# Changes in Pore Structure of Coal Caused by CS2 Treatment and Its Methane Adsorption Response

Authors: Run Chen; Yong Qin; Pengfei Zhang; Youyang Wang
Journal: Geofluids
 (2018)

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## Abstract

The pore structure and gas adsorption are two key issues that affect the coal bed methane recovery process significantly. To change pore structure and gas adsorption, 5 coals with different ranks were treated by CS2 for 3 h using a Soxhlet extractor under ultrasonic oscillation conditions; the evolutions of pore structure and methane adsorption were examined using a high-pressure mercury intrusion porosimeter (MIP) with an AutoPore IV 9310 series mercury instrument. The results show that the cumulative pore volume and specific surface area (SSA) were increased after CS2 treatment, and the incremental micropore volume and SSA were increased and decreased before and after Ro,max=1.3%, respectively; the incremental big pore (greater than 10 nm in diameter) volumes were increased and SSA was decreased for all coals, and pore connectivity was improved. Methane adsorption capacity on coal before and after Ro,max=1.3% also was increased and decreased, respectively. There is a positive correlation between the changes in the micropore SSA and the Langmuir volume. It confirms that the changes in pore structure and methane adsorption capacity due to CS2 treatment are controlled by the rank, and the change in methane adsorption is impacted by the change of micropore SSA and suggests that the changes in pore structure are better for gas migration; the alteration in methane adsorption capacity is worse and better for methane recovery before and after Ro,max=1.3%. A conceptual mechanism of pore structure is proposed to explain methane adsorption capacity on CS2 treated coal around the Ro,max=1.3%.


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## Body

## 1. Introduction

Coal bed methane (CBM) is a serious risk (gas outburst) to safe production in coalmines and also is one of the most important energies in recent decades, but it is not easy to recover due to the low porosity and permeability of the coal seam reservoir. Previous studies have confirmed that coal has a dual pore system including primary porosity consisting of micropore, transitional pore, and mesopore in the coal matrix and second porosity composed of nonuniformly distributed macropore [1–4]. CBM is held to the internal specific surface area (SSA) of coal with absorbed state mainly, and some free gas exists in the natural fractures of coal and some gas dissolves in waters in coal [3–8]. Thus, the quantification of the pore structure is essential to estimating coal bed methane storage capacity and predicting gas production in reservoir conditions.Various pore characterization techniques have been applied to quantify the pore structures from total porosity, pore volume, pore size distribution (PSD), SSA, and so on [2, 9–15]. These include low-pressure gas (N2/CO2) adsorption/desorption techniques [9–12], high-pressure mercury intrusion porosimetery (MIP) [12–14], ultra/small-angle neutron scattering (SANS) [15, 16], focused ion beam scanning electron microscopy [17], field emission scanning electron microscopy/transmission electron microscopy [18], nuclear magnetic resonance [19, 20], and X-ray computed tomography [17, 19, 20]. There are several types of pore classification systems employed for various pore scales in CBM research, including Hodot classification, the classification of International Union of Pure and Applied Chemistry (IUPAC), and Gan classification [21–23]. Hodot classification is accepted widely to describe the various scale pores of MIP.Coal rank is the degree of the transformation of peat through lignite as well as subbituminous, bituminous, semianthracite to anthracite, and meta-anthracite coal, and the rank classes in terms of vitrinite reflectance (Ro,max). Many studies have shown that the pore size distribution is affected by the coal rank and there is a U-shaped relationship between the pore size distribution and coal rank [24]. A number of studies concluded that micropores and transitional pores are the primary space for CBM storage, whereas meso- and macropores are responsible for CBM migration [1, 25–31].Methane adsorption in coal is controlled by internal factors, including coal rank, macerals (vitrinite, exinite, and inertinite), and pore size distribution [1, 26, 29, 30, 32], and influenced by external factors, such as temperature, pressure, and humidity [26, 33, 34]. The methane adsorption capacity in coal increases with coal rank and vitrinite content in macerals at high coal ranks, which is because vitrinite is more microporous with a higher SSA than inertinite is [35, 36]. The SSA of micropore has a positive relationship with CH4 adsorption capacity [37, 38].Those researches have confirmed the coal seam with low porosity and permeability, and the pore structures (PSDs, SSA, and pore volumes) are controlled by the coal rank and have an important impact on methane adsorption capacity; aroundRo,max=1.3%, the evolution tends to change obviously. Only limited studies have quantified the alteration of the pore structure and gas adsorption. In our study, we will try to quantify the effect of the CS2 treatment effect on pore structure and methane adsorption changes with coal rank. Such changes have potential impacts on coal bed methane recovery.


