Modelling of the gas-phase oxidation of cyclohexane

TL;DR

This study develops a detailed kinetic model for cyclohexane oxidation across a wide temperature range, successfully reproducing experimental data and elucidating reaction pathways, including the NTC zone, using a comprehensive mechanism with 513 species.

Contribution

A detailed low-temperature kinetic mechanism for cyclohexane oxidation with 513 species and 2446 reactions, including new reaction pathways and rate constants, validated against experimental data.

Findings

Mechanism accurately reproduces experimental results from rapid-compression and jet-stirred reactors.

Identifies key reaction pathways and intermediates in cyclohexane oxidation.

Provides insights into the negative temperature coefficient behavior.

Abstract

This paper presents a modeling study of the oxidation of cyclohexane from low to intermediate temperature (650-1050 K), including the negative temperature coefficient (NTC) zone. A detailed kinetic mechanism has been developed using computer-aided generation. This comprehensive low-temperature mechanism involves 513 species and 2446 reactions and includes two additions of cyclohexyl radicals to oxygen, as well as subsequent reactions. The rate constants of the reactions involving the formation of bicyclic species (isomerizations, formation of cyclic ethers) have been evaluated from literature data. This mechanism is able to satisfactorily reproduce experimental results obtained in a rapid-compression machine for temperatures ranging from 650 to 900 K and in a jet-stirred reactor from 750 to 1050 K. Flow-rate analyses have been performed at low and intermediate temperatures.