Pyrolysis of pigeon pea (Cajanus cajan) stalk: Kinetics and thermodynamic analysis of degradation stages via isoconversional and master plot methods

Detailed analysis of thermo-kinetics, reaction mechanism, and estimation of thermodynamic parameters are imperative for the design of reactor systems in thermochemical conversion processes. Present investigation was aimed at exploring the pyrolysis potential of pigeon pea stalk (PPS) by thermogravimetric experiments at 10, 20, and 30 degrees C/min heating rates. Maximum devolatilization of PPS was found to take place below 480 degrees C. The average activation energy for PPS pyrolysis was found to be 95.97, 100.74, 96.24, and 96.64 kJ/mol by Kissinger-Akahira-Sunose, Flynn-Wall-Ozawa, Starink, and Friedman method, respectively. Statistical analysis by one way analysis of variance method by employing Tukey test revealed that the difference in activation energy estimated from different methods was insignificant. Thermodynamic parameters (Delta H, Delta S, and Delta G) together with reaction mechanisms were also evaluated. Difference in the activation energy and enthalpy was found to be less than 5 kJ/mol. R2 and R3 models were found best fitted with experimental PPS pyrolysis data.