The kinetic model of cyclohexene–air combustion over a wide temperature range

Abstract

Cyclohexene is an important intermediate during the combustion process of hydrocarbon and oxygenated fuels. In view of the lack of study on the combustion of cyclohexene in air, an experimental and modeling study is performed to investigate the chemistry of cyclohexene–air mixtures under a wide temperature range. The shock tube experiments are conducted at pressures of 2 and 10 atm with equivalence ratios of 0.5, 1.0 and 2.0 to determine the ignition delay times. The ignition data under 10 atm cover a wide temperature range varying from a low temperature of 770 K to a high temperature of 1222 K. No typical negative-temperature-coefficient is observed, but the ignition at low temperatures is shorter than the extrapolation at high temperatures. A detailed kinetic model of cyclohexene oxidation is proposed based on the low temperature mechanism of 1,3-cyclohexadiene and the existing high temperature mechanism of cyclohexene. The developed model reproduces the ignition delay times in air well, but it over predicts the ignition delays in argon conditions at higher temperatures. Sensitivity analyses under different temperatures and equivalence ratios are carried out to identify the key reactions affecting ignition. The reactions of H + O₂ = O + OH and hydrogen abstraction reaction of cyclohexene with oxygen (CYHEXEN + O₂ = CYHEXEN-3J + HO₂) explain the change of ignition delay time of cyclohexene with equivalence ratios. Flux analysis gives the change of main reaction pathways under wide temperatures and different pressures. The retro-Diels–Alder reaction as the most important consumption channel of cyclohexene at the pressure of 2 atm and temperature of 1350 K is greatly suppressed when the pressure is increased to 10 atm, while the hydrogen abstraction reaction becomes the main consumption channel of cyclohexene at the high pressure. The proposed kinetic model for cyclohexene oxidation can be used to develop models of hydrocarbon and oxygenated fuels.