Synergistic Mechanism of Ultrasonic-Chemical Effects on the CH4 Adsorption-Desorption and Physicochemical Properties of Jincheng Anthracite.

Ultrasonic is a new method to enhance coalbed methane recovery. A deeper comprehension of the synergistic mechanisms of combined ultrasonic-chemical modification on the CH4 adsorption-desorption capability and physicochemical properties of coal is necessary for potential field implementation, as the modification of coal reservoirs frequently necessitates the addition of chemical reagents. This paper evaluated the CH4 adsorption-desorption properties of anthracite modified by sodium dodecyl sulfate (SDS) solution, ultrasonic modification, and combined ultrasonic-SDS modification. Fourier transform infrared spectroscopy, low-temperature nitrogen adsorption, and micro-CT were applied to elucidate the synergistic mechanism of the combined modification. The research results show that the SDS solution reduces the saturated adsorption capacity of anthracite and increases its final desorption rate by dissolving clay minerals and the physical adsorption masking effect of SDS micelles on the coal surface. Some surface groups with low bond energy are broken or evaporated under mechanical vibration and thermal effects generated by ultrasonic. The original fractures are expanded and connected, which changes the adsorption-desorption properties of anthracite. The synergistic effect of the combined modification of ultrasonic-SDS can promote the penetration range and chemical reaction efficiency of the SDS solution, which expands the effective range of ultrasonic. After combined modification, the amount of aromatics, oxygen-containing functional groups, and aliphatic hydrocarbons on the surface of coal is reduced. The connected porosity of coal samples accounts for 91.5% of the total porosity. As a result, the saturated adsorption capacity of anthracite reduces by 26.7%, and the final desorption rate increases by 28.0%. The effect of the combined ultrasonic-chemical modification is better than that of a single modification.

Characterization of Pore Structures with Mercury Intrusion Porosimetry after Electrochemical Modification: A Case Study of Jincheng Anthracite.

Quantitative characterization of the change in the cleat and pore structures and fractal dimensions in anthracite after electrochemical modification is crucial for better understanding of the modification effect. Thus, lump anthracite samples were electrochemically modified in our manufactured device with 0, 0.5, 1, and 2 V/cm potential gradients. The changes in heterogeneity and porosity after modification were tested and analyzed by mercury intrusion porosimetry (MIP) and fractal theory. The results indicated that the total volume of the pores increased after electrochemical treatment and continuously increased with increasing potential gradient during the treatment process. After modification, the number of pores or fractures with a pore size between 6 and 20 µm in coal after modification increases significantly. According to the intrusion pressure, three stages were defined as lower (P M < 0.1 MPa), intermediate (0.1 ≤ P M < 10 MPa), and higher regions (P M ≥ 10 MPa), which are characterized by fractal dimensions D 1, D 2, and compression stages, respectively. After modification, the fractal dimension D 1 showed an increasing trend, while the fractal dimension D 2 showed a decreasing trend, indicating that the fracture system became more complicated and that the pore system became more regular after electrochemical treatment. The evolution mechanism of heterogeneity and porosity and their fractal dimensions were explained by the dissolution of minerals, change in pH values, and dynamics of temperatures during the process of modification. The results obtained in this work are of important guiding significance for coalbed methane (CBM) extraction via in situ modification by electrochemical treatment.

Response of Molecular Structures and Methane Adsorption Behaviors in Coals Subjected to Cyclical Microwave Exposure.

