# Permeability Characteristics of Coal after Supercritical CO2 Adsorption at Different Temperatures

Authors: Xueying Liu; Jin Yu; Di Wu; Xiaochun Xiao
Journal: Geofluids
 (2020)

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## Abstract

CO2 storage in coal seams has become one effective method to reduce CO2 emission and help exploit coalbed methane (CBM). The permeability is a key parameter for CBM extraction. In deep coal seams (>800 m), CO2 exists in the supercritical state. In the present work, permeability tests were performed on briquettes before and after supercritical CO2 (SC-CO2) adsorption at various temperatures to investigate the effects of SC-CO2 adsorption on the permeability. Experimental results show that SC-CO2 adsorption leads to volumetric expansion and permeability augment. The permeability enhancement decreases continuously at 35°C, while it initially increases and reduces at pressures exceeding 9 or 10 MPa at 45 or 55°C, respectively. Besides, the permeability enhancement ratio shows a linear increase with the expansion. The research provides a basis for further research on the enhanced coalbed methane (ECBM) recovery.


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## Body

## 1. Introduction

The emission of CO2 has been increasing over the years, and carbon capture and storage (CCS) has been considered to mitigate greenhouse effects [1]. Among various storage options (oil reservoirs, saline aquifers, and coal seams), storage in coal seams is promising because of advantages: firstly, there are plenty of unmineable coal resources because of limited recovery, and potential reserves of CBM in China ranks third in the world [2]; secondly, due to greater affinity of CO2 to coal than CH4, it contributes to ECBM recovery. Researchers from America, Japan, and China have performed pilot experiments for ECBM feasibility [3–5]. Specifically, when the temperatures and pore pressures are above the critical point (31.06°C, 7.38 MPa), CO2 exists in a supercritical state in coal seams with a depth under 800 m [6]. SC-CO2 has the characteristics of strong diffusion, low viscosity, and surface tension.Research has been carried out on ECBM through experiments and numerical simulations [7–10]. When CO2 is pressurized into coal seams, gas transport mainly includes diffusion, seepage, and competitive adsorption [11]. Adsorption of CO2 has been investigated from the subcritical state to the supercritical state [12, 13], and various adsorption models have been assessed, such as Langmuir, Dubinin-Astakhov (D-A), and Dubinin-Radushkevich (D-R) models [14]. The adsorption could induce swelling [15, 16] and change the pore distribution, surface area, and function groups of coal [17, 18], leading to the variation in the seepage characteristics and mechanical properties [19, 20]. Pores are classified as micropores (<2 nm) for adsorption, mesopores (2-50 nm), and macropores (>50 nm) for seepage, and changes in pore structures have been investigated to reveal the mechanism. Sampath et al. compared the effects of short-term and long-term CO2 interaction on pore structures [21]. Considered the existence of water in coal seams, Ni et al. [22] and Liu et al. [23] investigated the interaction with SC-CO2 and water, indicating that the chemical reaction also influences pore structures.The permeability is a key parameter for gas exploitation, and it is influenced by the effective stress and CO2 adsorption, occasionally along with extraction and dissolution. Although previous studies have focused on permeability variation, however, the specific influence of each factor is uncertain, especially in the supercritical state. In the present work, a series of permeability tests were performed before and after SC-CO2 adsorption under nonconfining conditions at different temperatures. The effect of CO2 adsorption on the permeability is investigated, and porosity differences between specimens are reduced by using briquettes. Results can provide a basis for further field application of ECBM.


## 2. Experimental Specimens and Apparatus

### 2.1. Specimens

The porosity of specimens drilled from the same block may be different, and this difference can influence the permeability characteristics and adsorption capacity. Therefore, the briquettes are selected as the specimens because of homogeneity and controllable porosity.Blocks are extracted from Xinqiu Mine, Fuxin, Liaoning Province. The blocks are crushed and sieved until the diameter is below 0.25 mm. 255 g pulverized coal and 5 g rosin are put together into a cylinder with a thick wall, and a briquette is shaped in the cylinder with a loading of 460 kN as shown in Figure1. The diameter and length are 50 mm and 100 mm, respectively. All specimens are dried at the temperature of 105°C for 24 hours. The average porosity is 0.31 by comparing the apparent density of specimens and the true density of powdered coal, and it can be considered that there is no difference between specimens.Figure 1
The process of making a specimen.


