Study on the evolution characteristics of molecular surface active sites of low-rank coal in low-temperature oxidation stage

Compared with other coal types of coal, low - metamorphic coal contains numerous active sites, making it susceptible to spontaneous combustion and posing significant risks during production, transportation, and storage. To further reveal the evolution characteristics and laws of low-rank coal's active sites during the process of low-temperature oxidation of coal (LTOC), X-ray photoelectron spectroscopy (XPS), 13C nuclear magnetic resonance (13C NMR), and Fourier transform infrared (FTIR) experiments were used to determine the basic structural parameters such as the valence state of non-carbon features, types of carbon elements in coal macromolecules, and structure and quantity of functional groups. Combined with molecular modelling software (GaussView 6.0) and macromolecular calculation software (Grimme-XTB), macromolecular models of coal at different temperature points were constructed, and the surface energy field distribution was calculated. The number and energy change information of chemical and physical adsorption sites of low-rank coal during heating were obtained. The results show that during the LTOC, the chemical adsorption sites such as aliphatic hydrocarbons (-CH3/-CH2) have higher reactivity and can be converted into oxygen-containing functional groups (-CHO, –OH, –COOH); the number of physical adsorption sites increased first and then decreased, and reached the maximum at 50 °C. Coal exhibited a higher affinity for O2 at this temperature. The peroxide (-C-O-O-H) undergoes thermal decomposition, leading to H2O and weight loss of coal. The –CO and –COO structures undergo decarboxylation to generate CO, CO2, and other gases. This study comprehensively revealed the evolution of active sites through two key coal oxygen processes, physical and chemical adsorption, based on the gradual temperature elevation of low-rank coal. This holds immense significance for improving and enriching the understanding of the mechanism of coal spontaneous combustion(CSC), preparing more targeted CSC inhibition, and formulating efficient fire prevention and extinguishing measures.