Development of Detailed, Reduced and Skeletal Kinetic Mechanisms for Hydrocarbon Oxidation at Low and Intermediate Temperatures

In the absence of scalable alternative energy sources that are greenhouse gas (GHG) neutral, hydrocarbon fuels are expected to continue to be a large part of the energy mix for the foreseeable future. Nevertheless, combustion technologies and fuels will have to be improved and refined to reduce hazardous and GHG emissions and improve efficiency. Computer simulations using accurate chemical kinetic models are increasingly being used to aid the development of these technologies. This study presents approaches that can help improve kinetic models for combustion and aid the development of new engine technologies that are fuel efficient and produce lower GHG emissions.;A reduced kinetic mechanism that can predict cool flames for propane-air mixtures was developed. The mechanism is able to predict multiple cool flames, global variables and species concentrations within defined accuracy limits, and reduces computation time by a factor of three and computer memory for the computation by an order of magnitude.;This study also developed algorithms for the development of extended detailed kinetic mechanisms as well as skeletal models for primary fuels and fuel additives. This algorithm was used to develop a detailed mechanism for the combustion of Primary Reference Fuels (PRFs) and Di-Tertiary Butyl Peroxide (DTBP), a fuel additive. The detailed kinetic mechanism was able to help explain the impact of DTBP on PRF combustion in a PCI engine and identify the primary mode of action of DTBP depending on the PRF octane number. The skeletal model reduces the computation time by 99.6%, and requires approximately 0.1% computer memory compared to the detailed mechanism.;As a final objective, the first detailed kinetic mechanism accounting for the formation of lactones during low temperature combustion of hydrocarbons was developed. Lactones are cyclic ethers with a carbonyl function that have been observed experimentally by several research groups including the combustion chemistry group at Drexel University, but not predicted, by kinetic mechanisms available today. The proposed detailed kinetic mechanism, containing 206 new reactions and 35 new species, was able to achieve good agreement with published experimental data for the non-alkylated lactones produced during the oxidation of n-dodecane in a Pressurized Flow Reactor.