To better understand the methane adsorption behavior after microwave exposure, the importance of quantitatively characterizing the effect of cyclical microwave exposure on the molecular structures of coals cannot be overemphasized, with implications for enhancing coalbed methane (CBM) extraction. Thus, cyclical microwave exposure experiments of three different metamorphic coals were conducted, and the methane adsorption capacity before and after each microwave exposure (10 in total) for 120 s was evaluated. Fourier transform infrared spectroscopy analysis and peak fitting technology were applied to quantitatively characterize the changes in the structural parameters of coal molecules. The results showed that after modification, the structural parameters like aromatic carbon fraction (f a-F), aromaticity (I 1 and I 2), degree of condensation (DOC 1 and DOC 2), and the maturity of organic matter ("C") gradually increased with increasing exposure times, while the length of the aliphatic chain or its branching degree (CH 2/CH 3) and the hydrocarbon generating capacity ("A") showed a decreasing trend. The Langmuir volume (V L) of three different rank coal samples decreased from 29.2, 32.8, and 40.4 mL/g to 25.7, 29.3, and 35.7 mL/g, respectively; the Langmuir pressure (P L) increased from 0.588, 0.844, and 0.942 MPa to 0.626, 1.007, and 1.139 MPa, respectively. The modification mechanism was investigated by analyzing the relationship between the methane adsorption behaviors and molecular structures in coals. The release of alkane side chains and the oxidation of oxygen-containing functional groups caused by microwave exposure decreased the number of methane adsorption sites. As a result, the methane adsorption capability decreased. In addition, the decomposition of minerals affects methane adsorption behaviors in coals. This work provides a basis for microwave modification of coal as well as in situ enhancement of CBM extraction using microwave exposure.

Pore Fractal Characteristics of Suancigou Long-Flame Coal after Electrochemical Treatment: An Experimental Study through the Implementation of N2 Adsorption and Mercury Intrusion Prosimetry Techniques.

The application of electrochemical treatment in coal seams for enhancing coalbed methane (CBM) recovery can also decrease the risks of outburst disasters. The long-flame coal samples were electrochemically modified with 0, 1, 2, and 4 V/cm electric potential gradients, and the pore structures were measured and analyzed by combined low-temperature nitrogen gas adsorption, mercury intrusion prosimetry, and fractal theory. The experimental test results indicated that the pore volumes of macropores (>50 nm) and mesopores (2-50 nm) increased after electrochemical modification and further increased with the increase in electric potential gradient. The fractal dimensions of pores showed a decreasing trend except for the slight fluctuation of the mesopores with a size of 2-4.5 nm after modification, which indicated that the overall roughness and irregularity index of pores decreased. The evolution mechanisms of pore size distributions and their fractal dimensions were explained by the dissolution of minerals and the falling off of alkane side chains in the coal surface, which would expand and connect the pores during the electrochemical modification process. The results obtained from this work were crucial for CBM exploration via an electrochemical method.

Electrochemical Modification on CH4 and H2O Wettability of Qinshui Anthracite Coal: A Combined Experimental and Molecular Dynamics Simulation Study.

The wettability of gas and liquid on the coal surface is one of the fundamental factors that affect the depressurization process during the coalbed methane (CBM) extraction. The wettability of coal surface changed after electrochemical modification, leading to the change in methane adsorption/desorption and water movement in coal reservoirs. Thus, the CH4 adsorption amount, desorption ratio, and coal-water contact angle of raw and modified anthracite samples were measured and simulated. The mechanism of electrochemical modification was analyzed by functional groups, surface free energy, pore characteristics, interaction energies, and coal swelling. The experimental results showed that the saturated adsorption amount of methane decreased from 41.49 to 34.72 mL/g, and the simulation results showed that the saturated adsorption amount of methane decreased from 2.01 to 1.83 mmol/g. The coal-water contact angle also decreased from 81.9 to 68.6°. Electrochemical modification mainly affects the wettability of CH4 and H2O by changing the functional groups and pore structures of anthracite, and the influence on functional groups of coal surface is greater. This work provided a basis for enhancing CBM extraction by electrochemical modification.

Effect of Cyclical Microwave Modification on the Apparent Permeability of Anthracite: A Case Study of Methane Extraction in Sihe Mine, China.

The application of cyclical microwave modification for accelerating the extraction of coalbed methane (CBM) from anthracite is limited. In this study, the apparent permeability of anthracite samples before and after each microwave treatment (three in total) for 120 s was measured by a self-built permeability-testing platform. Microcomputed tomography (micro-CT) technology and image-processing technology were employed to analyze the 3D micron-scale pore structures, especially the quantitative characterization of connected pores and throats. After modification, the average apparent permeability increased from 0.6 to 5.8 × 10-3 µm2. The generation, expansion, and connection of micron-scale pores and fractures became more obvious with each treatment. The total porosity increased from 3.5 to 6.2%, the connected porosity increased from 0.9 to 4.8%, and the porosity of isolated pores decreased from 2.5 to 1.4% after three cycles. The number, volume, and surface area of the connected pores as well as the number, radius, and surface area of the throats were significantly increased. In addition, the release of alkyl side chains from the anthracite surface reduced the capacity of the anthracite to adsorb CH4 and the decomposition of minerals promoted the development and connectivity of pores. As a result, the gas seepage channels have been greatly improved. This work provides a basis for micron-scale pore characterization after cyclical microwave modification and contributes to CBM extraction.