## 2. Materials and Methods

### 2.1. Coal Samples

The coal samples were collected from undeformed Permian coal seams in Haitian coalmines located in eastern Yunnan Province and Tucheng, Yuni, Linyuan, and Jinjia located in Guizhou Province (Figure1). All of the samples were wrapped in black polyethylene bags after collection before being transported to the laboratory for analysis. To eliminate the effects of the sedimentology and the parent material of coals, vitrinites were first separated and collected by hand and then pulverized for passage through a 35-mesh sieve. Finally, they were enriched using the heavy liquid floatation method until the vitrinite content was above 85% (Table 1). The samples were divided into 2 parts. One part was dried for mercury intrusion measurements and methane isothermal adsorption. The second part was treated by CS2 and then was dried for mercury intrusion measurements and methane isothermal adsorption.Figure 1
Locations of coalmines for coal samples collected.Table 1
Vitrinite reflectance, macerals, and proximate analysis.
Samples
Haitian
Tucheng
Yuni
Linyuan
Jinjia
Ro,max (%)
0.73
1.04
1.28
1.53
2.06
Vitrinite (%)
95.54
87.42
85.77
89.67
93.95
Inertinite (%)
0.97
3.56
0.38
0.19
—
Exinite (%)
2.91
8.54
11.39
9.37
5.68
Mineral (%)
0.58
0.48
2.47
0.76
0.38
Mad (%)
3.28
0.98
1.12
0.96
1.01
Ad (%)
3.65
7.09
6.07
4.17
8.97
Vad (%)
33.34
34.07
23.96
17.27
13.45


### 2.2. CS2 Treatment

CS2 treatment was conducted using a Soxhlet extractor under ultrasonic oscillation conditions at room temperature using the following procedure with CS2. First, for each experiment, approximately 20 g of dry coal was placed into the flat container of the Soxhlet extractor. Then, approximately 600 mL of CS2 was added, and the extractor was sealed to begin treatment under ultrasonic oscillation. Each CS2 treatment was performed for approximately three hours. After the treatment, the liquid eluents were separated from coal, and the coal was dried at 80 ° C. The CS2 treatment was repeated until the mass of each treated coal was greater than 80 g.


### 2.3. Pore Structure Test

Measurements of the pore structures were conducted using a mercury intrusion porosimeter with an AutoPore IV 9310 series mercury instrument. For the mercury intrusion porosimetry measurements, a contact angle of 140° and a surface tension of 485 dyn/cm were assumed. All samples were dried at 80°C for at least three hours before the tests.


### 2.4. Methane Isothermal Adsorption Experiment

Methane isothermal adsorptions on samples were performed using a Laboratory Isotherm Adsorption System on an IS-100 adsorption system. Prior to measurement, the samples were crushed in accordance with the Chinese Standard GB/T 212-2001 and were dried at 80°C until the weight loss was less than 1%. The measurements were carried out at 30°C, and each isothermal adsorption curve includes six different pressures. Approximately 80 g of each sample was tested, and the adsorbate was 99.99% methane.


## 2.1. Coal Samples

The coal samples were collected from undeformed Permian coal seams in Haitian coalmines located in eastern Yunnan Province and Tucheng, Yuni, Linyuan, and Jinjia located in Guizhou Province (Figure1). All of the samples were wrapped in black polyethylene bags after collection before being transported to the laboratory for analysis. To eliminate the effects of the sedimentology and the parent material of coals, vitrinites were first separated and collected by hand and then pulverized for passage through a 35-mesh sieve. Finally, they were enriched using the heavy liquid floatation method until the vitrinite content was above 85% (Table 1). The samples were divided into 2 parts. One part was dried for mercury intrusion measurements and methane isothermal adsorption. The second part was treated by CS2 and then was dried for mercury intrusion measurements and methane isothermal adsorption.Figure 1
Locations of coalmines for coal samples collected.Table 1
Vitrinite reflectance, macerals, and proximate analysis.
Samples
Haitian
Tucheng
Yuni
Linyuan
Jinjia
Ro,max (%)
0.73
1.04
1.28
1.53
2.06
Vitrinite (%)
95.54
87.42
85.77
89.67
93.95
Inertinite (%)
0.97
3.56
0.38
0.19
—
Exinite (%)
2.91
8.54
11.39
9.37
5.68
Mineral (%)
0.58
0.48
2.47
0.76
0.38
Mad (%)
3.28
0.98
1.12
0.96
1.01
Ad (%)
3.65
7.09
6.07
4.17
8.97
Vad (%)
33.34
34.07
23.96
17.27
13.45


## 2.2. CS2 Treatment

CS2 treatment was conducted using a Soxhlet extractor under ultrasonic oscillation conditions at room temperature using the following procedure with CS2. First, for each experiment, approximately 20 g of dry coal was placed into the flat container of the Soxhlet extractor. Then, approximately 600 mL of CS2 was added, and the extractor was sealed to begin treatment under ultrasonic oscillation. Each CS2 treatment was performed for approximately three hours. After the treatment, the liquid eluents were separated from coal, and the coal was dried at 80 ° C. The CS2 treatment was repeated until the mass of each treated coal was greater than 80 g.


## 2.3. Pore Structure Test

Measurements of the pore structures were conducted using a mercury intrusion porosimeter with an AutoPore IV 9310 series mercury instrument. For the mercury intrusion porosimetry measurements, a contact angle of 140° and a surface tension of 485 dyn/cm were assumed. All samples were dried at 80°C for at least three hours before the tests.


