribution and which is positively correlated with CO2 adsorption capacity, is the
properties of coal in these subdivision show smaller variation controlling factor for high ACGSC. Based on the distribution of CO2
ranges. The division method used in this study can reasonably adsorption capacity with depth, it can be deduced that adsorption
reduce the influence of coal reservoir heterogeneity on assessment capacity of coals in this depth range is the largest. In the
results. By combining the CO2 geological storage model parameters Zhengzhuang-Fanzhuang area, the depth is less than 1000 m
of the different areas with Equation (5), we calculated the ACGSC (average 600 m). High ACGSC was observed in the area because the
values of No.3 coal and plotted their distribution using the inter- coals have been highly metamorphosed under the effect of high
polation method, see Fig. 6(b). temperature. Also, their vitrinite reflectance is generally greater

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than 3.5%. Coals with high CO2 adsorption capacity have high coal ranks, initial gas concentration ratio, temperature, injection
ACGSC under reservoir conditions, which further demonstrates that pressure and other relevant conditions, CH4 recovery can be
CO2 adsorption storage is the dominant category in CO2 geological significantly improved (even reaching 100%) after CO2 injection,
storage in coals. Low ACGSC areas are distributed in the Jinzhong [35e37]. The CO2-ECBM pilot test in Qinshui Basin also proved that
fault depression, the syncline axis where the coal depth is more injection of CO2 into coals can significantly improve CH4 recovery
than 2000 m, and the hanging wall of Jinhuo Fault where the coal rate up to 67% [38], which is lower than theoretical and experi-
depth is less than 500 m. Shallow depth (<500 m), deep depth mental results. This disparity is due to complex geology, restricted
(>2000 m), and low coal metamorphism are the main reasons for engineering, and immature technical conditions. For example, CO2
the relatively low ACGSC observed in the coals in these areas. Based cannot completely enter all micropores within a short time frame,
on the above distribution of the ACGSC, favorable areas for CO2 and a higher injection pressure and supercritical CO2 may be
geological storage in coals are high coal rank and gas-like super- needed to improve CBM recovery. By applying CBM recovery to
critical areas. This assertion supports recommendations from pre- CO2-ECBM projection, the ECGSC in No. 3 coal was calculated to be
vious studies that priority should be given to supercritical CO2- 6.54 Gt. Because the depth in gas subcritical area is the common
ECBM project in deep anthracite reservoir [33]. range for CBM development, a large number of CBM wells are
readily available for use. The area also presents the highest CO2
storage potential. Thus, at current economic and technical condi-
5.3.2. TCGSC and ECGSC of No.3 coal in the Qinshui Basin tions, the existing wells should be fully utilized, and the gas area
Monitoring data from CO2micro-pilot injection test in the deep should be considered as a priority for CO2-ECBM projection.
coal of well SX-001 in Qinshui Basin show that the CO2 storage
capacity is 19.75 cm3/g at 932 m depth [34]. The TCGSC of
anthracite in this well, calculated using Equation (5), ranges from 5.4. Comparison of various assessment results and their implication
36.56 cm3/g to 41.41 cm3/g The monitoring data are significantly for CO2-ECBM
lower than our assessment results because the range of observation
is from wellbore to well control boundary. In this range, the CO2 Many prospecting works have been carried out to assess CO2
storage capacity in coal gradually decreased from the wellbore to geological storage potential in the Qinshui Basin. Various methods
zero capacity at the boundary. Due to high CO2 injection pressure, and parameters were used to evaluate different depth intervals, but
CO2 concentration, and adequate contact reaction, complete CO2/ the results are inconsistent (Table 6). Interestingly, Zhao et al. [8]
CH4 replacement where displacement efficiency is 100% can only concluded that the TCGSC of coal in the Qinshui Basin is 1.78  1012 t,
occur near the injection well. Thus, CO2 can reach full saturation in which is significantly higher than other assessment results. This is
coals under reservoir conditions. By monitoring CO2 injection in because (1) all 16 coal seams in the Qinshui Basin were assessed, and
coals, it was discovered that CO2 concentration showed an (2) the selection of assessment parameters was simplified such that
approximate linear decrease [21]. Therefore, it can be concluded vertical variations of CO2 geological storage capacity, including the
that the CO2 storage capacity determined by the monitoring of well sharp decrease of CO2 adsorption capacity in deep coals, was not
SX-001 is 50% of the actual storage capacity (39.5 cm3/g), which considered. In additional, previous studies were based on conversion
corroborates our assessment. This implies that the assessment of CBM resources, and various values were assigned as CBM recovery
method for the CO2 geological storage capacity developed in this factor and CO2/CH4 replacement efficiency, to obtain multiple CO2
study is highly accurate and reliable for predicting CO2 storage geological storage capacities. All the assessments produced low
capacity and selecting CO2 injection site. storage capacity values. Although some studies have considered CO2
ACGSC was input into Equation (3), and TCGSC of 9.72 Gt was storage capacities at different depths, CBM resources conversion
obtained for No.3 coal. The TCGSCs in the gas area, gas-like su- method is limited to current economic and technical conditions. The
percritical area and liquid-like supercritical area are 76.41%, 13.61% method cannot effectively represent the CO2 storage potential of
and 9.97% of the total TCGSC in the Qinshui Basin. The proportion of coals and could result in waste of in-situ storage capacity and un-
CO2 adsorption storage capacity is higher than 90% in all cases. sustainable injection process. The reason for underestimation is that
According to the CO2 storage category, the adsorption, static and previous core methodology is based on the principle of recoverable
dissolution storage capacities are 7.15 Gt, 0.22 Gt and 0.097 Gt in the CBM resources and a fixed CO2/CH4 replacement efficiency. Under
gas area, 1.25 Gt, 0.042 Gt and 0.033 Gt in the gas-like supercritical actual coal reservoir conditions, this could result in the neglect of the
area, and 0.88 Gt, 0.063 Gt and 0.029 Gt in liquid-like supercritical increase production by CO2-ECBM and the mis-estimation of CO2/
area (Table 5). CO2 adsorption storage capacity is dominant in all CH4 displacement efficiency. While our assessment was based on
areas. However, its proportion in the total storage capacity experimental CO2 adsorption, in-situ CO2 storage capacity was
decreased with depth, while the static and dissolution storage ca- emphasized and variation of CO2/CH4 displacement efficiency at
pacities increased significantly due to the high-density attribute of different coal reservoir conditions was not considered. Experimental
supercritical CO2. Gas subcritical area has the largest TCGSC and simulation studies on CO2 displacement of methane in coals
because the No. 3 coal seam in this location is the most extensive showed that CO2/CH4 displacement efficiency can approach 100%
and thickest. Previous studies have shown that based on different due to improvement of CO2 injection technology [36,37]. Therefore,

