A Chemical Kinetic Investigation on Butyl Formate Oxidation: Ab Initio Calculations and Experiments in a Jet-Stirred Reactor

Zaras, Aristotelis M. and Szőri, Milán and Thion, Sebastien and Van Cauwenberghe, Pierre and Deguillaume, Fioan (2017) A Chemical Kinetic Investigation on Butyl Formate Oxidation: Ab Initio Calculations and Experiments in a Jet-Stirred Reactor. ENERGY AND FUELS, 31 (6). pp. 6194-6205. ISSN 0887-0624

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Abstract

Biofuels are expected to play a significant role in the quest for greener energy generation. In this perspective, esters produced from biomass are promising candidates. This work presents the first computational kinetic study on n-butyl formate (BF) oxidation under combustion conditions coupled to an experimental study in a jet-stirred reactor. Absolute rate constants for hydrogen abstraction reactions by the OH radical were calculated using the G3//MP2/aug-cc-pVDZ model chemistry, in conjunction with statistical rate theory (TST). Subsequently, the fate of the butyl formate radicals was also investigated by calculating absolute rate constants for combustion relevant decomposition channels such as β-scission and hydrogen transfer reactions. The derived rate expressions were used in the presently developed detailed kinetic mechanism, which was validated over experimental data obtained in a jet-stirred reactor at 10 atm and for three different mixtures (φ = 0.45, 0.9, and 1.8). Rate of production analyses were finally used to understand the oxidation kinetics of butyl formate over the temperature range of 500–1300 K and highlighted the importance of the unimolecular decomposition reactions of the fuel, producing formic acid and 1-butene.

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