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.