Fuel 283 (2021) 118886

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CO2 and CH4 adsorption on different rank coals: A thermodynamics study of T

surface potential, Gibbs free energy change and entropy loss
⁎
Xidong Dua, Yugang Chengb, , Zhenjian Liuc, Hong Yind, Tengfei Wue, Liang Huoa, Couxian Shua
a
State Key Laboratory of Nuclear Resources and Environment, School of Earth Sciences, East China University of Technology, Nanchang, Jiangxi 330013, China
b
National and Local Joint Engineering Research Center of Shale Gas Exploration and Development, Chongqing Institute of Geology and Mineral Resources, Chongqing
400042, China
c
College of Civil Engineering, Yancheng Institute of Technology, Yancheng, Jiangsu 224051, China
d
Engineering Research Center for Waste Oil Recovery Technology and Equipment, Chongqing Technology and Business University, Chongqing 400067, China
e
State Key Laboratory of Coal Mine Safety Technology, China Coal Technology & Engineering Group Shenyang Research Institute, Fushun 113122, China

A R T I C LE I N FO A B S T R A C T

Keywords: In this paper, the pore structures of three different rank coals sampled from China (anthracite, bituminous coal
Entropy loss and lignite) were characterized by CO2 and N2 adsorption. The isothermal adsorption curves of CO2 and CH4 on
Surface potential three samples were measured by gravimetric method and fitted by Langmuir model. The preferential selectivity
Gibbs free energy change (αCO2/CH4) was calculated using the Langmuir parameters of CO2 and CH4, and the Henry’s coefficient (KH) was
Selectivity
obtained with the help of virial equation. More importantly, a comparative analysis of adsorption thermo-
Coal rank
dynamics of CO2 and CH4 on three different rank coals, including surface potential (Ω), Gibbs free energy change
(ΔG) and entropy loss (ΔS), was presented according to the adsorption data. It is found that the uptakes of CO2
and CH4 on anthracite are the largest, followed by lignite and bituminous coal in sequence. αCO2/CH4 increases
with the increase of coal rank. Low temperature helps injected CO2 to displace pre-adsorbed CH4. The KH values
on anthracite are the biggest, while KH values on bituminous coal are the smallest. Ω, ΔG and ΔS of CO2 and CH4
all exhibit a U-shaped function with maturity. Anthracite has the highest Ω, ΔG and ΔS, while bituminous coal
has the lowest Ω, ΔG and ΔS. The thermodynamics parameters of Ω, ΔG and ΔS are affected by pore size
distributions of three coals. Ω, ΔG and ΔS of CH4 are smaller than those of CO2. CO2 adsorption on coal is more
favorable and spontaneous, and adsorbed CO2 molecules form a more efficient packing on coal.

1. Introduction
With the rapid growth of the demand of natural gas resource, coal
seam gas with the main component of methane (CH4) has been con-
sidered as a potential solution for the natural gas supply [1]. As the
adsorbed CH4 on coal matrix surface is difficult to desorb even at low
pressure, the recovery of CH4 in-place is always less than 50% using the
means of conventional pressure depletion [2]. To solve this problem,
the technology of carbon dioxide (CO2) storage with enhanced coalbed
methane recovery (CO2-ECBM) has been put forward and studied over
the past decades [3–10]. At present, the economic and technical feasi-
bility of CO2-ECBM technology has been extensively verified by many
researchers through numerical simulation study and laboratory ex-
periment, and the corresponding pilot tests have been successfully
implemented in Japan and America [11,12]. On the basis of greater
adsorption potential of CO2 on coal, injected CO2 can easily flow
through the fracture/cleat system, and then diffuse into the coal matrix
to directly displace the adsorbed CH4, and ultimately be trapped in the
ultra-micro-pores region [13].
The pore/fracture structure morphology, including pore size dis-
tribution, pore volume, specific surface area, pore shape, pore con-
nectivity and porosity, has obvious effect on the occurrence and mi-
gration mechanisms of fluid in coal seams [14,15]. In the process of
coalification, the chemical and physical features of coal materials can
change, leading to the difference in pore/fracture structures of different
rank coals [12,16]. Carrying out the investigation about the adsorption
and transport performances of CH4 on coals with different maturities is
of importance for the exploitation of coalbed methane from various
rank coal seams. Generally, due to larger possibility to be subjected to a
higher pressure and temperature condition, coal rank increases with
buried depth of coal seam. The technology of CO2-ECBM is usually
applied in deep unmineable coal seams with higher coal rank. However,
some of shallow coal sediments with lower metamorphism degree, such
as Victorian brown coal basin, also have great potential for the

⁎
Corresponding author.
E-mail address: chengyugang@cqu.edu.cn (Y. Cheng).

