ReaxFF molecular dynamics simulations of non-catalytic pyrolysis of triglyceride at high temperatures

ZQ Zhang and KF Yan and JL Zhang, RSC ADVANCES, 3, 6401-6407 (2013).

DOI: 10.1039/c3ra22902e

In order to investigate the initiation mechanisms associated with the pyrolysis of triglyceride that could potentially be used as petrochemical replacements, we carried out 500 ps molecular dynamics simulations employing the ReaxFF reactive force field using tripalmitin as the model molecule at 1500 and 2000 K. We find that the primary decomposition reactions of tripalmitin initiate with the successive scission of the alkyl-oxygen bond to form three straight chain C16H31O2 center dot (RCOO center dot) radicals and C3H5 center dot radical. The deoxygenated alkyl chain is produced through the decarboxylation of the RCOO center dot radical with concurrent production of CO2. The resulting alkyl and C3H5 center dot radicals further undergo recombination and decomposition to yield mainly alkanes and alkenes, with the actual product distribution being dependent on reaction temperature. beta- Scission plays an important role in alkyl chain decomposition with a concomitant release of C2H4. Compared to 1500 K, this reaction is accelerated at 2000 K. In addition, the formation of cyclic hydrocarbon is also observed at 2000 K. As opposed to previous proposed Diels-Alder reactions or intramolecular cyclizations of alkenyl radicals mechanisms, it is found that cyclopentane could be produced by intramolecular cyclization of a biradical.

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