## 2.4. Methane Isothermal Adsorption Experiment

Methane isothermal adsorptions on samples were performed using a Laboratory Isotherm Adsorption System on an IS-100 adsorption system. Prior to measurement, the samples were crushed in accordance with the Chinese Standard GB/T 212-2001 and were dried at 80°C until the weight loss was less than 1%. The measurements were carried out at 30°C, and each isothermal adsorption curve includes six different pressures. Approximately 80 g of each sample was tested, and the adsorbate was 99.99% methane.


## 3. Results and Discussion

### 3.1. Pore Structure and Its Evolution

The pore distributions of samples are shown in Figure2; the incremental macro- and mesopores have a very high percentage. It contradicts with the previous understandings [3, 37, 38]. It was regarded that there were so many gaps between sample particles in this study. Due to many gaps between sample particles, the pores that were over 10,000 nm in diameter were eliminated to reduce the interference on pore structure. Attributed to the lower limitation of 6 nm for AutoPore IV 9310, a modified Hodot classification was used as follows: micropores (6~10 nm), transitional pores (10~100 nm), mesopores (100~1000 nm), and macropores (1000~10,000 nm).Figure 2
Pore size distributions of samples.Previous studies have shown that the incremental macro- and micropores contribute the most to the cumulative pore volume and SSA, respectively [37, 38]. In our study, the cumulative pore volumes range from 0.0207 to 0.2332 cm3/g (Table 2), and the cumulative pore SSAs range from 4.7525 to 16.3162 m2/g (Table 3). The volumes from the incremental macropores and transitional pores account for over 65% of the cumulative volume, confirming that the big pores are the main contributors for the cumulative pore volume. The SSAs from the incremental transitional and micropores account for over 90% of the cumulative SSA, confirming that small pores are the main contributors to the cumulative pore SSA.Table 2
Pore volumes of the untreated and CS2-treated coals.
Sample
Pore volume (10−2 cm3/g)
Percentage of pore volume (%)
Vma
Vme
Vtr
Vmi
Vcu
Vma
Vme
Vtr
Vmi
Haitian coal
Untreated
1.9993
0.4217
2.2700
2.2268
6.9178
28.9005
6.0959
32.8139
32.1897
CS2-treated
2.2954
0.4452
2.2441
2.3203
7.3050
31.4223
6.0945
30.7201
31.7632
Tucheng coal
Untreated
1.8898
0.5251
1.1272
0.7675
4.3096
43.8509
12.1844
26.1556
17.8091
CS2-treated
4.7273
1.0533
1.2954
0.8447
7.9207
59.6829
13.2981
16.3546
10.6645
Yuni coal
Untreated
8.9632
1.2964
1.1858
0.8003
12.2457
73.1947
10.5866
9.6834
6.5354
CS2-treated
11.5381
1.3212
1.2022
0.7659
14.8274
77.8161
8.9105
8.1080
5.1654
Linyuan coal
Untreated
5.1626
1.0588
1.4258
0.9565
8.6037
60.0044
12.3063
16.5719
11.1173
CS2-treated
21.7167
2.4350
1.4867
0.8166
26.4550
82.0892
9.2043
5.6197
3.0868
Jinjia coal
Untreated
7.2069
0.9851
1.0027
0.6632
9.8579
73.1079
9.9930
10.1715
6.7276
CS2-treated
7.4285
1.0097
0.9863
0.5505
9.9750
74.4712
10.1223
9.8877
5.5188
ma: macropore; me: mesopore; tr: transitional pore; mi: micropore; cu: cumulative pore.Table 3
Pore surface areas of the untreated and CS2-treated coals.
Sample
Pore surface area (m2/g)
Percentage of pore surface area (%)
Sma
Sme
Str
Smi
Scu
Sma
Sme
Str
Smi
Haitian coal
Untreated
0.0207
0.0592
4.3972
11.4185
15.8956
0.1302
0.3725
27.6630
71.8340
CS2-treated
0.0242
0.0598
4.3316
11.9007
16.3162
0.1482
0.3663
26.5478
72.9375
Tucheng coal
Untreated
0.0234
0.0627
2.0713
3.7832
5.9406
0.3944
1.0548
34.8671
63.6843
CS2-treated
0.0569
0.1080
2.3548
4.2405
6.7602
0.8419
1.5977
34.8331
62.7270
Yuni coal
Untreated
0.1013
0.1236
2.0826
4.0518
6.3593
1.5930
1.9430
32.7487
63.7150
CS2-treated
0.1134
0.1303
2.1295
3.8570
6.2302
1.8199
2.0913
34.1803
61.9086
Linyuan coal
Untreated
0.0590
0.1189
2.3850
4.8200
7.3829
0.7997
1.6104
32.3044
65.2855
CS2-treated
0.2332
0.2209
2.3362
4.1257
6.9160
3.3718
3.1943
33.7796
