Development of a Chemical Kinetic Mechanism for Small Hydrocarbons

Abstract

A detailed chemical kinetic mechanism has been developed to describe the oxidation of small hydrocarbon and oxygenated hydrocarbon species. In order to understand the oxidation of large hydrocarbon and oxygenated hydrocarbon fuels it is necessary to first generate a detailed understanding of the pyrolysis and oxidation kinetics of simple fuels such as hydrogen and carbon monoxide as well as hydrocarbon fuels such as methane, ethane, ethylene, acetylene, propane, propene, allene, and propyne. Contributions were made to the development a detailed chemical kinetic C1-C2 mechanism. The largest part of the contribution to the C1-C2 sub-mechanism made by the author of this study was in the development of the methanol, acetaldehyde, and ethanol sub-mechanisms. Rate constants and thermochemical data were included in the mechanism from the most recent experimental and theoretical studies where available and optimisation was avoided as much as possible. An updated method for estimating thermochemical group values for higher order hydrocarbons was developed in a hierarchal and iterative manner. A large database of thermochemical data available from the literature for C1-C4 alkane, alkene, alcohols, hydroperoxides and alcoholic hydroperoxides species was collated. Updates were made to the allene and propyne sub-mechanism, incorporated into the mechanism are recent high-level rate constant calculations. The allene and propyne sub-mechanism is validated against the available experimental data. New experimental data for propene oxidation was obtained in a jet-stirred reactor. This data contributed to the development of a new sub-mechanism for propene oxidation that is capable of predicting combustion characteristics for propene across a wide range of conditions (T, p, phi, dilution).