Reactive molecular dynamics simulations of the initial stage of brown coal oxidation at high temperatures

Abstract

To investigate the detailed mechanisms for brown coal oxidation at high temperatures, a ReaxFF reactive forcefield was used to perform a series of molecular dynamics simulations from 1000 K to 2500 K. Analyses indicated that the chemical system tend to be more reactive with increasing temperature. It was found that the oxidation process of brown coal primarily initiates from hydrogen abstraction reactions by O2 and related oxygenated radicals from phenolic hydroxyl groups, methyl groups, especially carboxyl groups in lower temperature to form peroxygen species, or by either thermal decomposition of brown coal backbone in higher temperature. These peroxygen species usually could chemically adsorb on the C-centered radicals of brown coal backbone. The weak O–O bond in peroxygen makes them easier to break into oxygenated radical, which could also chemically adsorb on the C-centred radical to form hydroxyl group and other oxygenated compounds. In the oxidation process of brown coal, the decomposition and oxidation of aliphatic chain is easier than aromatic ring. The chemisorption of peroxygen radical induces the breakage of aromatic ring and accelerates the depth oxidation of brown coal. An increasing number of products are observed with increasing temperature.