59.6543
Jinjia coal
Untreated
0.0823
0.0961
1.7635
3.3377
5.2796
1.5587
1.8202
33.4022
63.2197
CS2-treated
0.0837
0.1058
1.7652
2.7978
4.7525
1.7616
2.2254
37.1424
58.8702
ma: macropore; me: mesopore; tr: transitional pore; mi: micropore; cu: cumulative pore.To further study the changes in pore volume and SSA caused by CS2 treatment, ΔV and ΔS were defined by the following equations, respectively:
(1)ΔV=Vt−Vu,ΔS=St−Su,where ΔV is the incremental pore volume change due to CS2 treatment, in cm3/g; Vt and Vu are the incremental pore volumes of the treated coal and the untreated coal, respectively, in cm3/g; ΔS is the change in the incremental SSA due to the treatment, in m2/g; St and Su are the incremental SSAs of the treated coal and the untreated coal, respectively, in m2/g.After CS2 treatment, the incremental pore volumes and SSAs changed substantially. As shown in Figures 3 and 4, ΔVmi and ΔSmi are positive and negative before and after Ro,max=1.3%, respectively; some of ΔVtr and ΔStr are positive and the others are negative, demonstrating no obvious regularity. ΔVma, ΔVme, ΔSma, and ΔSme all are positive. Those data indicate that after CS2 treatment, all incremental pore sizes are enlarged, the incremental micropore numbers before Ro,max=1.3% are increased, and the numbers of the incremental micropore and other pores are decreased in all samples.Figure 3
Plots of the changes in pore volume with coal rank: (a) pore volume change in micropore and transitional pore and (b) pore volume change in mesopore and macropore.
(a)
(b)Figure 4
Plots of the changes in SSA with coal rank: (a) SSA change in micropore and transitional pore and (b) SSA change in mesopore and macropore.
(a)
(b)Previous studies have shown that aliphatic groups containing oxygen link the multilayered stacks and have not yet been dissipated as volatiles at the early stage of coalification [37, 38]. It is compressed with coal rank increasing; the aliphatic groups containing oxygen link the multilayered stacks which began to dissipate and fill the pores and the micropores smaller, and then as maturation advances, oxygen-containing compounds and other volatiles are being lost. It indicates that the changes on pore structure due to CS2 treatment are controlled by the coal rank. The data indicate that the treatment of CS2 has enlarging effect on pore size and increasing effect on pore number. We concluded that the pore size-enlarging effect is the main result of the sample pore volumes, the pore number-increasing effect occurs in the micropores of sample SSAs before Ro,max=1.3%, and the evaluation of the pore structure due to CS2 treatment is controlled by the coal rank.Hysteresis between the intrusion and extrusion can use the Ink Bottle theory [39] or connectivity model [13] to interpret. In these theories, pores in samples are rarely of a uniform shape and would be broken at all the throats between pore amounts of mercury trapped inside the sample. A network of pores is used to introduce an additional component considering the connection effects between the pores.In this study, the hysteresises of the samples were reduced significantly by the treatment of CS2 (Figure 5). It could be explained using the Ink Bottle theory and/or connectivity model. Because of the treatment of CS2, small organic matters filled in open pores may be dissolved and flushed away to cause some incremental pore sizes to be enlarged and the number of incremental micropore to be increased, causing some closed and/or ink bottle pores with small organic matters to open and connect, indicating that CS2 treatment improves the connectivity of the pore; it is better for gas migration during the process of coalbed methane production.Figure 5
V/VCu of the samples as a function of pore diameter: (a) Haitian samples, (b) Tucheng samples, (c) Yuni samples, (d) Linyuan samples, and (e) Jinjia samples.
(a)
(b)
(c)
(d)
(e)