### 2.2. Experimental System

The experiments include two parts, permeability tests and adsorption experiments. Based on Darcy’s law, transient and steady-state methods are frequently used to determine permeability [24–26]. In the present work, the latter method is used because of the relatively high permeability of briquettes. The experimental system for permeability tests consists of the injection part (N2 cylinder), a seepage and reference cell, a pump with a regulator, and a flow meter as shown in Figure 2. After being vacuumed, confining pressures are applied by the pump firstly. N2 is pressured into the reference cell, and once the pressure is stable, N2 is injected into the seepage cell to start the test. The flow meter is used to measure the flow rate of N2, and the permeability is determined by [27]
(1)k=2μP2LQP12−P22A,where μ is the viscosity of N2, Q is the flow rate. P1 and P2 are the upstream and downstream pressures, respectively, and L and A are the length and cross-sectional area, respectively.Figure 2
Experimental system.The main parts of the experimental system for adsorption are the reference cell and adsorption cell. The adsorption amount is measured by the volumetric method, and the void volume is estimated by injecting He according to the national standard. The diameter and length of a specimen at several positions are measured with a vernier caliper to calculate the volume before and after the experiment, and volumetric expansion can be determined by(2)S=V−V0V0×100%,where S is volumetric swelling and V0 and V are the initial and final volume of the specimen, respectively.According to the measurement in Wu et al. [13], the adsorption amount can be determined by
(3)n=1mRTVRPR1ZR1−PR2ZR2−VA1PA1ZA1−VA2PA2ZA2,where n is the excessive adsorption amount per unit of a specimen. m is the weight of a specimen. R, the universal gas constant, is 8.314 J/(g·mol·K). T is the equilibrium temperature. VR and VA are the void volumes of reference and adsorption cells, and PR and PA are respective pressures of two cells. Subscripts 1 and 2 refer to the initial and final state, respectively. ZR1, ZR2, ZA1, and ZA2 are compressibility factors corresponding to PR1, PR2, PA1, and PA2, respectively, at the temperature of T.


### 2.3. Experimental Procedures

The experimental procedures cover three stages, determining the permeability, CO2 adsorption, and measuring the permeability after CO2 desorption.Stage one: a series of permeability tests are performed on a briquette placed in the seepage cell using N2 with the injection pressure of 2 MPa and confining pressure of 12 MPa at 35°CStage two: the specimen is taken out from the seepage cell and placed in the adsorption cell. Experiments of CO2 adsorption are conducted without confinement at the pressure of 8 MPa and temperature of 35°C. The experiment lasts for 24 hours according to the national standard, and the pressure reduction and deformation are recordedStage three: after desorption for 12 hours, permeability tests are repeated three times to investigate the variation and determine the effect of adsorption on the permeability.A new specimen is replaced in the adsorption cell, and the second and third stages are repeated at CO2 pressures of 9, 10, 11, 12, and 13 MPa. Subsequently, the temperature is increased to 45 or 55°C; this series of experiments are repeated.


## 2.1. Specimens

The porosity of specimens drilled from the same block may be different, and this difference can influence the permeability characteristics and adsorption capacity. Therefore, the briquettes are selected as the specimens because of homogeneity and controllable porosity.Blocks are extracted from Xinqiu Mine, Fuxin, Liaoning Province. The blocks are crushed and sieved until the diameter is below 0.25 mm. 255 g pulverized coal and 5 g rosin are put together into a cylinder with a thick wall, and a briquette is shaped in the cylinder with a loading of 460 kN as shown in Figure1. The diameter and length are 50 mm and 100 mm, respectively. All specimens are dried at the temperature of 105°C for 24 hours. The average porosity is 0.31 by comparing the apparent density of specimens and the true density of powdered coal, and it can be considered that there is no difference between specimens.Figure 1
The process of making a specimen.