https://doi.org/10.1016/j.fuel.2020.118886
Received 26 January 2020; Received in revised form 14 June 2020; Accepted 3 August 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
X. Du, et al.
sequestration of anthropogenic CO2 [17,18]. Thus, study related to the
sorption and transport characteristics of CO2 in coal samples with dif-
ferent metamorphism degrees is also significant for the safe storage of
injected CO2 into various rank coal seams.
To date, some researchers have addressed the adsorption, transport
and displacement behaviors of CO2 and CH4 on the coals with various
maturities [19–25]. For the sorption of CO2 and CH4, there are two
kinds of different conclusions [19,22]. One view is that the amounts of
adsorbed CO2 and CH4 enhance monotonically as the maturity im-
proves [22]. Another view is that the adsorption quantities of both
gases show a U-shape trend with the increase of the degree of meta-
morphism [19]. Concerning on the diffusion performances of CO2 and
CH4 on coal, the results of Liu et al. [21] showed that diffusivity of CH4
on high rank coal is smaller than that on low rank coal. Zhang et al.
[20] used volumetric method to perform the diffusion tests of CO2 and
CH4 on coals at 308–338 K and observed that the effective diffusivities
of CO2 and CH4 exhibit a U-shape function with coal rank rises. For the
displacement efficiency of CO2, Yang and Liang [24] discussed the rule
of the replacement of CH4 by CO2 in coals and pointed out the negative
correlation of the displacement efficiency of CO2 with the maturity of
coal. By contrary, Wang et al. [23] observed that high rank coal is more
favorable for the replacement of absorbed CH4 by injecting CO2.
Therefore, it can be noted that the influences of coal rank on adsorp-
tion, transport and displacement performances of CO2 and CH4 are
complex and need further research.
In addition, study related to the sorption of CO2 and CH4 on coal
from thermodynamics point of view can provide useful information to
recognize the intrinsic mechanisms of adsorption of both gases and to
verify the displacement ability of CO2. The thermodynamics variables,
including isosteric heat of adsorption (Qst), entropy loss (ΔS), enthalpy
change (ΔH), Gibbs free energy change (ΔG) and surface potential (Ω),
all possess the corresponding physical prospects to explain the sorption
phenomenon. So far, many efforts focused on the thermodynamics
study of CO2 and CH4 adsorption on coal have been conducted
[11,26–29]. Zhou et al. [27] showed that the surface free energy change
of coal matrix after the sorption of CH4 is smaller than that after the
sorption of CO2, and water can reduce the surface free energy of both
gases. Zhang et al. [26] discovered that Qst of CO2 on various rank coals
are within the range of 13.8–18.6 kJ/mol. Busch and Gensterblum [11]
indicated that with increasing moisture content, Qst of CO2 and CH4 on
coal decline slightly. Dong et al. [29] researched CO2 and CH4 ad-
sorption by molecular simulation analysis on coal, and revealed that
with sorption amount improves, Qst of CO2 and CH4 decrease at the
early phase, and then gradually enhance. According to the statement
above, we can find that the comparison of thermodynamics properties
of CO2 and CH4 adsorption on different rank coals is rare. Currently,
only Tang et al. [28] analyzed the affinity of different types of coal by
calculating the mean value of Qst of CH4. They noticed that the mean
value of Qst of CH4 reduces in the order: anthracite, lean coal and gas-
fat coal. Therefore, it is critical to perform the investigation to obtain a
comprehensive understanding of thermodynamics of CO2 and CH4 ad-
sorption on different rank coals.
In this article, the isothermal adsorption curves of CO2 and CH4 on
three coals (anthracite, bituminous coal and lignite) were acquired
using the gravimetric method and then dealt with Langmuir model. The
preferential selectivity (αCO2/CH4) was calculated using the Langmuir
parameters of CO2 and CH4. The Henry’s coefficients (KH) of CO2 and
CH4 were obtained with the help of virial equation. Surface potential
(Ω), Gibbs free energy change (ΔG) and entropy loss (ΔS), were ana-
lyzed according to the adsorption data. It is expected that the results of
this study could offer some theoretical support for the application of
CO2 geological storage in coal formations.
2
Fuel 283 (2021) 118886
2. Theory models
2.1. Langmuir model
Adsorption isotherms exhibit the relationship of adsorption amount
with pressure at isothermal condition and are often treated with various
sorption models, such as Henry equation, Langmuir model, pore-filling
model and Brunauer-Emmett-Teller (BET) model [30]. Langmuir model
is the most extensively adopted model, which assumes that adsorption
is occurring by the mechanism of monolayer adsorption on a homo-
geneous surface [3]. The isothermal sorption curves of CO2 and CH4 on
different rank coals were fitted by Langmuir model in this paper. Eq. (1)
gives the form of Langmuir model.
qm bP
q=
1 + bP (1)
where q is the adsorption amount at equilibrium pressure P and tem-
perature T; qm is the maximum sorption ability; and b represents
Langmuir constant.
The preferential selectivity (αCO2/CH4), which can be taken as a
quantified index to evaluate the displacement ability of CO2, can be
gained by [31]:
αCO2/ CH 4 = (x CO2 / yCO2 )/(x CH 4 / yCH 4 ) (2)
where yCO2 and xCO2 are CO2 mole proportions in bulk phase and ad-
sorbed phase, respectively; yCH4 and xCH4 are CH4 mole proportions in
bulk phase and adsorbed phase, respectively.
When the sorption of CO2 and CH4 satisfy Langmuir form, Eq. (2)
can be rewritten as [32]:
qm, CO2 bCO2
αCO2/ CH 4 =
qm, CH 4 bCH 4 (3)
where qm,CO2 and qm,CH4 are the maximum sorption abilities of CO2 and
CH4, respectively; bCO2 and bCH4 are the Langmuir constants of CO2 and
CH4, respectively.
2.2. Henry’s law
For an adsorption system, the adsorption quantity is proportional to
pressure at low pressure range, which is called Henry’s law [28]. In
Henry’s region, the force of surface-molecule is dominated in the ad-
sorption process [33]. Accordingly, the adsorption affinity of adsorbate
molecules on porous media surface can be evaluated by Henry’s coef-
ficient (KH). The larger the Henry’s coefficient, the stronger the ad-
sorption affinity.
Using the virial equation, the relationship of equilibrium pressure
and adsorption quantity can be expressed as [34]:
P 1
= exp(A1 q + A2 q2 + A3 q3 + ···)
q KH (4)
where A1, A2 and A3 are the virial coefficients.
Then, Eq. (5) can be obtained.
ln(P / q) = A0 + A1 q + A2 q2 + A3 q3 + ··· (5)
where A0 corresponds to Henry’s coefficient, as KH = exp(-A0).
At low pressure condition, adsorption amount shows a linear re-
lationship with pressure, and the high-order terms in Eq. (5) can be
deleted. Thereby, we can receive:
ln (P / q) = A0 + A1 q (6)
Through fitting the linear region of ln(P/q) vs. adsorption amount q,
KH can be calculated.
2.3. Thermodynamics of adsorption
Adsorption thermodynamics characteristics help to elucidate the
X. Du, et al. Fuel 283 (2021) 118886

