Measuring radical concentration in varied coals, as a function of reaction with O2. Dependency of radical formation within this process.

Coal is one of the major fuels for power generation, and it will continue in this capacity for the next several decades. Two types of coal are mainly used: lignite and bituminous coals. When exposed to air, post-mining, the coal surface undergoes LTO (low-temperature oxidation) at RT-150 °C according to the atmospheric oxygen level. The LTO process decreases the calorific value of the coal, and consequently, different gases are released [mainly carbon oxides (CO, CO2), water vapor, hydrogen (H2), and also some low molecular-weight organic gases (C1–5)]. Some of these gases are toxic and flammable. In extreme cases, fires erupt. The mechanism by which the molecular oxygen oxidizes the coal macromolecule at the temperature range of 30–150 °C (LTO process) is complex and also involves a chain of radical reactions that take place; however, the exact underlying mechanism is not yet clear. The LTO process was studied in detail by simulating the processes occurring in the coal piles by using two coal types: an American Bailey coal, used in Israeli coal-fired utilities and a German Hambach lignite, used in German utilities. The mechanism underlying the LTO process and the radical reactions that are involved are discussed in detail.

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 O 2 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.