## 2.2. Experimental System

The experiments include two parts, permeability tests and adsorption experiments. Based on Darcy’s law, transient and steady-state methods are frequently used to determine permeability [24–26]. In the present work, the latter method is used because of the relatively high permeability of briquettes. The experimental system for permeability tests consists of the injection part (N2 cylinder), a seepage and reference cell, a pump with a regulator, and a flow meter as shown in Figure 2. After being vacuumed, confining pressures are applied by the pump firstly. N2 is pressured into the reference cell, and once the pressure is stable, N2 is injected into the seepage cell to start the test. The flow meter is used to measure the flow rate of N2, and the permeability is determined by [27]
(1)k=2μP2LQP12−P22A,where μ is the viscosity of N2, Q is the flow rate. P1 and P2 are the upstream and downstream pressures, respectively, and L and A are the length and cross-sectional area, respectively.Figure 2
Experimental system.The main parts of the experimental system for adsorption are the reference cell and adsorption cell. The adsorption amount is measured by the volumetric method, and the void volume is estimated by injecting He according to the national standard. The diameter and length of a specimen at several positions are measured with a vernier caliper to calculate the volume before and after the experiment, and volumetric expansion can be determined by(2)S=V−V0V0×100%,where S is volumetric swelling and V0 and V are the initial and final volume of the specimen, respectively.According to the measurement in Wu et al. [13], the adsorption amount can be determined by
(3)n=1mRTVRPR1ZR1−PR2ZR2−VA1PA1ZA1−VA2PA2ZA2,where n is the excessive adsorption amount per unit of a specimen. m is the weight of a specimen. R, the universal gas constant, is 8.314 J/(g·mol·K). T is the equilibrium temperature. VR and VA are the void volumes of reference and adsorption cells, and PR and PA are respective pressures of two cells. Subscripts 1 and 2 refer to the initial and final state, respectively. ZR1, ZR2, ZA1, and ZA2 are compressibility factors corresponding to PR1, PR2, PA1, and PA2, respectively, at the temperature of T.


## 2.3. Experimental Procedures

The experimental procedures cover three stages, determining the permeability, CO2 adsorption, and measuring the permeability after CO2 desorption.Stage one: a series of permeability tests are performed on a briquette placed in the seepage cell using N2 with the injection pressure of 2 MPa and confining pressure of 12 MPa at 35°CStage two: the specimen is taken out from the seepage cell and placed in the adsorption cell. Experiments of CO2 adsorption are conducted without confinement at the pressure of 8 MPa and temperature of 35°C. The experiment lasts for 24 hours according to the national standard, and the pressure reduction and deformation are recordedStage three: after desorption for 12 hours, permeability tests are repeated three times to investigate the variation and determine the effect of adsorption on the permeability.A new specimen is replaced in the adsorption cell, and the second and third stages are repeated at CO2 pressures of 9, 10, 11, 12, and 13 MPa. Subsequently, the temperature is increased to 45 or 55°C; this series of experiments are repeated.


## 3. Experimental Results and Discussion

### 3.1. Permeability Characteristics before and after SC-CO2 Adsorption

Figure3 shows that the permeability enhances remarkably after SC-CO2 adsorption at different temperatures. After the adsorption, the permeability decreases by 0.4 mD with pressures ranging from 8 MPa to 9 MPa, and it reduces by approximately 0.7 mD at pressures increasing from 9 MPa to 13 MPa at 35°C. Nevertheless, the permeability after CO2 adsorption increases slightly initially and subsequently decreases moderately with the increase of CO2 pressures at 45 and 55°C, and peaks are observed obviously at the pressures of 9 MPa at 45°C. Compared with the initial permeability, the permeability enhancement ratio, η, can be determined by
(4)η=k−k0k0×100%,where k0 and k are permeability values before and after CO2 adsorption, respectively.Figure 3
Permeability enhancement at different temperatures.
(a)
35°C(b)
45°C(c)
55°CTo reveal the variation ofη with temperatures, the ratio is replotted as shown in Figure 4. The ratio decreases by approximately 13% at the pressure of 8 MPa, while it increases by 10% before decreasing at 9 MPa. When pressures are in the range of 10-13 MPa, the proportion increases slightly with temperatures ranging from 35 to 45°C, and it continues rising moderately with the increase of temperatures to 55°C.Figure 4
Permeability enhancement ratio with the increase of temperatures.


