Toward the Accurate Prediction of Liquid Phase Oxidation of Aromatics: A Detailed Kinetic Mechanism for Toluene Autoxidation

Abstract

Toluene is an important compound in the chemical industry as well as an often chosen simple surrogate compound for aromatic components in transport fuels. As a result, an improved understanding of the liquid phase oxidation of toluene is of interest to both the chemical industry and the transportation sector. In this work, a detailed autoxidation mechanism for the liquid phase oxidation of toluene is developed using an automated mechanism generation tool. The resultant mechanism is significantly improved using quantum chemistry calculations to update the thermodynamic parameters of key species in solution. Comparisons are made between the predicted and experimentally measured induction period and the obtained mechanism. The agreement between both is found to be within 1 order of magnitude. Rate of production analysis and sensitivity analysis are carried out to explain and understand the reactions paths present in the mechanism. The behavior of the mechanism is commented upon qualitatively; however, no quantitative data could be obtained with the selected test method.