More insight into cyclohexanone oxidation: Jet-stirred reactor experiments and kinetic modeling

Abstract

The kinetics of cyclohexanone oxidation was studied in a jet-stirred reactor (JSR) at atmospheric pressure, over the temperature range 740–1250 K, and for equivalence ratios of φ = 1 and 2 and a residence time of 70 ms. Concentration profiles of reactants, stable intermediates and products were measured by gas chromatography (GC) and Fourier transform infrared spectrometry (FTIR) after sonic probe sampling. Reaction intermediates measured during oxidation are mainly: methane, ethane, ethylene, propene, cyclohex-2-en-1-one and methyl vinyl ketone. To a less extent, cyclic intermediates such as cyclopentene, 1,3-cyclopentadiene were also detected. These new data complete those obtained by Serinyel et al. [1] through jet-stirred reactor experiments performed at 10 atm. Moreover, in this study, rate constants of important reactions were calculated at the G3//MP2/aug-cc-pvdz level of theory with strict convergence criterion. These rate constants involve hydrogen abstraction reactions from the fuel by H, OH, and CH3 radicals, decomposition and isomerization reactions of the fuel radicals. The resulting kinetic mechanism was tested against all the available JSR data with satisfactory agreement.