The oxidation of trichloroethene with methane: experiment and kinetic modeling

Abstract The oxidation of C 2 HCl 3 with industrial grade CH 4 has been studied in a laboratory-scale flow reactor under fuel-rich, stoichiometric, and fuel-lean conditions from 575 to 850 °C, with an average gas residence time of 0.3–1.5 s. The major products, C 2 Cl 2 , C 2 H 4 , CO, CO 2 , and HCl, were found at lower temperatures with high [O 2 ]. The minor intermediates included C 2 H 3 Cl, C 2 HCl, CH 3 Cl, COCl 2 , trans -CHClCHCl, cis -CHClCHCl, trans -ClHCCClCH 3 , C 6 H 6 , C 3 s, C 4 s, Cl 2 , and other C 6 compounds. Writing − d [C 2 HCl 3 ]/ dt = k [C 2 HCl 3 ]; global values of k (s −1 ) were found to be 3.21×10 6 exp (−116 ( kJ / mol )/RT) , 1.61×10 6 exp (−112 ( kJ / mol )/RT) , and 1.27×10 6 exp (−112 ( kJ / mol )/RT) , respectively, for fuel-lean, stoichiometric, and fuel-rich conditions. Modeling with a detailed mechanism involving 149 species and 795 elementary reactions revealed that C 2 HCl 3 mainly disappears via C 2 HCl 3 →C 2 Cl 2 +HCl. Sensitivity analyses were performed to rank the significance of every reaction in the mechanism. Agreement between modeling and experiment was satisfactory for most major species.