Novel insights into the problem of enthalpy and entropy convergence in thermal decomposition of coal slag using the data from non-isothermal kinetic measurements

Thermochimica Acta(2024)

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Abstract
This study provides insight into benefits of thermo-chemical conversion of coal slag as recovery process into value-added products. This research involves kinetic analysis of process conducted through non-isothermal thermal analysis measurements, with additional raw material characterization. Kinetic results showed that decomposition proceeds through two consecutive reactions steps (first one, including anorthite P1̅ → I1̅ phase transition, and then production of incongruent melting product (ternary system: CaO·Al2O3·2SiO2 (CAS2), where viscosity of slag changes), and second one including dehydration and formation of meta-muscovite, and subsequently, thermal disruption of muscovite de-hydroxylated phase, which proceeds with breaking of octahedral Al–O bonds), and one single-step reaction (attributed to CO-reduction of hematite to magnetite). Thermodynamic results showed an existence of physically meaningful isokinetic temperature (Tiso), which corresponds to active vibrational frequency of surroundings of SiO2 reaction site, manifested through Si‒O bond weakening by catalytic reaction of freed hydroxide ion (OH−). It was concluded that at temperature T = Tiso, the course of process loses its dependence on temperature and pressure, regulating changes between thermodynamic parameters, through enthalpy-entropy compensation (EEC) effect.
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Key words
Alumina-silicate,Slag composition,Non-isothermal kinetics,Enthalpy-entropy compensation,Isokinetic temperature
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