Chemical looping pyrolysis of biomass using ferrite-based oxygen carrier: Kinetics, thermodynamics and compensation...

This study investigated the chemical looping pyrolysis (CLP) of xylan, a hemicellulose compound, using MnFe₂O₄ and CoFe₂O₄ as oxygen carriers (OCs). The presence of OCs accelerated the xylan decomposition, lowering peak temperatures from 256-329 °C to 194-245 °C and 198-242 °C, respectively. Kinetic analysis using model-free methods revealed a reduction in the average activation energy from 127.74 kJ mol^-1 for xylan to 105.48 kJ mol^-1 and 111.35 kJ mol^-1 with the one-dimensional diffusion model providing the best fit. Both enthalpy and Gibbs free energy changes decreased in the presence of oxygen carriers, indicating improved reactivity and thermodynamic feasibility. Among the oxygen carriers, CoFe₂O₄ demonstrated superior reactivity, suggesting its potential for efficient, scalable CLP-based bioenergy systems. These results will provide mechanistic insights into oxygen carrier behavior and establish a kinetic-thermodynamic foundation for process optimization and scale-up in CLP of biomass.