mechanism of this spontaneous process [31]. In this work, the ther- 3.2. Characterization of coals
modynamics analysis focuses on surface potential Ω, Gibbs free energy
change ΔG and entropy loss ΔS. Ω is an indicator of isothermal work 3.2.1. Characterization of Macropore and mesopore
needed to achieve adsorption equilibrium. ΔG is an important factor for The low-pressure N2 adsorption at 77 K was applied to measure the
evaluating the degree of spontaneity of adsorption process. Entropy is mesopore and macropore morphology of three samples using an ASAP
the criterion of the patter or disorder in which a thermodynamics ad- 2020 system (Micromeritics Instruments, USA). Owing to the pore
sorption system is rearranged, and ΔS can reflect the specific interaction shrinkage effect at 77 K, injected N2 molecules do not possess plenty
of adsorbent-adsorbate and the limited mobility of adsorbed molecules energy to overcome the potential barrier to diffuse into the ultrafine
[32]. micropore [4]. Therefore, low-pressure N2 adsorption can only offer the
The surface potential Ω was calculated by Eq. (7) [35]. accurate information about mesopore and macropore.
The BET model was used to analyze surface area (SBET). The form of
P
Ω = −RT ∫0 qd (ln P ) (7) BET model is shown in Eq. (12) [30]. The non-local density functional
theory (NLDFT) was employed to analyze pore size distribution (PSD).
where R is universal gas constant. The mesopore volume (Vmes) and micropore volume (Vmic) were ac-
The Gibbs free energy change ΔG was got by Eq. (8) [36]. quired by Barrett-Joyner-Halenda (BJH) model [38] and t-point
method, respectively. The total volume (Vt) was received when relative
P
Ω RT ∫0 qd (ln P ) pressure (P/P0) is 0.995. By subtracting Vmes and Vmic from Vt, the
ΔG = =−
q q (8) macropore volume (Vmac) can be determined.

The entropy change ΔS can be acquired by the following equations na =

1 1
1 C − 1 P P0
[32]: n0 C
+ n 0 C P0 P
−1 (12)
∂ ln P
Qst = RT 2 ( )q where na is the specific adsorbed quantity at P/P0; P0 is saturated vapor
∂T (9)
pressure; n0 is the specific capacity of monolayer adsorption; and C is a
Qst parameter in relation to the energy of monolayer adsorption.
ln P = − +L
RT (10)

ΔH − ΔG 3.2.2. Characterization of micropore

ΔS = Compared with N2 molecule, CO2 molecule has smaller kinetic
T (11)
diameter and is able to access the pores with the size of 0.3–1.5 nm
where L is integration constant; and ΔH = -Qst. [39]. Therefore, CO2 sorption was used to probe the microporosity of
three samples by an ASAP 2020 system at 273.15 K. On the basis of
obtained sorption results, the micropore volume (VDA) and micropore
3. Materials and experimental methods
surface area (SDR) were gained by Dubinin-Astakhov (DA) model and
Dubinin-Radushkevich (DR) model, respectively [40,41]. The PSD of
3.1. Origin of coals
micropore was analyzed using NLDFT model.
The three samples adopted in this work were Songzao anthracite,
Heze bituminous coal and Shendong lignite. The Songzao (SZ) anthra-
3.3. Adsorption isotherm measurement
cite was collected from Songzao coalfield in the southeast district of
Sichuan Basin of China. The Heze (HZ) bituminous coal was sampled
The intelligent gravimetric adsorption apparatus with high resolu-
from Heze coalfield in the east district of Huabei Basin of China. The
tion (IGA-100B, U.K.) was adopted to acquire the isothermal sorption
Shendong (SD) lignite was got from the Shendong coalfield in the north
curves of CO2 and CH4. The experiment temperatures were 288 K,
district of Ordos Basin of China. In previous studies, the size of used
308 K and 328 K. The experiment pressure was up to 1800 kPa. The
coal particle for adsorption experiment ranges from decades of microns
degassing conditions were 378 K and 10−5 Pa, and the degassing time
to several centimetres [37]. In this work, three coal samples were all
was 10 h.
crushed and sieved into particles with the size of 0.18–0.25 mm.

Fig. 1. Adsorption and desorption isotherms of N2 on three coal samples at 77 K (a) and pore size distributions of mesopore and macropore (b).

