Kinetic and thermodynamic compensation phenomena in C3 and C4 energy crops pyrolysis: Implications on reaction mechanisms and product distributions

This work provides insight into possibilities of maximum utilization of C3-C4 energy crops for thermo-chemical conversion (slow pyrolysis) into high value biochemicals, platform chemicals, drop-in fuels and combustible gases, using coupled kinetic and thermodynamic analyses. In order to examine the kinetics of decomposition of lignocellulosic components, model-free and model-based methods faded from thermal analysis data were used. Thermodynamic compensation was used for explicatory of entropy controlled process, where conformational changes and chemical exchange directly affect the type and distribution of obtained pyrolytic products. It was shown that external variable (i.e. the heating rate/temperature) does not change either an entire reaction mechanism (mechanistic nature of MG and AD pyrolyses) or transition state, but it changes activation enthalpy and activation entropy which lead to differences in terms of heat energy consumption, pyrolysis favorability and thus rates of generation of activated complex among feedstocks. To investigate the interplay of catalysts (present in feedstocks as minerals) and reactants, selective energy transfer (SET) model was applied. The model showed an activity of catalyst with different outputs towards two reactants, lignin part of the structure in MG and 1,8-cineole in AD. It was shown that AD is more convenient for thermal conversion than MG, regarding to lower transformation energy requirement, higher reactivity, as well as much faster accumulation of products.