An accurate understanding of molecular structure evolution during pyrolysis is essential for the clean utilization of coal. In this study, middle-rank coal was taken as the research subject, and vitrinite and inertinite samples were stripped from coal using a hand picking and sink–float separation process. In situ Fourier transform infrared (FTIR) spectroscopy and in situ X-ray diffraction (XRD) were performed to compare the macromolecular structure changes between vitrinite and inertinite during pyrolysis. The results show that the aromaticity (I), the polycondensation degree of aromatic rings (DOC), the average lateral sizes (L_a) of basic structure unit (BSU), and the stacking heights (L_c) of BSU in both vitrinite and inertinite during pyrolysis increase continuously with increasing temperature. The values of these parameters for inertinite are higher than those of vitrinite, suggesting that the aromatization degree of inertinite has always been higher than that of vitrinite. In situ FTIR spectroscopy shows that the macromolecular structure evolution of vitrinite and inertinite could be divided into three stages based on temperature: 30–200 °C, 200–300 °C, and 300–500 °C. The content of C–O–C, aromatic C=O, O–H groups, and aromatic ring C=C gradually decreases, while that of the CH₂ in aliphatic hydrocarbons increases between 30 °C and 200 °C. The 200–300 °C stage is mainly filled by the synergistic effects of aliphatic and aromatic groups. The content of aliphatic groups, C–O–C groups, aromatic C=O, and aromatic ring C=C of both vitrinite and inertinite decreases greatly. The 300–500 °C stage is dominated by the aromatization and condensation of macromolecules. The substituents of the aromatic system gradually detach, leading to an increase in I and DOC. From 30 °C to 1000 °C, in situ XRD results reveal a difference in macromolecular structural evolution between vitrinite and inertinite. The arrangement of aromatic layers in vitrinite tends to be ordered during pyrolysis, whereas there are no significant changes in the inertinite. However, the aromatic layers of inertinite are always more compact than that of vitrinite. In addition, the aliphatic side chains of inertinite are more stable than that of vitrinite during the pyrolysis process.

The effect of SiO₂ on coal graphitization was investigated by adding SiO₂ as an additive to vitrinite in coal from the Gemudi mining area in Guizhou province (SW China) via a high-temperature heating treatment. The graphitization products of the samples were analyzed by X-ray diffraction (XRD), Raman spectroscopy, and high-resolution transmission electron microscopy (HRTEM), and the influence of the SiO₂ additive on the process of coal graphitization was investigated. The results showed that, with the temperature increases, the graphitization degree of all samples was promoted, and the orderliness of the microcrystalline structure in the vitrinite increased. Compared with the samples without additives, the graphitization degree, graphite lamellae ductility, and stacking degree of the samples with SiO₂ additives were higher, and the carbon layer spacing reached 0.3379 nm at 3000 °C, entering the graphite stage. The Raman spectra showed that the peak intensities of the defect structures (D1 and D2) in the samples with SiO₂ were lower than those of the samples without additives, exhibiting fewer in-plane and interlayer defects in the samples with SiO₂. The microstructures of the experimental samples were observed by HRTEM; at the same temperature, the carbon layer stacking degree of the samples with the SiO₂ additives was higher than that of the samples without SiO₂, and large graphite lamellae with smoother and clearer edges were observed.

The Erdaoling Mining area, located in Inner Mongolia, NW China, is recognized for its considerable potential in coalbed methane (CBM) exploration and development. However, the complex structures in this region have significant influences on coal reservoir characteristics, particularly pore structure features. This study focuses on the No. 2 coal seam of the Middle Jurassic Yan’an Formation. Three structural patterns were classified based on the existing structural characteristics of the study area. Coal samples of No. 2 coal seam were collected from different structural positions, and were subjected to low-temperature CO₂ adsorption (LTCO₂A), low-temperature N₂ adsorption/desorption (LTN₂A), low-field nuclear magnetic resonance (LF-NMR), and scanning electron microscopy (SEM) experiments, so that the structural controlling effects on pore structure would be revealed. Quantitative analysis results indicate that in terms of asymmetric syncline, from the limb to the core, the total porosity and movable fluid porosity of the coal decreased by 1.47% and 0.31%, respectively, reaching their lowest values at the core. Meanwhile, the dominant pore type shifted from primarily one-end closed pores to “ink-bottle” pores, indicating increased pore complexity. In the fold-thrust structure, the micropore specific surface area, micropore volume, mesopore specific surface area, mesopore volume, and total porosity show clear correlations with variations in coal seam structure. These parameters all reach their maximum values in the fault-cut zone at the center of the syncline, measuring 268.26 m²/g, 0.082 cm³/g, 0.601 m²/g, 1.262 cm³/g, and 4.2%, respectively. Simple pore types, like gas pores and vesicular pores, were identified in the syncline limbs, while open pores, “ink-bottle” pores, and complex multiporous types were mainly developed at fault locations, indicating that faults significantly increase the complexity of coal reservoir pore types. For the broad and gentle syncline and small-scale reverse fault combination, porosity exhibits a decreasing trend from the syncline limbs toward the core. Specifically, the mesopore specific surface area and movable fluid porosity increased by 52.24% and 43.69%, respectively, though no significant effect on micropores was observed. The syncline core in this structural setting developed normal gas pore clusters and tissue pores, with no occurrence of highly complex or heterogeneous pore types, indicating that neither the broad gentle syncline nor the small-scale faulting significantly altered the pore morphology. Comparatively, the broad and gentle syncline and small-scale reverse fault combination was determined to exert the strongest modification on pore structures of coal reservoir, followed by the asymmetric syncline, while the broad syncline alone demonstrated minimal influence.