3
X. Du, et al.
4. Results and discussion
4.1. Pore structure analysis
4.1.1. Macropore and mesopore analysis
The N2 desorption and adsorption isotherms of these samples are
presented in Fig. 1(a). It can be found that N2 adsorption isotherms on
three samples all belong to type Ⅱ, suggesting the occurrence of capil-
lary condensation phenomenon at higher relative pressure. The hys-
teresis loops between desorption and adsorption isotherms of three
samples belong to type H2, which indicates that the pores structures of
three samples are slit shape pore with parallel walls. It is clear that the
sorption ability of N2 on lignite is the highest, followed by bituminous
coal and anthracite in sequence. There is a negative correlation of N2
adsorption ability with coal rank. Meanwhile, the hysteresis loops of
lignite and bituminous coal are not closed at low relative pressure,
which may be due to the swelling of coal matrix during adsorption
process [42]. In addition, the smaller hysteresis loop always implies the
poorer connectivity of pores [43]. Accordingly, macropore and meso-
pore within anthracite are not highly connected, and lignite has bigger
possibility for fluid to move easily, agreeing with the report of Perera
[44].
The PSD of mesopore and macropore of three samples are displayed
in Fig. 1(b). As plotted in Fig. 1(b), these different rank coals all have
continuous PSD of mesopore and macropore. SD lignite has the widest
and richest mesopore and macropore distribution. The mesopore and
macropore distributions of SZ anthracite are the narrowest, and ac-
cordingly SZ sample has the least mesopore and macropore.
Table 1 summarizes the mesopore and macropore parameters of
three samples. Obviously, SBET and Vt decrease with the improvement
in coal rank. It should be noted that the vitrinite-rich coals have more
microporous structure. As pointed out by Merkel et al. [45], the content
of vitrinite increases with maturity, and lots of bigger pores are trans-
lated into micropore during the coalification process. Meanwhile, due
to N2 molecule can only effectively measure the information of meso-
pore and macropore. Therefore, SBET and Vt are lower for high rank
coal. Moreover, Vmes values are all much higher than the values of Vmac,
which indicates that SBET and Vt on three coals are mainly offered by
mesopore.
4.1.2. Micropore analysis
CO2 sorption isotherms at 273.15 K are depicted in Fig. 2(a), and
micropore PSD are given in Fig. 2(b). We can find that the uptake of
CO2 shows a U-shaped relationship with the degree of metamorphism.
The PSD of micropore for bituminous coal is the narrowest, mainly
centering on 0.8–0.9 nm. Contrary to bituminous coal, anthracite and
lignite have abundant micropore and possess wide PSD at the range of
less than 0.95 nm. The main micropore distribution for anthracite is
around 0.58 nm, 0.66 nm, 0.76 nm and 0.88 nm. Micropore PSD for
lignite has the major peaks at 0.60 nm, 0.80 nm and 0.85 nm.
Table 2 gives the results of micropore of three coals. It is obvious
that SDR and VDA of anthracite are the highest, followed by lignite and
bituminous coal. SDR and VDA follow a polynomial trend with increasing
coal rank, which is in accordance with the characterization results of Li
et al. [14]. Owing to the positive relationship between SDR and mi-
cropore adsorption capacity, CO2 sorption ability also has the same
polynomial function with coal rank as recorded in Fig. 2(a).
Table 1
Mesopore and macropore structure parameters of three samples.
Sample SBET (m2·g−1) Vmic (10−3cm3·g−1) Vmes (10−3cm3·g−1)
anthracite 0.1866 0 0.2729
bituminous coal 0.7446 0 0.7682
lignite 1.4840 0 1.9600
Fuel 283 (2021) 118886
4.2. Isothermal adsorption curves of CO2 and CH4 on coals
Fig. 3 describes the isothermal adsorption curves of CO2 and CH4 on
three samples. The uptakes of both gases decline with increasing tem-
perature, revealing that low temperature is conducive to the accumu-
lation of coalbed methane and the storage of substantial amounts of
CO2. Increasing temperature can promote adsorbed molecules to
overcome electrostatic interaction and van der Waals force and to es-
cape from adsorption sites [33]. Therefore, decreasing temperature
facilitates CO2 and CH4 sorption. At the same condition, CO2 and CH4
sorption amounts on anthracite are the largest, followed by lignite and
bituminous coal, which is consistent with the order of the values of SDR
and VDA as listed in Table 2. This is mainly because micropore offers the
main adsorption sites for CO2 and CH4 on coal. Anthracite with abun-
dant micropore has greater sorption quantity for gas.
The uptakes of CO2 and CH4 on coals at 1800 kPa are described in
Fig. 4. As shown in Fig. 4, the adsorption amounts of both gases at
maximum equilibrium pressure of 1800 kPa show a U-shaped trend
with improving the degree of metamorphism. At other equilibrium
pressures, the relationship between the uptake of gas and coal rank is
the same as that at 1800 kPa. Thereby, there is a U-shaped function
between coal rank and gas adsorption ability, which has been found and
verified by many research workers [19,46].
The adsorption capacity of coal is mainly determined by pore
structure and surface chemistry, which can be influenced by coalifica-
tion process. With increasing coal rank, the content of vitrinite con-