### 3.2. Adsorption and Deformation

Figure5 demonstrates that CO2 adsorption induces various swelling at different pressures and temperatures. The volumetric swelling reduces by 4% at 35°C, while the expansion increases slightly before 9 MPa and subsequently decreases by 3.5% and 1.2% at 45 and 55°C, respectively. When pressures exceed 10 MPa, the expansion at 55°C is greater than that at other temperatures.Figure 5
Volumetric swelling at different pressures and temperatures.Although the Langmuir model is generally applied to estimate the adsorption amount and deformation, however, it is poorly applied to adsorption at pressures exceeding 6 MPa mainly due to the assumption of monolayer adsorption. Alternatives such as the modified D-R model have been found more suitable to fit with the adsorption amount and swelling [28, 29]. In this model, gas densities replace the pressures and adsorbed densities replace the saturated vapor pressures, which avoids the limitation of saturated vapor pressure in the supercritical state, as shown in
(5)S=Smaxexp−Dln2ρaρ+aρ,where Smax is the maximum swelling. For adsorption amount, D is related to the adsorption heat and affinity of the gas to the sorbent, while for swelling it is possibly regarded as an empirical parameter. ρ, CO2 density, varies with temperatures and pressures and is obtained from the website of the US National Institute of Standards and Technology (NIST), as shown in Figure 6. ρa, the density of the adsorbed phase, is considered as 1000 kg/m3 [28, 29].Figure 6
CO2 density at different temperatures and pressures.The deformations of specimens at three temperatures are fitted with the modified D-R model with a great determination as shown in Figure7 and Table 1. Smax decreases by 13% with temperatures ranging from 35 to 55°C, while it does not vary significantly with the temperatures in the previous study [29]. This difference is mainly because the briquette structure is loose, while the structure of raw coal specimens is dense. The adsorbed density of CO2 is approximately close to liquid CO2 density, revealing that the adsorbed CO2 requires less volume than gaseous CO2. The a term is related to CO2 solubility, and this term can be used to describe the compression at great pressures.Figure 7
Expansion fits with CO2 densities.Table 1
Fitting parameters for the modified D-R model.
Temperature (°C)SmaxDa350.320.28−2.7×10−4450.230.11−1.6×10−4550.190.07−1.1×10−4


### 3.3. Adsorption and Swelling

Figure8 demonstrates that the swelling of specimens decreases linearly by 1.5% with the increase of adsorption amount by 1 mmol/g, which is shown in the previous study [13]. Studies reported an increase in deformation with the augment of absolute adsorption, along with a stable trend at CO2 pressures approaching 10 MPa [15, 29]. The process of CO2 adsorption and specimen deformation is from the disequilibrium state to the dynamic equilibrium state. With CO2 injection, CO2 diffuses due to pressure differences and it is absorbed by the matrix. CO2 acts as the plasticizer and enables coal structure rearrangement, reducing the softening temperatures [30]. CO2 adsorption can reduce the surface energy of the coal and weak mechanical properties. These are the main reasons that matrix swells significantly after adsorption. High-pressure CO2 can constrain matrix swelling and the expansion shows a downward trend when CO2 pressures exceed 10 MPa.Figure 8
Volumetric swelling with excessive adsorption.


