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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. [ABSTRACT FROM AUTHOR]

The remarkable differences between the infrared spectra of oxygen adsorption and nitrogen desorption in coal have been experimentally and theoretically investigated. Density functional theory calculations were performed to better explain the mechanism of oxygen adsorption using six different molecular models of coal. In addition, the remarkable differences of infrared spectra between oxygen adsorption and nitrogen desorption was defined as the indexV, which was used to classify the spontaneous combustion tendency of coal. The experimental data indicated that the spectra in the 4000–2000 cm−1and 1250–1050 cm−1regions exhibited significant changes. These results suggest that the mechanism of oxygen adsorption is the alteration and transfer of charge density around the activated sites, which leads to the observed changes of the infrared spectra. TheV, which is related to the alteration of spectral intensity, is found to decrease with the increase of adiabatic oxidation time and the relative spontaneous combustion period of coal. This observation solidifies the connection between sample spectral intensity and oxygen chemisorption. These data suggest that the hydroxy in hydroxy and carboxyl groups on the surface of coal particles is the site of oxygen chemisorption, and theVcan be used to rapidly and accurately categorize the spontaneous combustion tendency of coal. [ABSTRACT FROM PUBLISHER]

Abstract: The extinction coefficient differs for different functional groups making the quantitative analysis of their infrared spectra problematic. Although the coefficients of some functional groups have been researched previously, they are inaccurate because of deviations in techniques used and linear fitting. The distribution and structural characteristics of functional groups from coal infrared spectra is therefore inaccurate. In this study, quantum chemistry methods are used for the quantification of coal infrared spectra based on the Beer–Lambert law. The effect of the extinction coefficients of different functional groups is eliminated. The experimental infrared intensities, unit absorption intensities and their ratios are obtained to calculate the percentage composition of coal functional groups and molecular structure parameters. Accurate distribution and structural characteristics of coal functional groups are obtained. A linear relationship between the distribution of some functional groups and structural parameters is obtained. Multiple structural parameters are used to determine the grade and maturity of coal samples. The ethylene in coal oxidation experiments below 200°C is consistent with the hydrocarbon-generating potential parameters. These results will improve the accuracy of the quantitative analysis of infrared spectra for determining coal structural features and provide an index for the utilization and prevention of the spontaneous combustion of coal. [Copyright &y& Elsevier]