sistently enhances, while the content of liptinite gradually decreases
[42]. Previous investigation has shown that vitrinite is the most porous
maceral group and mainly micro- and mesoporous, and liptinite is the
least porous maceral with substantial macropores [47]. Hence, it is
expected that the micropore surface area and adsorption capacity rise
as the coal rank improves. However, as reported in Table 2, there is
actually not a positive relationship between coal rank and micropore
surface area, leading to the lowest adsorption capacity for bituminous
coal with medium metamorphism degree. It seems that the micropore
structure being blocked by low boiling point hydrocarbon solids or
minerals during coalification process [19] can account for the poly-
nomial function between coal rank and micropore surface or gas ad-
sorption capacity.
In addition to pore structure, the change of surface chemistry
characteristics with coal rank also should be taken into consideration.
As reported by Li et al. [14], the concentration of functional groups
reduces with the degree of metamorphism improves due to the func-
tional group elimination and hetero-aromatic bonds breaking. Because
the oxygen-containing groups or polar groups have the priority for gas
sorption especially for CO2, the low rank coal with higher functional
groups density has the greater adsorption potential for CO2 and CH4.
This is one reason why lignite has a higher sorption ability than bitu-
minous coal. However, for lignite and anthracite, even though the
functional groups concentration of lignite is higher than that of an-
thracite, the micropore surface area of anthracite is clearly larger than
that of lignite. The combined effect results in the biggest adsorption
capacity of anthracite.
Vmac (10−3cm3·g−1) Vt (10−3cm3·g−1) Vmic/Vt (%) Vmes/Vt (%) Vmac/Vt (%)
0.0892 0.3621 0 75.37 24.63
0.0817 0.8499 0 90.39 9.61
0.1900 2.1500 0 91.17 8.83
4
X. Du, et al.
Fig. 2. CO2 adsorption isotherms at 273.15 K (a) and PSD of micropore (b).
Table 2
Micropore structure parameters of three samples.
Sample SDR (m2·g−1) VDA (cm3·g−1)
anthracite 120.3937 0.02414
bituminous coal 54.5440 0.01848
lignite 98.7143 0.02161
4.3. Simulation of isothermal adsorption curves of CO2 and CH4 on coals
4.3.1. Simulated results of isothermal adsorption curves on coals
The simulated results of isothermal adsorption curves on coal
samples are given in Fig. 3, and the obtained Langmuir parameters of
CO2 and CH4 are tabulated in Table 3. The experiment data are in better
agreement with simulated results, and the nonlinear regression coeffi-
2
cients Rnrc are all larger than 0.99. Thereby, employing Langmuir model
to analyze the adsorption data is acceptable. As displayed in Table 3,
the values of b of CO2 and CH4 decrease with temperature, and the
value of b of CO2 is clearly bigger than that of CH4.
Fig. 5 illustrates the ratios of sorption quantity of CO2 relative to
CH4 (qCO2/qCH4) on three samples. qCO2/qCH4 values are greater than
one and within the range of 1.81–7.22 depending on experiment con-
dition and coal rank, suggesting that the feasibility of enhanced coalbed
methane recovery by injecting CO2 into different rank coal seams. The
values of qCO2/qCH4 on various rank coals vary from 1.13 to 3.52 in the
report of Zhang et al. [26] and vary from 1.62 to 4.20 in the report of
Fig. 3. Isothermal adsorption curves of CH4 (a) and CO2 (b) on coals at different temperatures.
5
Fuel 283 (2021) 118886
Wang et al. [4]. As equilibrium pressure increases, qCO2/qCH4 declines,
which implies that the decrease in adsorption rate of CO2 induced by
enlarging pressure is more obvious. This reducing trend of qCO2/qCH4
with pressure has also been confirmed by Bae and Bhatia [48]. For CO2
and CH4 sorption on anthracite and lignite, low temperature is bene-
ficial to obtaining bigger qCO2/qCH4 value. However, for CO2 and CH4
sorption on bituminous coal, the relation between temperature and
qCO2/qCH4 is complex. qCO2/qCH4 at 288 K is higher than that at 308 K
over the whole pressure range on bituminous coal. At 328 K, qCO2/qCH4
on bituminous coal is the highest at the pressure range of 0–800 kPa,
while qCO2/qCH4 is the lowest at the pressure range of 1300–1800 kPa.
At the pressure range of 800–1300 kPa, the values of qCO2/qCH4 on
bituminous coal at 328 K are moderate.
The stronger sorption ability for CO2 than CH4 on coal can be in-
terpreted by the physical–chemical features of CO2 and CH4 molecules
and the interaction of adsorbate molecules with coal matrix [49].
Firstly, CO2 molecule with smaller kinetic diameter and linear shape
can easily transport into the ultramicropores and retain in the forma-
tion. In the previous finding of Liu et al. [50], the available organic
nanopore volume for CO2 adsorption is 40% more than that for CH4.
Secondly, CO2 has a bigger boiling point, meaning that adsorbed CO2
molecules are more difficult to desorb from surface by “evaporation”
[51]. Moreover, the dissolution of CO2 in coal body is more significant
[26], which can also bring about bigger uptake of CO2 on coal. Lastly,
the research result of Clarkson et al. indicated that in addition to the
monolayer adsorption in micropore, CO2 can also be adsorbed in larger
pores by multilayer adsorption mechanism, while the adsorption of CH4
X. Du, et al. Fuel 283 (2021) 118886