### 3.4. Analysis of the Permeability Changes Induced by CO2

The permeability ratio shows a linear augment with the volumetric swelling as shown in Figure9. It is noted that the proportion at 55°C is slightly lower than that at other temperatures. The adsorption-induced swelling indicates greater porosity and wider seepage channels, and therefore, permeability is enhanced. This reveals that the permeability enhancement under nonconfinement is influenced mostly by the adsorption.Figure 9
Permeability enhancement ratio with volumetric swelling.For CO2 geological storage in deep coal seams, where strata pressures restrict the swelling, the permeability variation after CO2 interaction is a coupled result of CO2 adsorption and effective stresses, along with extraction or dissolution. For CO2 adsorption in the confined stress, due to gas injection, both the reduction in effective stresses and CO2 adsorption induce matrix expansion (equations (6) and (7)). Under the great confinement, the coal matrix expands inward and cleats narrow, leading to permeability reduction. Ranathunga et al. observed shrinkage in macropores with the help of scanning electron microscopy (SEM) [31]. All microcleats, the main channels of gas seepage, can be observed closely by micro-CT scanning after SC-CO2 injection, and permeability decreases drastically by 2 orders of magnitude [32]. After CO2 adsorption under a constraint pressure, the permeability reduction ratio augments linearly with the increase of swelling [33].
(6)ε=εe+S,(7)εe=‐σ−P3K,where ε is the total deformation induced by effective stresses and adsorption. εe is the volumetric deformation caused by effective stresses, namely, σ−P, and K is the bulk modulus. In equation (7), the minus indicates compression.As a solvent, SC-CO2 can extract organic minerals and alter the pore surface, tarnishing the surface. Li et al. observed permeability augment after CO2 cycling adsorption and desorption under a constraint pressure, along with the expansion in macro- and mesopores but few changes in micropores [34]. Because of noticeable fractures on the surface, the extraction is attributed to the remarkable permeability improvement. The solubility varies with CO2 density, and therefore, it is difficult to quantify the effects of extraction.Another influencing factor is the chemical reaction. Water exists in coal seams, and the interaction of CO2 and water can dissolve the carbonate minerals. CO2 could dissolve in water forming an acid solution, in which calcite is dissolved. The interaction of water and SC-CO2 causes an increment in pores, and the permeability is improved [23]. Nevertheless, some silicate minerals could form precipitation and block pore connections, reducing the permeability [22].


### 3.5. Discussion for CO2-ECBM

CO2-ECBM is injecting CO2 through wells into deep coal seams at a certain injection pressure. The permeability is the key factor during gas production. Although the permeability becomes greater at high pressures without considering the Klinkenberg effect [7], however, increasing CO2 pressures cannot be effective for improving exploitation efficiency according to the previous analysis. Among the four factors, the effect of extraction and solution on permeability is limited and estimated difficultly. Swelling decreases gradually with the increase of CO2 pressure. Besides, injecting high-pressure CO2 is liable to induce disasters and weaken the mechanical properties. Therefore, the permeability could be not enhanced significantly by only increasing CO2 pressures.According to the national standard, numerous adsorption experiments last for 24 hours, after which the surface area decreases, while the surface area augments remarkably after 7 days and 14 days [21]. Kutchko et al. summarized no significant variations in macropores after 104 days considering the offset [35]. Due to limited observation, SEM images cannot reflect total surface changes, while those changes can be estimated in other methods such as CT and nuclear magnetic resonance (NMR) [36, 37]. The interaction time should be taken into consideration, and further studies are required to investigate the long-term changes and mechanical behavior for coal of different ranks.


## 3.1. Permeability Characteristics before and after SC-CO2 Adsorption

Figure3 shows that the permeability enhances remarkably after SC-CO2 adsorption at different temperatures. After the adsorption, the permeability decreases by 0.4 mD with pressures ranging from 8 MPa to 9 MPa, and it reduces by approximately 0.7 mD at pressures increasing from 9 MPa to 13 MPa at 35°C. Nevertheless, the permeability after CO2 adsorption increases slightly initially and subsequently decreases moderately with the increase of CO2 pressures at 45 and 55°C, and peaks are observed obviously at the pressures of 9 MPa at 45°C. Compared with the initial permeability, the permeability enhancement ratio, η, can be determined by
(4)η=k−k0k0×100%,where k0 and k are permeability values before and after CO2 adsorption, respectively.Figure 3
Permeability enhancement at different temperatures.
(a)
35°C(b)
45°C(c)
55°CTo reveal the variation ofη with temperatures, the ratio is replotted as shown in Figure 4. The ratio decreases by approximately 13% at the pressure of 8 MPa, while it increases by 10% before decreasing at 9 MPa. When pressures are in the range of 10-13 MPa, the proportion increases slightly with temperatures ranging from 35 to 45°C, and it continues rising moderately with the increase of temperatures to 55°C.Figure 4
Permeability enhancement ratio with the increase of temperatures.


