The structural parameters of five bituminous coals were analyzed by using X-ray diffraction and attenuated total reflection–Fourier transform infrared spectroscopy. The combustion behavior of coal was investigated by using a thermogravimetric analyzer under air conditions. Furthermore, the relationships between combustion parameters and the coal structure were established. The results show that bituminous coals contain crystalline and amorphous carbon. The aromaticity, interlayer spacing, average stacking height, aliphatic chain length, and the hydrocarbon-generating potential varied with the different bituminous coals. The coal samples exhibited similar weight changes during the combustion process, and the combustion parameters increased with increments in heating rate. The maximum combustion rate and activation energy increased with declining interlayer spacing and hydrocarbon-generating potential and increasing aromaticity, average stacking height, and aliphatic chain length. The bituminous coal for the utilization of combustion should have high aromaticity, a degree of graphitization, crystalline, long aliphatic chain length, and weak hydrocarbon-generating potential.
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