Thermogravimetric pyrolysis of onion skins: Determination of kinetic and thermodynamic parameters for devolatilization stages using the combinations of isoconversional and master plot methods.

Thermogravimetric pyrolysis of onions skins was studied thoroughly for the first time. Kinetic calculations of devolatilization stages were performed applying direct Arrhenius plot (DAP) method and combinations of isoconversional and Criado's Z(α) master plot (CZMP) methods. The kinetic parameters calculated using combined methods were utilized successfully to reproduce the experimental kinetic curves whereas those calculated using DAP method failed in this sense. The average Ea values of isoconversional methods were between 164.0 and 172.0 kJ/mol. The CZMP method yielded multiple F-type reaction mechanisms. The simplified kinetic models of combined methods were also developed by using single reaction mechanisms deduced from multiple reaction mechanisms. The Friedman-CZMP combination was the best option for developing simplified/unsimplified kinetic models. Determination of reaction mechanism using DAP method by searching for the highest R2 value of regression equation among several candidates was found unreliable. ΔH, ΔG and ΔS values were calculated for 10 °C/min heating rate.

Determination of kinetic triplet, thermal degradation behaviour and thermodynamic properties for pyrolysis of a lignocellulosic biomass.

Kinetic triplet, thermal degradation behaviour and thermodynamic properties of peanut shells were determined on the basis of non-isothermal thermogravimetric experiments conducted at three different heating rates under N2 atmosphere. A single differential peak was observed for the devolatilization stage. The kinetic triplet of devolatilization stage was determined using Coats-Redfern and a combined method consisting the utilization of isoconversional and Criado methods. Kinetic validation revealed that the kinetic triplet determined using the combined method described the experimental values more precisely. The reaction mechanism ascertained by the combined method was D5-D3 combination. The Ea value was strong function of conversion, and computed using isoconversional methods (Boswell, Flynn-Wall-Ozawa, Starink, Tang) between 169 and 268 kJ/mol. Entalphy, entrophy and Gibbs energy changes were computed in 164-259 kJ/mol, -37-141 J/(mol.K) and 173-187 kJ/mol ranges, respectively. The comprehensive pyrolysis index values were also calculated, and shown to increase with increasing heating rate.