Effects of Electrolyte pH on the Electro-Osmotic Characteristics in Anthracite.

Accelerating the drainage of water in coal reservoirs can significantly improve the extraction efficiency of coalbed methane (CBM). The movement of water with different pH values in anthracite was tested and analyzed. The results showed that the electro-osmotic flow velocity increased first and then slightly decreased with the increase of time up to 120 h. The electro-osmotic flow was markedly strengthened under a strong acid (pH 2) or strong alkaline (pH 13) environment, and the direction of electro-osmosis was reversed at a pH of 3-4. The changes in zeta potential, surface groups, and minerals in anthracite were tested to analyze the mechanism of electro-osmotic characteristics. The results obtained from this work will provide a basis for the process of drainage and depressurization during the CBM extraction.

Effect of Electric Potential Gradient on Methane Adsorption and Desorption Behaviors in Lean Coal by Electrochemical Modification: Implications for Coalbed Methane Development of Dongqu Mining, China.

The application of electrochemical modification for accelerating methane extraction in lean coal seams is limited due to the lack of experimental and theoretical research studies. Therefore, electrochemical modification with different electric potential gradient values was selected to modify lean coals in this study; meanwhile, the amount of methane adsorption and the methane desorption ratio were tested and analyzed. The results showed that the maximum amount of methane adsorption in coal samples decreased after electrochemical modification and the decrease in methane adsorption increased with an increase in electric potential gradient. The methane desorption ratio increased from 83.20% up to 87.84 and 86.90% at the anode and cathode zone, respectively, after electrochemical modification using a 4 V/cm electric potential gradient. A higher electric potential gradient performs better in the electrochemical modification. The mechanism of electrochemical modification using different electric potential gradients was revealed based on the measurements of Fourier transform infrared spectroscopy and liquid nitrogen adsorption. It is due to an increase in acid groups in coal molecular structure and the change of the specific surface area of coal after modification. The results obtained from this work contribute to the methane extraction via the electrochemical method in lean coal seams.

Effect of Pressure and Temperature on CO2/CH4 Competitive Adsorption on Kaolinite by Monte Carlo Simulations.

The adsorption of CO2 and CO2/CH4 mixtures on kaolinite was calculated by grand canonical Monte Carlo (GCMC) simulations with different temperatures (283.15, 293.15, and 313.15 K) up to 40 MPa. The simulation results show that the adsorption amount of CO2 followed the Langmuir model and decreased with an increasing temperature. The excess adsorption of CO2 increased with an increasing pressure until the pressure reached 3 MPa and then decreased at different temperatures. The S C O 2 / C H 4 decreased logarithmically with increasing pressure, and the S C O 2 / C H 4 was lower with a higher temperature at the same pressure. The interaction energy between CO2 and kaolinite was much higher than that between CH4 and kaolinite at the same pressure. The interaction energy between the adsorbent and adsorbate was dominant, and that between CO2 and CO2 and between CH4 and CH4 accounted for less than 20% of the total interaction energy. The isothermal adsorption heat of CO2 was higher than that of CH4, indicating that the affinity of kaolinite to CO2 was higher than that of CH4. The strong adsorption sites of carbon dioxide on kaolinite were hydrogen, oxygen, and silicon atoms, respectively. CO2 was not only physically adsorbed on kaolinite, but also exhibited chemical adsorption. In gas-bearing reservoirs, a CO2 injection to displace CH4 and enhance CO2 sequestration and enhanced gas recovery (CS-EGR) should be implemented at a low temperature.

The Effect of Mg, Fe(II), and Al Doping on CH4: Adsorption and Diffusion on the Surface of Na-Kaolinite (001) by Molecular Simulations.

