Study on the Influence of Water Immersion on the Heating and Oxidation Stage of Bituminous Coal and the Evolution Law of Key Groups.

In complex geological mining conditions, residual coal often collapses into the goaf, where it becomes saturated with water and undergoes air drying. This process ultimately leads to the formation of water-immersed coal. Coal that has been immersed in water shows a much greater tendency for spontaneous combustion than untreated coal, posing a significant safety hazard in mining operations. This study seeks to investigate how water immersion affects the heating and oxidation processes of bituminous coal along with the changes in key chemical groups during these stages. Long-flame coal and fat coal were selected as the research materials, and water-immersed coal samples were prepared with water to coal mass ratios of 1:2, 1:1, and 2:1. Experiments using scanning electron microscopy, low-temperature nitrogen adsorption, programmed temperature gas chromatography, and in situ Fourier transform infrared spectroscopy were conducted to examine the alterations in the microscopic physical structure, oxidation behavior, and active functional groups of coal samples before and after water immersion. Pearson correlation analysis was utilized to determine the primary active groups in coal samples throughout each phase of heating and oxidation. The research results indicate that (1) as the duration of water immersion increased, both the pore and fracture structures of long-flame coal and fat coal exhibited a progressive enlargement. The average pore diameter of the raw coal increased from 4.16 and 7.33 nm to 5.12 and 9.09 nm in the C2:1 and F2:1 coal samples, respectively. The proportions of mesopores and macropores increased to 21.87, 19.64, and 78.16, 73.24%, respectively. (2) In the early stages of coal spontaneous combustion and oxidation, water immersion acts to hinder the oxidation process of bituminous coal. However, as the temperature rises, the moisture inside the coal pores evaporates, causing the water immersion to reversely promote the oxidation of bituminous coal. During the rapid oxidation stage, the highest oxygen consumption for C1:2 and F1:1 coal samples was 9.94 and 10.93%, respectively. Their oxygen consumption rates were 1.43 and 1.21 times that of raw coal, respectively. During the intense oxidation stage, the highest CO production for C1:2 and F1:1 coal samples was 23,157 and 25,699 ppm, respectively. Compared to raw coal, this represents an increase of 1.83 and 1.48 times, respectively. (3) Water immersion results in a higher concentration of hydroxyl and oxygen-containing functional groups in the coal, while simultaneously reducing the proportion of aliphatic and aromatic hydrocarbon groups. Hydroxyl groups are the key functional groups in the slow oxidation stage, exhibiting correlation coefficients of -0.955 and -0.941 with untreated long-flame coal and bituminous coal, respectively. Aliphatic hydrocarbons also serve as critical functional groups during the slow oxidation stage, with correlation coefficients of -0.876 and -0.892 for untreated long-flame coal and bituminous coal, respectively. In the intense oxidation stage, oxygen-containing functional groups are pivotal, where untreated long-flame coal and fat coal show correlation coefficients of 0.934 and 0.980 with carbonyl (C=O) groups and 0.859 and 0.913 with carboxyl (-COOH) groups, respectively.