Fig. 4. Adsorption amounts of CH4 (a) and CO2 (b) on coals at 1800 kPa under different temperatures.

on coal is mainly in micropore [52]. As a result of multiple factors ef-
fect, the adsorption quantity of CO2 on coal is larger.
4.3.2. Preferential selectivity on coals
Table 4 gives the results of preferential selectivity (αCO2/CH4) on
three samples at different temperatures. αCO2/CH4 values are all appar-
ently bigger than 1.0, demonstrating the effectiveness of direct re-
placement of pre-adsorbed CH4 by injecting CO2. Therefore, applying
the technique of CO2-ECBM into deep high-ranked coal reservoir and
even shallow low-ranked coal seam is technically feasible. The coal
seams with different metamorphism degrees can all be taken as the
promising geological structures for CO2 storage.
With the increases of temperature, αCO2/CH4 on three coals show a
decreasing trend. Low temperature promotes injected CO2 to effectively
displace adsorbed CH4 molecules [53]. Liu et al. [54] investigated the
mixture of CO2/CH4 sorption on modeled nanochannels and also re-
vealed that increasing temperature can reduce αCO2/CH4 due to the
improvement of thermal motion and the subsequent abscission of a part
of adsorbed molecules from the surfaces. We can see that αCO2/CH4 in-
creases with increasing coal rank, which points out that the high-ranked
coal is conductive to the enrichment of CO2 in the adsorbed state. Yu
et al. [55] also reported that the preferential adsorption of CO2 en-
hances with the coal rank increases. Thus, deep unminable coal seams
with higher maturity are more suitable for the technique of CO2-ECBM.
However, Merkel et al. [45] discovered that αCO2/CH4 declines in the
coalification process of translating subbituminous coal to anthracite.
They thought that the decrease in αCO2/CH4 is mainly caused by the
change of surface chemistry property at the coalification stage. The
oxygen content decreases with the increase in maturity and has a linear
relationship with the amount of surface functional groups such as hy-
droxyl and carboxyl groups [45]. As the functional groups containing
oxygen have the preferential sorption for CO2, αCO2/CH4 is higher on the
subbituminous coal. On the contrary, anthracite with a carbon-domi-
nated surface is not as easily polarized compared with oxygen-con-
taining functional groups. Once anthracite stage is achieved, only the
rearrangement of aromatic ring cluster mainly occurs. Owing to the
higher affinity of oxygen-containing functional groups for CO2 com-
pared to aromatic ring structure, αCO2/CH4 is lower on anthracite than
that on subbituminous coal. The difference in the relationship between
αCO2/CH4 and coal rank in our study and in the study of Merkel et al.
[45] may be due to the influence of pore structure change during
coalification process on αCO2/CH4 is more obvious than the influence of
surface chemistry change in our work. Thereby, the relationship be-
tween coal rank and αCO2/CH4 needs to be further studied.
The result of comparison of αCO2/CH4 on different coal samples is
presented in Table 5. αCO2/CH4 in this study fall within the range of
αCO2/CH4 in previous studies, indicating that the calculated αCO2/CH4
values on different rank coals in this work are reliable.
4.4. Henry’s coefficients of CO2 and CH4 on coals
Table 6 shows the results of gained Henry’s coefficients (KH) of CO2
and CH4 on three samples. Clearly, improving experiment temperature
reduces KH values of CO2 and CH4. Hence, high temperature decreases
the adsorption affinities of CO2 and CH4 on matrix surface and lowers
the adsorption quantities of CO2 and CH4 as plotted in Fig. 3. Mean-
while, KH values of CH4 are much lower than those of CO2 at same
condition, illustrating that CO2 sorption strength on coal surface is
stronger. The higher KH of CO2 is because of the possession of quad-
rupole moment, which brings about stronger electrostatic interaction
between adsorbent surface and adsorbate molecules [31].
It is noticeable that the values of KH on three samples are as follows:
anthracite > lignite > bituminous coal. The sorption affinities of CO2
and CH4 on anthracite are the largest, while on bituminous coal the

Table 3
Langmuir parameters of CO2 and CH4 on three coal samples.
Sample T (K) CO2 CH4

−1 −1
qm (mmol·g ) 3
b ((10 kPa) ) 2
Rnrc qm (mmol·g−1) b ((103kPa)−1) 2
Rnrc

anthracite 288 2.29 2.36 0.9982 2.87 0.24 0.9996

308 2.02 2.01 0.9972 2.82 0.21 0.9998
328 1.74 1.70 0.9975 2.71 0.20 0.9993
bituminous coal 288 2.08 0.47 0.9974 0.83 0.20 0.9967
308 1.69 0.46 0.9984 0.79 0.18 0.9945
328 1.47 0.45 0.9980 0.76 0.16 0.9982
lignite 288 2.02 0.90 0.9979 1.49 0.22 0.9990
308 1.64 0.89 0.9983 1.37 0.21 0.9996
328 1.32 0.87 0.9982 1.31 0.19 0.9991

6
X. Du, et al. Fuel 283 (2021) 118886

Fig. 5. Ratios of adsorption amount of CO2 relative to CH4 on different samples: (a) anthracite, (b) bituminous coal, and (c) lignite.

Table 4 Table 6
αCO2/CH4 on three coals at 288 K, 308 K and 328 K. Henry’s coefficients of CO2 and CH4 on three samples.
Sample 288 K 308 K 328 K Sample Gas T (K) KH (mmol/g/ Gas T (K) KH (mmol/g/
(103·kPa)) (103·kPa))
anthracite 7.85 6.86 5.46
bituminous coal 5.89 5.47 5.44 anthracite CO2 288 5.56 CH4 288 0.71
lignite 5.55 5.07 4.61 308 4.38 308 0.58
328 3.34 328 0.56
bituminous coal CO2 288 1.22 CH4 288 0.19
308 0.93 308 0.15
Table 5
328 0.79 328 0.12
Comparison of αCO2/CH4 on different coal samples.
lignite CO2 288 1.87 CH4 288 0.32
Sample P (103kPa) T (K) αCO2/CH4 Reference 308 1.67 308 0.28
328 1.30 328 0.25
anthracite 0–1.80 288–328 5.46–7.85 This study
bituminous coal 0–1.80 288–328 5.44–5.89
lignite 0–1.80 288–328 4.61–5.55 with the most developed micropore structure has the greatest adsorp-
anthracite 0–3 318 6.5–10.5 [45]
tion potential and accordingly the biggest KH. Lignite with the least
high-volatile bituminous 0–3 318 5.0–9.0
coal micropore has the weakest adsorption potential and the smallest KH.
subbituminous 0–3 318 8.5–10
modeled bituminous coal 0–3 370.2 1.8–3.0 [5]
modeled bituminous coal 0–3 300–340 4.5–6.80 [56] 4.5. Adsorption thermodynamics of CO2 and CH4 on coals
middle-rank coal 0–3 283.15–313.15 1.50–9.0 [29]
heterogeneous coal 0–3 298 2.20–10.0 [57]
4.5.1. Surface potentials of CO2 and CH4 on coals
surface models
Fig. 6 displays the obtained Ω of CO2 and CH4 on three coal samples
under different temperatures. It is clear that Ω values are all negative.
sorption affinities of both gases are the smallest. The order of KH on With increasing pressure, the absolute values of Ω of CO2 and CH4
three coals is the same as the order of adsorption amount on three coals. continue to grow. This is because at high pressure stage more iso-
Xiong et al. [58] reported that the adsorption sites within the smaller thermal work is necessary to load adsorbate molecules into the pore
pore space have the higher energy for adsorption. Thereby, anthracite structure than that at the early phase [32,59].
It can be seen from Fig. 6 that Ω of CO2 and CH4 approach zero