### 3.2. Methane Isothermal Adsorption Capacity and Its Evolution

Excess methane isothermal adsorption was measured using the volumetric method, and the results are shown in Figure6. The adsorbed volumes are expressed on a dry ash-free basis. The measured methane adsorption capacities of samples range from 14.99 to 28.87 cm3/g. Generally, the methane adsorption capacities of untreated coals increase with coal rank increasing, confirming that methane adsorption capacity on untreated coal is affected by the coal rank.Figure 6
Curves of methane isothermal adsorption on samples: (a) samples of Haitian and Tucheng coals and (b) samples of Yuni, Linyuan, and Jinjia coals.
(a)
(b)Based on the curves of the methane adsorption on samples, the Langmuir model can be used to describe the isothermal adsorption curves of the samples:(2)V=VLPPL+P,where V is the methane adsorption volume at equilibrium conditions, in cm3/g; P is the equilibrium pressure, in MPa; VL is the Langmuir volume at standard state with a pressure of 101 kPa and a temperature of 273.15 K, in cm3/g; and PL is the Langmuir pressure, in MPa.The Langmuir constants of the untreated and CS2-treated coals are shown in Table 4. To further study the changes in methane adsorption capacity that is due to CS2 treatment and the effect on coal bed methane recovery, ΔVL and ΔPL are defined using the following equations, respectively:
(3)ΔVL=VLt−VLu,ΔPL=PLt−PLu,where ΔVL is the change in VL due to CS2 treatment, in cm3/g; VLt and VLu are the VL for CS2-treated coal and untreated coal, respectively, in cm3/g; ΔPL is the change in PL due to the treatment, in MPa; and ΔPLt and ΔPLu are the PL for CS2-treated coal and untreated coal, respectively, MPa.Table 4
Langmuir constants of untreated and CS2-treated coals.
Sample
VL (cm3/g)
PL (MPa)
Haitian coal
Untreated
14.99
5.19
CS2-treated
21.80
5.52
Tucheng coal
Untreated
22.12
4.26
CS2-treated
24.05
3.53
Yuni coal
Untreated
25.86
2.77
CS2-treated
25.23
2.75
Linyuan coal
Untreated
27.46
2.60
CS2-treated
27.33
2.83
Jinjia coal
Untreated
28.87
3.00
CS2-treated
27.89
2.82As shown in Figure7, after CS2 treatment, the ΔVL of Haitian coal and Tucheng coal is positive, while that of other coal samples is negative (Figure 7(a)). The ΔPL of Haitian coal and Linyuan coal is positive and that of others is negative (Figure 7(b)). Thus, the treatment of CS2 increased and decreased the methane adsorption capacities in coals before and after Ro,max=1.3%, respectively, and there was no consistent trend for ΔPL. The changes in the methane adsorption capacities due to CS2 treatment are controlled by the coal rank, which indicates that CS2 could be used for ECBM recovery for coals after Ro,max=1.3% from the view of methane adsorption, but not for low-rank coals.Figure 7
Methane isothermal adsorption constant changes with the coal rank increasing: (a)ΔVL changes with the coal rank increasing and (b) ΔPL changes with the coal rank increasing.
(a)
(b)


### 3.3. Effects of Pore Structure Changes on Methane Adsorption Capacity

The effect of pore structure changes due to CS2 treatment on the methane adsorption capacities are shown in Figure 8. ΔVL increased when ΔSmi increased, and there is no relation to ΔStr, ΔSme, ΔSma, and ΔV. Previous studies have shown that the methane adsorption capacity in coal is primarily controlled by the magnitude of the pore SSA, and the pore SSA is controlled by the coal rank and influenced by the maceral composition [37, 40]. In this study, the relation of ΔVL to ΔV and ΔS shows that the methane adsorption capacity is closely related to the micropore SSA, demonstrating that the pore number is increased for coal before Ro,max=1.3% and the pore size is enlarged in all diameters for all coals due to CS2 treatment. It also confirms that the changes of pore structures and methane adsorption capacities due to CS2 treatment are controlled by the coal rank.Figure 8
ΔVL versus ΔV and ΔS: (a) ΔVL changes with ΔV increasing and (b) ΔVL changes with ΔS increasing.
(a)
(b)


### 3.4. A Conceptual Pore Structure Evolution Model with CS2 Treatment

As previously mentioned, the discrepancy in the sense of the change in pore structure may be attributed to changes in the size and connectivity of the micron-scale inaccessible pores. Lee’s study has provided evidence that the amount of normal alkanes drops at the early stage of coalification, then fill in pores and cause the size of small pores to be reduced; as maturation advances, more methane is generated and normal alkanes are lost [41]. Therefore, there are some differences in pore structure changes for CS2-treated coal before and after Ro,max=1.3%. A conceptual model for pore structure evolution resulting from CS2 treatment is proposed, as shown in Figure 9. Due to CS2 treatment, some closed and or ink bottle pores filled with small organic molecules of coal open and connect before Ro,max=1.3%, and the amount of micropores which can be measured by MIP was increased (Figure 9(a)); the pore sizes were enlarged in all coals (Figures 9(a) and 9(b)), and the connectivity of the pores was improved (Figure 9(c)). However, further studies will be needed to confirm this hypothesis for the changes in pore structures of coal caused by CS2 treatment.Figure 9
A conceptual mechanism of pore structure for CS2-treated coal. (a) Pore structure changes for CS2-treated coal before Ro,max=1.3%; (b) pore structure changes for CS2-treated coal after Ro,max=1.3%; (c) the change of pore connectivity of CS2-treated coal.
(a)
(b)
(c)Studies have shown that there is a positive relation between micropore SSA and methane adsorption [1, 26, 29, 32]. In this study, after CS2 treatment, the change in methane adsorption capacity on coal before and after Ro,max=1.3% is increased and decreased, which confirms the changes in pore structure due to CS2 treatment.


