Thermal Stability of Carbon-Centered Radicals Involved in Low-Temperature Oxidation of Bituminous and Lignite Coals as a Function of Temperature

Coal is intensively used worldwide as a main fuel source. However, it may undergo oxidation processes [i.e., low-temperature oxidation (LTO)] when stored under an air atmosphere in piles post-mining at low temperatures ranging from 300 to 425 K, specifically, a surface gas/solid reaction with molecular oxygen. Therefore, it is of major importance to prevent or appreciably slow down such reactions, which result in a loss in the energy content (calorific value) of coal. Previously, we showed that radicals are formed during the LTO process. In this work, the dependence of radical formation on coal rank as a function of heating (temperature) and the presence of oxygen gas were studied using electron paramagnetic resonance spectroscopy. It was shown that lignite coals are more sensitive than bituminous coals to the atmospheric environment (i.e., molecular oxygen and nitrogen content) and to temperature, as reflected by the formation of surface carbon-centered radicals. Moreover, this is the first publication showing the effects of LTO on micro- and macro-pores by assessing how these structures affect O2 diffusion. The LTO process blocks the micro-pores, such that radicals form mainly at the surface of the coal macromolecules, in both bituminous and lignite coals.