Table 5
Assessment results of CO2 storage capacity in coal in the Qinshui Basin.

Storage category Gas subcritical area Gas-like supercritical area Liquid-like supercritical area

Capacity/  107t Proportion/% Capacity/  107t proportion/% Capacity/  107t Proportion/%

Adsorption 714.51 95.75 125.46 94.37 88.24 90.59

Static 22.06 2.96 4.24 3.19 6.25 6.42
Dissolution 9.69 1.30 3.25 2.44 2.92 3.00
TCGSC 746.26 76.41 132.95 13.61 97.41 9.97
ECGSC 499.99 89.08 65.26

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Table 6
Comparison of assessment results of CO2 geological storage capacity in the Qinshui Basin.

Source Coal Core methodology Depth/m Capacity/108t

Zhao et al. [8] No. 1-16 Conversion from recoverable CBM resources þ storage category division 300e2000 17800
Liu et al. [9] Undefined Conversion from recoverable CBM resources 300e1500 6.13
Yu et al. [10] Undefined Conversion from recoverable CBM resources þ area division 0e2000 229.86
Fang & Li [39] Undefined Conversion from recoverable CBM resources 1000e2000 1.85
Wang et al. [40] No. 3, No. 15 Conversion from recoverable CBM resources þ area division 600e1500 37.4
Jiang et al. [41] Undefined Conversion from recoverable CBM resources þ area division þ storage category division 1000e2000 3.32
This study No. 3 In-situ CO2 storage capacity in coal þ area division þ storage category division 500e2000 97.2

in terms of CO2 storage potential of coals, it is suggested that more consistent with the monitoring data of CO2 pilot test in deep
attention should be focused on in-situ storage capacity as this could coal in the Qinshui Basin, indicating that our assessment
aid the selection of suitable sites for injection. Our assessment method has a high reliability.
method is based on CO2 adsorption isotherm combined with area (3) The TCGSC of No.3 coal in the Qinshui Basin is 9.72 Gt and the
and storage classification. The technique is more aligned with in-situ ECGSC, 6.54 Gt CO2 geological storage capacity in the gas
coal reservoir environment thereby producing high precision out- subcritical area reached 76.41% of total storage capacity in
comes. The results generated in this study can be used not only the Qinshui Basin. Adsorption capacity accounted for more
directly to assess CO2 geological storage potential of No. 3 coal in the than 90% of the total storage capacity, but its value pro-
Qinshui Basin, but to also provide a scientific basis for deep coal CCS gressively decreased with depth. Future CO2-ECBM projects
project in the future. Also, the experimental-based method provides are important part of China CCUS national strategy that
a more accurate assessment of CO2 geological storage capacity of should be focused on carbon emissions reduction and
deep coals. resource utilization in coal mining areas.
In response to the 1.5
C warming limit and national strategy on
carbon emissions peak and carbon neutrality, CO2-ECBM needs to Acknowledgement
be urgently replaced by CO2 geological storage in coal for carbon
emission reduction and resource utilization. Enhancing the effec- We are grateful to the anonymous reviewers for their insightful
tiveness of CO2 geological storage capacity of coal seams through comments and suggestions. The authors would like to acknowledge
injection technology optimization will become the key driving the financial support provided by National Natural Science Foun-
force for the development of CO2-ECBM engineering in the future. dation of China (Nos. 42102207, 42141012 and 41727801), Major
Although the process of CO2 injection into coal can significantly Project supported by Jiangsu Key Laboratory of Coal-based Green-
improve methane recovery and provide more storage space for CO2, house Gas Control and Utilization, China University of Mining and
the real engineering outcome is far from experimental and theo- Technology (2020ZDZZ01C), the Peng Cheng Shang Xue Education
retical observations. This is because CO2/CH4 replacement effi- Fund of CUMT Education Development Foundation (PCSX202203)
ciency is impacted by coal reservoir heterogeneity, temperature and A Project Funded by the Priority Academic Program Develop-
and pressure conditions, and injection technology during opera- ment of Jiangsu Higher Education Institution (PAPD).
tion. However, CO2 injection efficiency and CO2/CH4 replacement
efficiency can be improved continuously through technology
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