Thermal Conversion of Coal Bottom Ash and Its Recovery Potential for High-Value Products Generation: Kinetic and Thermodynamic Analysis with Adiabatic Predictions.

Thermal decomposition (pyrolysis) of coal bottom ash (collected after lignite combustion in coal-fired power plant TEKO-B, Republic of Serbia) was investigated, using the simultaneous TG-DTG techniques in an inert atmosphere, at various heating rates. By using the XRD technique, it was found that the sample (CBA-TB) contains a large amount of anorthite, muscovite, and silica, as well as periclase and hematite, but in a smaller amount. Using a model-free kinetic approach, the complex nature of the process was successfully resolved. Thermodynamic analysis showed that the sample is characterized by dissociation reactions, which are endothermic with positive activation entropy changes, where spontaneity is achieved at high reaction temperatures. The model-based method showed the existence of a complex reaction scheme that includes two consecutive reaction steps and one single-step reaction, described by a variety of reaction models as nucleation/growth phase boundary-controlled, the second/-th order chemical, and autocatalytic mechanisms. It was established that an anorthite 1 phase breakdown reaction into the incongruent melting product (CaO·AlO·2SiO) represents the rate-controlling step. Autocatalytic behavior is reflected through chromium-incorporated SiO catalyst reaction, which leads to the formation of chromium(II) oxo-species. These catalytic centers are important in ethylene polymerization for converting light olefin gases into hydrocarbons. Adiabatic prediction simulations of the process were also carried out. Based on safety analysis through validated kinetic parameters, it was concluded that the tested sample exhibits high thermal stability. Applied thermal treatment was successful in promoting positive changes in the physicochemical characteristics of starting material, enabling beneficial end-use of final products and reduction of potential environmental risks.