## 3.2. Adsorption and Deformation

Figure5 demonstrates that CO2 adsorption induces various swelling at different pressures and temperatures. The volumetric swelling reduces by 4% at 35°C, while the expansion increases slightly before 9 MPa and subsequently decreases by 3.5% and 1.2% at 45 and 55°C, respectively. When pressures exceed 10 MPa, the expansion at 55°C is greater than that at other temperatures.Figure 5
Volumetric swelling at different pressures and temperatures.Although the Langmuir model is generally applied to estimate the adsorption amount and deformation, however, it is poorly applied to adsorption at pressures exceeding 6 MPa mainly due to the assumption of monolayer adsorption. Alternatives such as the modified D-R model have been found more suitable to fit with the adsorption amount and swelling [28, 29]. In this model, gas densities replace the pressures and adsorbed densities replace the saturated vapor pressures, which avoids the limitation of saturated vapor pressure in the supercritical state, as shown in
(5)S=Smaxexp−Dln2ρaρ+aρ,where Smax is the maximum swelling. For adsorption amount, D is related to the adsorption heat and affinity of the gas to the sorbent, while for swelling it is possibly regarded as an empirical parameter. ρ, CO2 density, varies with temperatures and pressures and is obtained from the website of the US National Institute of Standards and Technology (NIST), as shown in Figure 6. ρa, the density of the adsorbed phase, is considered as 1000 kg/m3 [28, 29].Figure 6
CO2 density at different temperatures and pressures.The deformations of specimens at three temperatures are fitted with the modified D-R model with a great determination as shown in Figure7 and Table 1. Smax decreases by 13% with temperatures ranging from 35 to 55°C, while it does not vary significantly with the temperatures in the previous study [29]. This difference is mainly because the briquette structure is loose, while the structure of raw coal specimens is dense. The adsorbed density of CO2 is approximately close to liquid CO2 density, revealing that the adsorbed CO2 requires less volume than gaseous CO2. The a term is related to CO2 solubility, and this term can be used to describe the compression at great pressures.Figure 7
Expansion fits with CO2 densities.Table 1
Fitting parameters for the modified D-R model.
Temperature (°C)SmaxDa350.320.28−2.7×10−4450.230.11−1.6×10−4550.190.07−1.1×10−4


## 3.3. Adsorption and Swelling

Figure8 demonstrates that the swelling of specimens decreases linearly by 1.5% with the increase of adsorption amount by 1 mmol/g, which is shown in the previous study [13]. Studies reported an increase in deformation with the augment of absolute adsorption, along with a stable trend at CO2 pressures approaching 10 MPa [15, 29]. The process of CO2 adsorption and specimen deformation is from the disequilibrium state to the dynamic equilibrium state. With CO2 injection, CO2 diffuses due to pressure differences and it is absorbed by the matrix. CO2 acts as the plasticizer and enables coal structure rearrangement, reducing the softening temperatures [30]. CO2 adsorption can reduce the surface energy of the coal and weak mechanical properties. These are the main reasons that matrix swells significantly after adsorption. High-pressure CO2 can constrain matrix swelling and the expansion shows a downward trend when CO2 pressures exceed 10 MPa.Figure 8
Volumetric swelling with excessive adsorption.


