An experimental and kinetic modeling study on the high-temperature ignition and pyrolysis characteristics of cyclohexylamine

Abstract

Amine compounds are an important class of nitro-containing fuels and represent as promising renewable fuels. However, the structural effect from the alkyl group on the combustion characteristics of amines remains an urgent problem to promote their usage in practical engines. To probe and replenish the combustion properties of amine fuels, this work reported an experimental and kinetic modeling study on the high-temperature ignition and pyrolysis characteristics of cyclohexylamine over a wide range of conditions. Specifically, a high-pressure shock tube is used to measure the ignition delay times under the temperature range from 1100 K to 1700 K with pressure of 2 and 5 bar and the equivalence ratios of 0.5, 1.0 and 2.0. The pyrolysis characteristics is studied using a single-pulse shock tube at fuel concentration of 0.5% diluted by argon in the temperature range 950–1400 K at 5 and 10 bar with the residence time around 1.6 microsecond. A detailed kinetic mechanism is developed to simulate the experimental results. To improve the accuracy of the detailed mechanism, primary initial reactions of cyclohexylamine including the hydrogen abstraction reactions and the CN decomposition reaction are theoretically studied at G4//M06–2X/6–311++G(d, p) level of theory with transition state theory and RRKM/mater equation. The detailed kinetic mechanism shows good prediction accuracy of the ignition delay times and pyrolysis product distributions under different temperature, pressure and equivalence ratio conditions. Sensitivity analysis results indicate that the most sensitive reaction is O2 + H = O + OH with the most negative sensitivity coefficient and the abstraction reaction of vinylamine with OH radical, C2H3NH2 + OH = C2H3NH + H2O also exhibits large sensitivity coefficients. Reaction path analysis reveals that the abstraction reactions control the initial oxidation of cyclohexylamine and cyclohexen-1-amine, cyclohexen-2-amine, and cyclohexen-3-amine are also major intermediates during the oxidation of cyclohexylamine besides small pyrolysis products.