The oxidation of benzene under conditions encountered in waste incinerators

The oxidation of benzene was studied as a function of residence time (tau(res) = 0-2.5 s), temperature (850-960 K), and oxygen concentration (O-2 = 0.2-2.3%) in a heated laminar flow reactor at atmospheric pressure. Nitrogen, doped with 350 ppm benzene, was injected downstream of the burned gas from a near stoichiometric flame of methane + air. Gas samples were taken at different heights up the reactor and analyzed using GC-FID/TCD and HPLC techniques. Phenol and partially oxidized hydrocarbons such as acetaldehyde, formaldehyde, and acrolein were found with concentrations up to 50 ppm. At relatively low temperatures, the conversion of benzene was observed to proceed considerably more slowly at higher oxygen concentrations. Measured concentration profiles were modeled using detailed reaction schemes. A modified mechanism for the oxidation of benzene called BenWas was constructed from the mechanism of Zhang and McKinnon (Combust. Sci. Technol. 107 (1995) 261) by incorporating a submechanism for benzoquinone (OC6H4O) and by updating and enlarging the reaction scheme of cyclopentadiene (C5H6). The agreement between observed and predicted concentration profiles, e.g., of phenol (C6H5OH), acetylene (C2H2), and carbon monoxide (CO), was considerably improved by the use of the BenWas mechanism for rich and lean conditions, mainly due to the introduction of an additional pathway for phenyl oxidation (C6H5 + O-2 = OC6H4O + H) and due to the changed kinetics of the oxidation of cyclopentadienyl (C5H5) in C5H5 + O-2 = C5H4O + OR The measured retardation of benzene oxidation with higher amounts of oxygen can be explained by the formation and reactions of peroxy radicals. (c) 2005 The Combustion Institute. Published by Elsevier Inc. All rights reserved.