## 3.1. Pore Structure and Its Evolution

The pore distributions of samples are shown in Figure2; the incremental macro- and mesopores have a very high percentage. It contradicts with the previous understandings [3, 37, 38]. It was regarded that there were so many gaps between sample particles in this study. Due to many gaps between sample particles, the pores that were over 10,000 nm in diameter were eliminated to reduce the interference on pore structure. Attributed to the lower limitation of 6 nm for AutoPore IV 9310, a modified Hodot classification was used as follows: micropores (6~10 nm), transitional pores (10~100 nm), mesopores (100~1000 nm), and macropores (1000~10,000 nm).Figure 2
Pore size distributions of samples.Previous studies have shown that the incremental macro- and micropores contribute the most to the cumulative pore volume and SSA, respectively [37, 38]. In our study, the cumulative pore volumes range from 0.0207 to 0.2332 cm3/g (Table 2), and the cumulative pore SSAs range from 4.7525 to 16.3162 m2/g (Table 3). The volumes from the incremental macropores and transitional pores account for over 65% of the cumulative volume, confirming that the big pores are the main contributors for the cumulative pore volume. The SSAs from the incremental transitional and micropores account for over 90% of the cumulative SSA, confirming that small pores are the main contributors to the cumulative pore SSA.Table 2
Pore volumes of the untreated and CS2-treated coals.
Sample
Pore volume (10−2 cm3/g)
Percentage of pore volume (%)
Vma
Vme
Vtr
Vmi
Vcu
Vma
Vme
Vtr
Vmi
Haitian coal
Untreated
1.9993
0.4217
2.2700
2.2268
6.9178
28.9005
6.0959
32.8139
32.1897
CS2-treated
2.2954
0.4452
2.2441
2.3203
7.3050
31.4223
6.0945
30.7201
31.7632
Tucheng coal
Untreated
1.8898
0.5251
1.1272
0.7675
4.3096
43.8509
12.1844
26.1556
17.8091
CS2-treated
4.7273
1.0533
1.2954
0.8447
7.9207
59.6829
13.2981
16.3546
10.6645
Yuni coal
Untreated
8.9632
1.2964
1.1858
0.8003
12.2457
73.1947
10.5866
9.6834
6.5354
CS2-treated
11.5381
1.3212
1.2022
0.7659
14.8274
77.8161
8.9105
8.1080
5.1654
Linyuan coal
Untreated
5.1626
1.0588
1.4258
0.9565
8.6037
60.0044
12.3063
16.5719
11.1173
CS2-treated
21.7167
2.4350
1.4867
0.8166
26.4550
82.0892
9.2043
5.6197
3.0868
Jinjia coal
Untreated
7.2069
0.9851
1.0027
0.6632
9.8579
73.1079
9.9930
10.1715
6.7276
CS2-treated
7.4285
1.0097
0.9863
0.5505
9.9750
74.4712
10.1223
9.8877
5.5188
ma: macropore; me: mesopore; tr: transitional pore; mi: micropore; cu: cumulative pore.Table 3
Pore surface areas of the untreated and CS2-treated coals.
Sample
Pore surface area (m2/g)
Percentage of pore surface area (%)
Sma
Sme
Str
Smi
Scu
Sma
Sme
Str
Smi
Haitian coal
Untreated
0.0207
0.0592
4.3972
11.4185
15.8956
0.1302
0.3725
27.6630
71.8340
CS2-treated
0.0242
0.0598
4.3316
11.9007
16.3162
0.1482
0.3663
26.5478
72.9375
Tucheng coal
Untreated
0.0234
0.0627
2.0713
3.7832
5.9406
0.3944
1.0548
34.8671
63.6843
CS2-treated
0.0569
0.1080
2.3548
4.2405
6.7602
0.8419
1.5977
34.8331
62.7270
Yuni coal
Untreated
0.1013
0.1236
2.0826
4.0518
6.3593
1.5930
1.9430
32.7487
63.7150
CS2-treated
0.1134
0.1303
2.1295
3.8570
6.2302
1.8199
2.0913
34.1803
61.9086
Linyuan coal
Untreated
0.0590
0.1189
2.3850
4.8200
7.3829
0.7997
1.6104
32.3044
65.2855
CS2-treated
0.2332
0.2209
2.3362
4.1257
6.9160
3.3718
3.1943
33.7796
59.6543
Jinjia coal
Untreated
0.0823
0.0961
1.7635
3.3377
5.2796
1.5587
1.8202
33.4022
63.2197
CS2-treated
0.0837
0.1058
1.7652
2.7978
4.7525
1.7616
2.2254
37.1424
58.8702
ma: macropore; me: mesopore; tr: transitional pore; mi: micropore; cu: cumulative pore.To further study the changes in pore volume and SSA caused by CS2 treatment, ΔV and ΔS were defined by the following equations, respectively:
(1)ΔV=Vt−Vu,ΔS=St−Su,where ΔV is the incremental pore volume change due to CS2 treatment, in cm3/g; Vt and Vu are the incremental pore volumes of the treated coal and the untreated coal, respectively, in cm3/g; ΔS is the change in the incremental SSA due to the treatment, in m2/g; St and Su are the incremental SSAs of the treated coal and the untreated coal, respectively, in m2/g.After CS2 treatment, the incremental pore volumes and SSAs changed substantially. As shown in Figures 3 and 4, ΔVmi and ΔSmi are positive and negative before and after Ro,max=1.3%, respectively; some of ΔVtr and ΔStr are positive and the others are negative, demonstrating no obvious regularity. ΔVma, ΔVme, ΔSma, and ΔSme all are positive. Those data indicate that after CS2 treatment, all incremental pore sizes are enlarged, the incremental micropore numbers before Ro,max=1.3% are increased, and the numbers of the incremental micropore and other pores are decreased in all samples.Figure 3
Plots of the changes in pore volume with coal rank: (a) pore volume change in micropore and transitional pore and (b) pore volume change in mesopore and macropore.
(a)
(b)Figure 4
Plots of the changes in SSA with coal rank: (a) SSA change in micropore and transitional pore and (b) SSA change in mesopore and macropore.
(a)
(b)Previous studies have shown that aliphatic groups containing oxygen link the multilayered stacks and have not yet been dissipated as volatiles at the early stage of coalification [37, 38]. It is compressed with coal rank increasing; the aliphatic groups containing oxygen link the multilayered stacks which began to dissipate and fill the pores and the micropores smaller, and then as maturation advances, oxygen-containing compounds and other volatiles are being lost. It indicates that the changes on pore structure due to CS2 treatment are controlled by the coal rank. The data indicate that the treatment of CS2 has enlarging effect on pore size and increasing effect on pore number. We concluded that the pore size-enlarging effect is the main result of the sample pore volumes, the pore number-increasing effect occurs in the micropores of sample SSAs before Ro,max=1.3%, and the evaluation of the pore structure due to CS2 treatment is controlled by the coal rank.Hysteresis between the intrusion and extrusion can use the Ink Bottle theory [39] or connectivity model [13] to interpret. In these theories, pores in samples are rarely of a uniform shape and would be broken at all the throats between pore amounts of mercury trapped inside the sample. A network of pores is used to introduce an additional component considering the connection effects between the pores.In this study, the hysteresises of the samples were reduced significantly by the treatment of CS2 (Figure 5). It could be explained using the Ink Bottle theory and/or connectivity model. Because of the treatment of CS2, small organic matters filled in open pores may be dissolved and flushed away to cause some incremental pore sizes to be enlarged and the number of incremental micropore to be increased, causing some closed and/or ink bottle pores with small organic matters to open and connect, indicating that CS2 treatment improves the connectivity of the pore; it is better for gas migration during the process of coalbed methane production.Figure 5
V/VCu of the samples as a function of pore diameter: (a) Haitian samples, (b) Tucheng samples, (c) Yuni samples, (d) Linyuan samples, and (e) Jinjia samples.
(a)
(b)
(c)
(d)
(e)


