Reaction mechanisms for toluene pyrolysis

Abstract

The rich chemistry occurring during the pyrolysis of toluene has been investigated by studying its decomposition in a single-pulse shock tube coupled with detailed chemical kinetic modeling to describe product formation. This work provides information on the initial decomposition steps of toluene and its primary radical benzyl as well as the detailed steps leading to the formation of polyaromatic hydrocarbons. Temperatures ranged from approximately 1200 to 1850 K for 1% toluene in argon, total pressures of approximately 10 atm, and residence times near 600 μ s. Pyrolysis products were collected and analyzed using gas chromatography. Profiles of hydrogen and hydrocarbons ranging from methane to pyrene were obtained. These semiquantitative data have been interpreted to help resolve many of the existing uncertainties involving the pyrolytic process. In particular, this work supports arguments for a low activation energy process for benzyl radical decomposition as evidenced by the low-temperature formation of cyclopentadiene and the radical recombination product, benzyl-cyclopentadienyl (b-cpd). Also, the data support suggestions for an important role of the methylphenyl radical, specifically in the formation of isomers of dimethyldiphenyl and as a key intermediate in the production of anthracene. Minimal evidence for rapid toluene decomposition to phenyl and methyl was found. Importantly, the data support general mechanisms proposed for ring growth sequences, although an additional important step involving ring closure and direct H 2 elimination is suggested by the data. In addition, the data indicate rapid anthracene/phenanthrene isomerization above 1600 K.