7
X. Du, et al.
Fig. 6. Surface potentials of CH4 (a) and CO2 (b) on coals at different temperatures.
when equilibrium pressure approaches zero. On the basis of Van Ness’
definition of Ω, the specific chemical potential of adsorbent contacted
with adsorbate is the same as that uncontacted with adsorbate at the
low loading condition [35]. Therefore, at the pressure closed to zero, Ω
approaches zero. In addition, decreasing temperature improves the
absolute values of Ω of CO2 and CH4. In particular, the influence of
temperature on Ω of CO2 is more remarkable, which agrees well with
the influence of temperature on uptake of CO2. Surface potential is a
criterion that the work is needed to attain equilibrium condition.
Greater loading of adsorbate gives rise to the bigger Ω [34]. Thus, high
temperature not only reduces the adsorption quantity, but also lowers
surface potential. It can be also found that Ω of CO2 is higher than that
of CH4, manifesting that CO2 sorption on three coal samples is more
favorable.
As detailed in Fig. 6, the order of Ω of CO2 and CH4 on these coals is
as follows: anthracite > lignite > bituminous coal. The calculated
results illustrate a U-shaped relationship between surface potential and
coal rank. Ridha and Webley [35] reported that the cavities with bigger
dimension are easily interconnected, and injected molecules are shared
among these interconnected cavities. As discussed in Section 4.1, the
micropore in anthracite is the most abundant, and the fluctuation of
adsorbate molecules from one cavity to another in the micropore
structure of anthracite needs more isothermal work. Contrarily, the
number of micropore in bituminous coal is the least. Within bituminous
coal, adsorbates are preferably considered to share molecules among
crystals, i.e. adsorbed in mesopores, and thus less isothermal work is
needed for the fluctuation of molecules. Therefore, anthracite has the
highest Ω, while Ω of bituminous coal is the lowest.
4.5.2. Gibbs free energy changes of CO2 and CH4 on coals
Once the pore structure of coal is formed, the force applied on
surface carbon atoms is unbalanced, and the carbon atoms on surface
are attracted by the force of vertically pointing coal body. Thereby,
carbon atoms on surface have the tendency to move towards the in-
terior of coal. This will provide carbon atoms an extra energy, that is,
surface free energy. When the temperature and pressure are constant,
the enhancement of free energy of sorption system with the increase of
unit area of adsorbent is taken as Gibbs free energy change ΔG [27].
Fig. 7 describes the gained ΔG of CO2 and CH4. ΔG values are all ne-
gative, indicating that CO2 and CH4 sorption on three coal samples are
spontaneous. As pressure rises, the absolute values of ΔG of both gases
increase. High pressure improves the degree of spontaneity of adsorp-
tion and promotes the adsorption process. At the same condition, ΔG of
CO2 is apparently more negative, which suggests that CO2 adsorption
on coal has a higher spontaneity.
Based on the principle of minimum energy, any interface has the
8
Fuel 283 (2021) 118886
trend to decrease spontaneously surface energy. The interface of solid
can only reduce the surface free energy by the sorption of other ad-
sorbates. The bigger change of surface free energy results in a bigger
motivation to reduce energy by adsorbing gas and accordingly a larger
adsorption amount, which can be used to account for the bigger ad-
sorption amount of CO2 than CH4 on coals [27]. Nie et al. [60] con-
cluded that the change of surface free energy determines not only gas
adsorption capacity but also the difficulty of coal body fracture. When
the free energy changes greatly, the coal is more likely to fracture. To
better assess the safety of CO2 sequestration into coal seams, the change
of mechanical strength of coal body after CO2 adsorption also should be
taken into consideration. As plotted in Fig. 7, anthracite has the biggest
ΔG for CO2 and CH4, while ΔG of CO2 and CH4 on bituminous coal are
the smallest, suggesting that coal rank shows a U-shaped relationship
with Gibbs free energy changes of CO2 and CH4. Moreover, the influ-
ence of coal rank on ΔG of CO2 is more apparent than that of CH4.
4.5.3. Entropy losses of CO2 and CH4 on coals
Fig. 8 illustrates entropy losses of CO2 and CH4 on three samples. It
should be noted that ΔS values of both gases are negative, exhibiting
that CO2 and CH4 adsorption are from a disorder phase to an ordered
phase on different rank coals. Hence, the adsorption processes of both
gases include the formation of a more orderly rearrangement on coal
and the loss of the freedom degree for gas molecule.
At the temperature range of 273–423 K, ΔS of CH4 varies from
−82 J/mol/K to −87 J/mol/K [32]. ΔS of CH4 on three coals ranges
from −1.52 J/mol/K to −9.55 J/mol/K at the temperature range of
288–328 K. The smaller entropy loss of CH4 reveals that injected CH4
molecules are not completely adsorbed on surface but trapped in free
gas in the pore spaces. With increasing pressure, entropy loss of CH4 on
different rank coals decline considerably. As a result, as the surface
coverage (or loading) improves, the orderliness degree of adsorption
