o:30414 Kinetic and thermodynamic compensation phenomena in C3 and C4 energy crops pyrolysis: Implications on reaction mechanisms and product distributions Fenomeni kinetičke i termodinamičke kompenzacije u pirolizi C3 i C4 energetskih useva: implikacije na reakcione mehanizme i raspodelu proizvoda en ABSTRACT 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. energy crops, slow pyrolysis, thermodynamic compensation, isokinetic temperature, catalytic activity, bio-fuels 1552099 10.1016/j.indcrop.2023.116275 2023-07-18T11:22:06.810Z 44 yes 46 Bojan Janković University of Belgrade, Department of Physical Chemistry, VINČA, Institute of Nuclear Sciences-National Institute of the Republic of Serbia, Serbia Nebojša Manić University of Belgrade, Faculty of Mechanical Engineering, Serbia person Mina Popović University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Serbia person Slobodan Cvetković University of Belgrade, Institute of Chemistry, Technology and Metallurgy, Serbia person Željko Dželetović University of Belgrade, Institute for the Application of Nuclear Energy INEP, Serbia doktor biotehničkih nauka person 0000-0001-9166-7094 Dragoslava Stojiljković University of Belgrade, Faculty of Mechanical Engineering, Serbia person application/pdf 7579859 https://phaidrabg.bg.ac.rs/o:30414 no yes 1 70 92000001 11A28 11A2806 11A30 11A24 11A29 11A2906 Industrial crops & Products 194 Elsevier B.V. 2023