## 3.2. Methane Isothermal Adsorption Capacity and Its Evolution

Excess methane isothermal adsorption was measured using the volumetric method, and the results are shown in Figure6. The adsorbed volumes are expressed on a dry ash-free basis. The measured methane adsorption capacities of samples range from 14.99 to 28.87 cm3/g. Generally, the methane adsorption capacities of untreated coals increase with coal rank increasing, confirming that methane adsorption capacity on untreated coal is affected by the coal rank.Figure 6
Curves of methane isothermal adsorption on samples: (a) samples of Haitian and Tucheng coals and (b) samples of Yuni, Linyuan, and Jinjia coals.
(a)
(b)Based on the curves of the methane adsorption on samples, the Langmuir model can be used to describe the isothermal adsorption curves of the samples:(2)V=VLPPL+P,where V is the methane adsorption volume at equilibrium conditions, in cm3/g; P is the equilibrium pressure, in MPa; VL is the Langmuir volume at standard state with a pressure of 101 kPa and a temperature of 273.15 K, in cm3/g; and PL is the Langmuir pressure, in MPa.The Langmuir constants of the untreated and CS2-treated coals are shown in Table 4. To further study the changes in methane adsorption capacity that is due to CS2 treatment and the effect on coal bed methane recovery, ΔVL and ΔPL are defined using the following equations, respectively:
(3)ΔVL=VLt−VLu,ΔPL=PLt−PLu,where ΔVL is the change in VL due to CS2 treatment, in cm3/g; VLt and VLu are the VL for CS2-treated coal and untreated coal, respectively, in cm3/g; ΔPL is the change in PL due to the treatment, in MPa; and ΔPLt and ΔPLu are the PL for CS2-treated coal and untreated coal, respectively, MPa.Table 4
Langmuir constants of untreated and CS2-treated coals.
Sample
VL (cm3/g)
PL (MPa)
Haitian coal
Untreated
14.99
5.19
CS2-treated
21.80
5.52
Tucheng coal
Untreated
22.12
4.26
CS2-treated
24.05
3.53
Yuni coal
Untreated
25.86
2.77
CS2-treated
25.23
2.75
Linyuan coal
Untreated
27.46
2.60
CS2-treated
27.33
2.83
Jinjia coal
Untreated
28.87
3.00
CS2-treated
27.89
2.82As shown in Figure7, after CS2 treatment, the ΔVL of Haitian coal and Tucheng coal is positive, while that of other coal samples is negative (Figure 7(a)). The ΔPL of Haitian coal and Linyuan coal is positive and that of others is negative (Figure 7(b)). Thus, the treatment of CS2 increased and decreased the methane adsorption capacities in coals before and after Ro,max=1.3%, respectively, and there was no consistent trend for ΔPL. The changes in the methane adsorption capacities due to CS2 treatment are controlled by the coal rank, which indicates that CS2 could be used for ECBM recovery for coals after Ro,max=1.3% from the view of methane adsorption, but not for low-rank coals.Figure 7
Methane isothermal adsorption constant changes with the coal rank increasing: (a)ΔVL changes with the coal rank increasing and (b) ΔPL changes with the coal rank increasing.
(a)
(b)