system gradually decreases, and injected CH4 is slowly adsorbed in the
bigger pores at the late stage instead of adsorbed in the smaller pores at
the initial stage (fresh adsorbent). The reduction of entropy loss of CH4
with pressure also illuminates that the interaction between CH4 mole-
cules is weaker within the bigger pores.
As shown in Fig. 8(b), ΔS of CO2 on three coals increase as pressure
enhances, and the orderliness degree of adsorption system is becoming
higher with pressure. High pressure is helpful for adsorbed CO2 mole-
cules to constitute a more stable packing. Meanwhile, at the late stage,
the interaction of CO2 molecules is stronger in the bigger pores, and the
movement of adsorbed molecules becomes severely limited. ΔS of CO2
on three coals ranges from −6.10 J/mol/K to −62.5 J/mol/K at the
temperature range of 288–328 K.
It is worth noting that decreasing temperature increases ΔS of CO2
X. Du, et al.
Fig. 7. Gibbs free energy changes of CH4 (a) and CO2 (b) on coals at different temperatures.
and CH4, which reveals that low temperature is favorable for adsorbed
CO2 and CH4 molecules to form a more efficient packing. Consequently,
the adsorption amount gets less under high temperature. At the same
condition, ΔS of CO2 is higher than that of CH4. The adsorbate with
permanent quadrupole moment can cause the stronger interaction with
electrostatic field, facilitating the occurrence of structured fluid and the
more efficient packing by orientating the adsorbate molecules into
cavity pores [61]. In the finding of Ridha and Webley [35], the entropy
loss of CO2 on chabazite zeolites is more pronounced than that of N2
owing to the bigger permanent quadrupole moment of CO2. When
studying CO2 and CH4 sorption on coals, the permanent quadrupole
moment of CO2 will promote the localized sorption and effective
packing, leading to larger ΔS for CO2 than that for CH4. The greater ΔS
denotes that adsorbed CO2 composes a more orderly configuration, and
this is one reason why CO2 adsorption on coals has a priority.
The order of ΔS on three samples is as follows: anthracite >
lignite > bituminous coal. There is also a U-shaped function between
coal rank and entropy loss. The value of ΔS on coal is related to the pore
size distribution of coal sample. Myers [62] reported that entropy loss
varies inversely with pore size due to the hindered rotational and
transitional movement. The results of Keffer at al. [63] indicated that
the entropy loss in the cavity is larger than that in the bigger pores, and
the bigger pore dimension boosts the formation of distinct layers and
the decrease of intensive entropy. Hence, ΔS for CO2 and CH4 on an-
thracite with abundant micropore are the highest, while bituminous
coal with a small amount of micropore has the lowest ΔS for CO2 and
CH4.
Fig. 8. Entropy losses of CH4 (a) and CO2 (b) on coals at different temperatures.
9
Fuel 283 (2021) 118886
5. Conclusion
The uptakes of CO2 and CH4 on anthracite are the largest, followed
by lignite and bituminous coal, agreeing with the order of the values of
micropore surface area and micropore volume of these coals. αCO2/CH4
increases with the increase in coal rank. Low temperature is beneficial
for the replacement of pre-adsorbed CH4 by injecting CO2. The smaller
KH of CH4 than CO2 reveals that the affinity of CH4 is lower on coal.
Increasing temperature lowers KH for CO2 and CH4. Anthracite has the
biggest KH, while KH on bituminous coal is the smallest.
Ω, ΔG and ΔS all exhibit a U-shaped relationship with coal rank. The
absolute values of Ω, ΔG and ΔS on three coal samples are in the order:
anthracite > lignite > bituminous coal. Ω, ΔG and ΔS are affected by
pore size distributions of these coals. Ω, ΔG and ΔS of CH4 are lower
than those of CO2. CO2 sorption is more favorable and spontaneous, and
adsorbed CO2 molecules form a more efficient packing on coal surface.
6. Data availability
The data applied to support the results in this study are available
from the corresponding author upon request.
CRediT authorship contribution statement
Xidong Du: Writing - original draft. Yugang Cheng:
Conceptualization, Methodology, Project administration. Zhenjian Liu:
Resources. Hong Yin: Data curation. Tengfei Wu: Investigation,
X. Du, et al.
Formal analysis. Liang Huo: Supervision, Funding acquisition.
Couxian Shu: Writing - review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work was supported by Special Youth Project of Science and
Technology Innovation Enterprise Capital of China Coal Technology
Engineering Group Co., Ltd. (Grant no. 2018-2-QN016), Doctoral
Startup Foundation of East China University of Technology (Grant no.
DHBK2018020), Fund of State Key Laboratory of Nuclear Resources
and Environment, East China University of Technology (Grant nos.
NRE1606 and NRE1917), the National Natural Science Foundation of
China (Grant no. 51904049), the Natural Science Foundation of
Chongqing (General Program, Grant no. cstc2019jcyj-msxmX0702),
Chongqing Basic Science and Advanced Technology Research Program
(Grant no. cstc2019jcyj-msxmX0756) and Natural Science Foundation
of Jiangxi (Grant no. 20202BABL214020).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2020.118886.
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