## 3.4. Analysis of the Permeability Changes Induced by CO2

The permeability ratio shows a linear augment with the volumetric swelling as shown in Figure9. It is noted that the proportion at 55°C is slightly lower than that at other temperatures. The adsorption-induced swelling indicates greater porosity and wider seepage channels, and therefore, permeability is enhanced. This reveals that the permeability enhancement under nonconfinement is influenced mostly by the adsorption.Figure 9
Permeability enhancement ratio with volumetric swelling.For CO2 geological storage in deep coal seams, where strata pressures restrict the swelling, the permeability variation after CO2 interaction is a coupled result of CO2 adsorption and effective stresses, along with extraction or dissolution. For CO2 adsorption in the confined stress, due to gas injection, both the reduction in effective stresses and CO2 adsorption induce matrix expansion (equations (6) and (7)). Under the great confinement, the coal matrix expands inward and cleats narrow, leading to permeability reduction. Ranathunga et al. observed shrinkage in macropores with the help of scanning electron microscopy (SEM) [31]. All microcleats, the main channels of gas seepage, can be observed closely by micro-CT scanning after SC-CO2 injection, and permeability decreases drastically by 2 orders of magnitude [32]. After CO2 adsorption under a constraint pressure, the permeability reduction ratio augments linearly with the increase of swelling [33].
(6)ε=εe+S,(7)εe=‐σ−P3K,where ε is the total deformation induced by effective stresses and adsorption. εe is the volumetric deformation caused by effective stresses, namely, σ−P, and K is the bulk modulus. In equation (7), the minus indicates compression.As a solvent, SC-CO2 can extract organic minerals and alter the pore surface, tarnishing the surface. Li et al. observed permeability augment after CO2 cycling adsorption and desorption under a constraint pressure, along with the expansion in macro- and mesopores but few changes in micropores [34]. Because of noticeable fractures on the surface, the extraction is attributed to the remarkable permeability improvement. The solubility varies with CO2 density, and therefore, it is difficult to quantify the effects of extraction.Another influencing factor is the chemical reaction. Water exists in coal seams, and the interaction of CO2 and water can dissolve the carbonate minerals. CO2 could dissolve in water forming an acid solution, in which calcite is dissolved. The interaction of water and SC-CO2 causes an increment in pores, and the permeability is improved [23]. Nevertheless, some silicate minerals could form precipitation and block pore connections, reducing the permeability [22].


## 3.5. Discussion for CO2-ECBM

CO2-ECBM is injecting CO2 through wells into deep coal seams at a certain injection pressure. The permeability is the key factor during gas production. Although the permeability becomes greater at high pressures without considering the Klinkenberg effect [7], however, increasing CO2 pressures cannot be effective for improving exploitation efficiency according to the previous analysis. Among the four factors, the effect of extraction and solution on permeability is limited and estimated difficultly. Swelling decreases gradually with the increase of CO2 pressure. Besides, injecting high-pressure CO2 is liable to induce disasters and weaken the mechanical properties. Therefore, the permeability could be not enhanced significantly by only increasing CO2 pressures.According to the national standard, numerous adsorption experiments last for 24 hours, after which the surface area decreases, while the surface area augments remarkably after 7 days and 14 days [21]. Kutchko et al. summarized no significant variations in macropores after 104 days considering the offset [35]. Due to limited observation, SEM images cannot reflect total surface changes, while those changes can be estimated in other methods such as CT and nuclear magnetic resonance (NMR) [36, 37]. The interaction time should be taken into consideration, and further studies are required to investigate the long-term changes and mechanical behavior for coal of different ranks.


## 4. Conclusions

Permeability characteristics were investigated on briquettes before and after SC-CO2 adsorption under nonconfinement. The main results are as follows:
(1)
Permeability enhances significantly after CO2 adsorption in briquettes. The permeability enhancement reduces continuously with the increase of CO2 pressure at 35°C, while it augments slightly before decreasing moderately at 45 and 55°C(2)
CO2 adsorption could cause volumetric swelling, and expansion is fitted well with the modified D-R model at the considering temperatures(3)
The permeability enhancement ratio is a linear function with swelling. The permeability enhancement under nonconfinement is influenced mainly by SC-CO2 adsorption(4)
For CO2 storage in coal seams, the permeability is influenced by four factors, effective stresses, dsorption, extraction, and solution, and the limited effects of extraction and solution are difficult to quantify. Further research is required to study long-term variations in permeability and mechanical properties



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*Source: 8836349-2020-09-09.xml*