## 3.3. Effects of Pore Structure Changes on Methane Adsorption Capacity

The effect of pore structure changes due to CS2 treatment on the methane adsorption capacities are shown in Figure 8. ΔVL increased when ΔSmi increased, and there is no relation to ΔStr, ΔSme, ΔSma, and ΔV. Previous studies have shown that the methane adsorption capacity in coal is primarily controlled by the magnitude of the pore SSA, and the pore SSA is controlled by the coal rank and influenced by the maceral composition [37, 40]. In this study, the relation of ΔVL to ΔV and ΔS shows that the methane adsorption capacity is closely related to the micropore SSA, demonstrating that the pore number is increased for coal before Ro,max=1.3% and the pore size is enlarged in all diameters for all coals due to CS2 treatment. It also confirms that the changes of pore structures and methane adsorption capacities due to CS2 treatment are controlled by the coal rank.Figure 8
ΔVL versus ΔV and ΔS: (a) ΔVL changes with ΔV increasing and (b) ΔVL changes with ΔS increasing.
(a)
(b)


## 3.4. A Conceptual Pore Structure Evolution Model with CS2 Treatment

As previously mentioned, the discrepancy in the sense of the change in pore structure may be attributed to changes in the size and connectivity of the micron-scale inaccessible pores. Lee’s study has provided evidence that the amount of normal alkanes drops at the early stage of coalification, then fill in pores and cause the size of small pores to be reduced; as maturation advances, more methane is generated and normal alkanes are lost [41]. Therefore, there are some differences in pore structure changes for CS2-treated coal before and after Ro,max=1.3%. A conceptual model for pore structure evolution resulting from CS2 treatment is proposed, as shown in Figure 9. Due to CS2 treatment, some closed and or ink bottle pores filled with small organic molecules of coal open and connect before Ro,max=1.3%, and the amount of micropores which can be measured by MIP was increased (Figure 9(a)); the pore sizes were enlarged in all coals (Figures 9(a) and 9(b)), and the connectivity of the pores was improved (Figure 9(c)). However, further studies will be needed to confirm this hypothesis for the changes in pore structures of coal caused by CS2 treatment.Figure 9
A conceptual mechanism of pore structure for CS2-treated coal. (a) Pore structure changes for CS2-treated coal before Ro,max=1.3%; (b) pore structure changes for CS2-treated coal after Ro,max=1.3%; (c) the change of pore connectivity of CS2-treated coal.
(a)
(b)
(c)Studies have shown that there is a positive relation between micropore SSA and methane adsorption [1, 26, 29, 32]. In this study, after CS2 treatment, the change in methane adsorption capacity on coal before and after Ro,max=1.3% is increased and decreased, which confirms the changes in pore structure due to CS2 treatment.


## 4. Conclusions

Alteration of the pore structure for 5 sets of untreated and CS2-treated coals was characterized by MIP, and methane adsorption capacity was estimated by the volumetric method. Based on these results, several conclusions are summarized as below:
(1).
After CS2 treatment, the cumulative pore volume and SSA were increased, and the incremental micropore volume and SSA were increased and decreased before and after Ro,max=1.3%, respectively; the incremental big pore (greater than 10 nm in diameter) volumes were increased and SSA were decreased for all coals, and pore connectivity was improved. The pore number is increased for coal before Ro,max=1.3%, and the pore size is enlarged in all diameters for all coals due to CS2 treatment; the changes are controlled by the coal rank. The change in pore structure is better for gas migration.
(2).
Methane adsorption isotherms of CS2 treatment coals followed the Langmuir model. After CS2 treatment, the methane adsorption capacity on coal is increased and decreased before and after Ro,max=1.3%, which indicates that the change in methane adsorption capacity due to CS2 treatment is controlled by the coal rank, and the solvent of CS2 can be used to enhance coal bed methane recovery for the coal after Ro,max=1.3%. The alteration in methane adsorption capacity is worse and better for methane recovery before and after Ro,max=1.3%.
(3).
There is a positive relationship betweenΔVL and ΔSmi, while there is no obvious relation with ΔVL and other ΔS, confirming that the pore number is increased for coal before Ro,max=1.3% and the pore size is enlarged in all diameters for all coals due to CS2 treatment.
(4).
A conceptual mechanism of the effect of CS2 treatment coal is proposed which is consistent with the observed evolution of the pore structure and methane adsorption response.



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*Source: 7578967-2018-08-06.xml*