Multi-distribution activation energy model on slow pyrolysis of cellulose and lignin in TGA/DSC

Developing a kinetic model to analyze the multi-step reaction of biomass pyrolysis is pivotal to elucidate the mechanism of the pyrolysis. For this purpose, a model-fitting method such as multi-distribution the Distributed Activation Energy Model (DAEM) is one of the most reliable methods. DAEM with 4 different distribution functions of Gaussian, Logarithmic, Gumbel, and Cauchy was utilized to characterize the pyrolysis of cellulose and lignin during Thermogravimetric Analysis/Differential Scanning Calorimetry (TGA/DSC) instrumentation. By comparing Derivative Thermogravimetry (DTG) and DSC profiles, determination of pseudo-components can be done more accurately. A kinetics analysis on the pyrolysis of cellulose with a single Gaussian distribution DAEM yielded a single activation energy of 178 kJ mol^-1 with a narrow standard deviation. This result was justified by a single and dominant endothermic peak followed by minor exothermic peaks in the DSC result. For lignin pyrolysis, the presence of multiple peaks is characterized by four pseudo-components in DAEM with activation energies of 157, 174, 194, and 200 kJ mol^-1. These pseudo-components were confirmed by the DSC result which indicated the occurrences of two exothermic peaks with two lesser exothermic or possibly endothermic peaks at the same temperature range. These findings imply the importance of DSC to support a kinetics study of thermogravimetric pyrolysis.