Studying the effect of oxygen in coal oxidation is very important for understanding and controlling coal spontaneous combustion. However, the oxygen effect is not very easy to determine clearly due to the large effect of heat source on coal oxidation in temperature rising experiments. Here, focused on sub-bituminous coal, the oxygen effect was separated from coal oxidation by continuously measuring FTIR spectra of coal with respect to varying temperatures and under oxygen and nitrogen. The active groups’ real-time changes of coal oxidation, thermal treatment and oxygen effect were measured. The carboxylic ester and carboxyl units are the main functional groups that increase with temperatures increasing under oxygen and nitrogen, while the other functional groups decrease in quantity. The oxygen effect promoted the consumption of aliphatic hydrocarbons and hydroxyl groups and also promoted the formation of oxygen-containing groups (except hydroxyl). Four characteristic temperature stages involved in the oxygen effect and their key functional groups were identified. Simultaneously, the relationship of oxygen consumption and chemisorption in oxygen effect was analyzed. The starting temperature of oxygen chemisorption is between 50 and 60°C. The maximum contribution of oxygen effect was observed in methyl and methylene groups. These results are important for chemical control of coal spontaneous combustion. The oxidation of aliphatic hydrocarbon should be controlled before oxygen chemisorption. The value of oxygen consumption between 70 and 80°C can be measured accurately due to the constant chemisorption rate, which help to identify the tendency for spontaneous combustion. These results will help in better understanding of the reaction mechanism of coal oxidation, especially the oxygen effect.

Coal spontaneous combustion (CSC) is a disaster that seriously threatens safe production in coal mines. Revealing the mechanism of CSC can provide a theoretical basis for its prevention and control. Compared with experimental research is limited by the complexity of coal molecular structure, the quantum chemical calculation method can simplify the complex molecular structure and realize the exploration of the mechanism of CSC from the micro level. In this study, toluene and phenylacetaldehyde were used as model compounds, and the quantum chemical calculation method was adopted. The reaction processes of the methyl and aldehyde groups with oxygen were investigated with the aid of the Gaussian 09 software, using the B3LYP functional and the 6-311 + G(d,p) basis set and including the D3 dispersion correction. On this basis, the generation mechanisms of CO and CO₂, two important indicator gases in the process of CSC, were explored. The calculation results show that the Gibbs free energy changes and enthalpy changes in the two reaction systems are both of negative values. Accordingly, it is judged that the reactions belong to spontaneous exothermic reactions. In the reaction processes, the activation energy of CO is less than that of CO₂, indicating that CO is formed more easily in the above-two reaction processes. In addition, the variations in concentrations of important oxidation products (CO and CO₂) and main active functional groups (such as methyl, carboxyl and carbonyl) with temperature were revealed through a low-temperature oxidation experiment. The experimental results verify the accuracy of the above quantum chemical reaction path. Moreover, it is also found that the generation mechanisms of CO and CO₂ in coal samples with different metamorphic degrees are different. To be specific, for low-rank coal (HYH), CO and CO₂ mainly come from the oxidation of alkyl side chains; for high-rank coal (CQ), CO is produced by the oxidation of alkyl side chains, and CO₂ is attributed to the inherent oxygen-containing structure.

Coalfield fire area reburning is one of the serious disasters in fire prevention and safety production. In this study, a synchronous thermal analyzer was used to conduct isothermal pyrolysis of jet coal at different temperatures, and the reaction characteristic parameters of different pyrolysis residual structures were analyzed. FTIR was used to measure group contents in raw coal and different pyrolysis residues. Programmed oxidation thermogravimetric experiments were carried out on the residues to obtain their oxidation characteristic parameters. The results demonstrated that the reaction characteristic parameters of the residual structures changed at 450 °C. The pyrolysis reaction mainly affected the variation of hydroxyl, aliphatic hydrocarbon, and aromatic hydrocarbon groups. The increase in pyrolysis temperature resulted in the decline in hydroxyl and aliphatic hydrocarbon groups as well as the increase in the aromatic hydrocarbon group. After pyrolysis, the ignition point temperature of the coal sample decreased, which causes the coal more likely to spontaneously ignite. It indicated that the pyrolysis residue at 450 °C is most likely to reburn. Compared with raw coal, the maximum combustion intensity of the pyrolysis residue was greatly increased, which reached the peak at 500 °C.