Construction of reaction mechanism for decomposition of biofuel blend - methyl levulimate radicals.

Abstract

Employing explicitly CBS-QB3 method for obtaining structure geometry and energy of species involved in mechanism of methyl levulinate radicals (MLRs) decomposition, time-resolved profiles of species and temperature and pressure – dependent rate constants (from 300 – 2000 K and 0.001 – 100 atm) of reactions have been derived using stochastic model within master equation/Rice-Ramsperger-Kassel-Marcus framework (ME/RRKM). The formation of methyl acrylate (MAC) and methyl vinyl ketone (MVK) dominates other pathways at temperature range above 700 K, which agrees with previous study, while isomerization reactions are the most important in the remaining temperature range. MAC especially becomes main product regardless of temperature and pressure condition in the consumption of MLR-. The difference in pressure – dependent behavior of products brings about extreme complexity of outcome. At high pressure, unique TS pathways are more of the importance characterized by the dominance of formaldehyde formation in MLR-m consumption (above 100 atm) and ketene formation in MLR- consumption (above 10 atm). Keyword: Methyl levulinate, thermodynamic, kinetics, time-resolved profile, branching ratio, temperature and pressure dependent rate constant.