Detailed kinetic reaction mechanism for cyclohexane oxidation at pressure up to ten atmospheres

A detailed reaction mechanism for cyclohexane oxidation has been evaluated by comparison of computed and experimental species mole fraction profiles measured in a jet-stirred reactor at 0.5 less than or equal to phi less than or equal to 1.5 and 1. 2, and 10 atm. Major and minor species mole fractions were obtained by gas chromatography: O-2, CO, CO2, H-2, CH2O, CH3HCO, acrolein, CH4, C2H6, C2H4, C3H6, C2H2, allene, 1-C4H8, 2-C4H8 (trans and cis), 1,3-C4H6, cyclopentene, cyclohexadiene, 1-hexene, cyclohexene, and C6H6. The main objective of this work was to extend the validity of a previously proposed mechanism for cyclohexane oxidation at 10 atm to lower pressure and to refine it by taking into account some new species analyzed in this work: 1-C4H8, 2-C4H8 (trans and cis), and aC(6)H(12). Good agreement was obtained for most molecular species, especially intermediate olefins, dienes, and oxygenated species (CH2O, acrolein). Computed benzene, cyclopentene. and cyclohexene concentrations are also in reasonable agreement with experimental data. The mechanism also was validated at higher temperature by modeling the laminar flame speeds of cyclohexane/air flames measured by Davis and Law in a wide range of equivalence ratios. The model correctly reproduces experimental values. Reaction path analyses were used to interpret the results.