Because kaolinite includes a large range of defect elements, the effects of Mg, Fe(II), and Al doping on the CH4 adsorption and diffusion on the surface of Na-kaolinite (001) were investigated by molecular simulations. The simulation results illustrate that ion doping can significantly reduce the amount of CH4 adsorbed by kaolinite, but the type of doped ions has little effect on the amount of adsorption. The specific surface area of kaolinite and the interaction energy between CH4 and the kaolinite's surface are two key factors that can determine CH4 adsorption capacity. The first peak value of the radial distribution functions (RDFs) between CH4 and the pure kaolinite is larger than that between Mg-, Fe(II)-, and Al-doped kaolinite, which indicates that ion doping can reduce the strength of the interactions between CH4 and the kaolinite's surface. Besides hydrogen and oxygen atoms, interlayer sodium ions are also strong adsorption sites for CH4 and lead to a weakened interaction between CH4 and the kaolinite's surface, as well as a decrease in CH4 adsorption. Contrary to the adsorption results, ion doping facilitates the diffusion of CH4, which is beneficial for actual shale gas extraction.

Experimental and mechanistic research on methane adsorption in anthracite modified by electrochemical treatment using selected electrode materials.

The strong adsorption capacity of methane in anthracite can seriously affect the methane extraction. Electrochemical treatment is an effective way to weaken the capacity of methane adsorption in coal. Iron, copper, aluminum and graphite as four kinds of electrode materials were selected to modify anthracite by electrochemical treatment. The adsorption of methane in anthracite, before and after modification, was tested under different adsorption pressure. Based on the changes of pore characteristics and chemical groups of anthracite, the modification process of different electrode materials was analyzed. The results showed that after electrochemical modification, the adsorption of methane decreased, when the graphite electrode was used, the methane adsorption decreases the most, followed by copper and iron electrodes, and the aluminum electrode decreased the least. After electrochemical modification using aluminum, iron, copper and graphite electrodes, the Langmuir constant a reduced by 5.22%, 8.48%, 9.24% and 11.33%, respectively, and the degree of reduction is graphite > copper > iron > aluminum. After electrochemical modification using the graphite electrode, the Langmuir constant b was reduced by 23.52%. On the contrary, after electrochemical modification using the mental electrodes, the Langmuir constant b was increased by about 5%. The surface free energy of anthracite decreased with the adsorption of CH4, the higher the pressure, the more the free energy decreased, and the reduction of surface energy decreased after electrochemical modification. The difference of the electrode reactions was the main reason for the electrochemical results, the Mn+ ions generated in the anode changed the properties of the clay mineral in the coal, and the H+ ions corroded the calcite minerals in the coal. The results obtained from this work indicate that the selection of electrode materials is crucial for the electrochemical modification, and graphite electrode is optimum for anthracite when accelerating methane extraction by electrochemical method.

Measurement and modeling of the adsorption isotherms of CH4 and C2H6 on shale samples.

CH4 and C2H6 are two common components in shale gas. Adsorption isotherms of CH4, C2H6, and their binary mixtures on shale samples are significant for understanding the fundamental mechanisms of shale gas storage and the recovery of shale resources from shale reservoirs. In this study, the thermogravimetric method is applied to obtain the adsorption isotherms of CH4, C2H6 and their binary mixtures on two typical shale core samples. A simplified local density theory/Peng-Robinson equation of state (SLD-PR EOS) model is then applied to calculate the adsorption of CH4 and C2H6 on shale, and the efficiency of the SLD-PR EOS model is thus evaluated. The results show that C2H6 exhibits a higher adsorption capacity than CH4 on shale samples, indicating the greater affinity of C2H6 to organic shale. As the molar fraction of C2H6 increases in the CH4/C2H6 mixtures, the adsorption capacity of the gas mixtures increases, indicating the preferential adsorption of C2H6 on shale. Based on the predicted results from the SLD-PR EOS model, a reasonable agreement has been achieved with the measured adsorption isotherms of CH4 and C2H6, validating the reliability of the SLD-PR EOS model for predicting adsorption isotherms of CH4 and C2H6 on shale samples. In addition, the SLD-PR EOS model is more accurate in predicting the adsorption of CH4 on shale than that of C2H6. This study is expected to inspire a new strategy for predicting the adsorption of hydrocarbons on shale and to provide a basic understanding of competitive adsorption of gas mixtures in shale reservoirs.