Styrene thermal decomposition and its reaction with acetylene under shock tube pyrolysis conditions: An experimental and kinetic modeling study.

Styrene is an important compound for polymer production and a key intermediate in gas-phase kinetics of polycyclic aromatic hydrocarbons (PAHs). For the first time, the pyrolysis of styrene with and without the presence of acetylene is investigated in a single-pulse shock tube coupled to gas chromatography and mass spectrometry. For each reaction system, quantitative speciation profiles are probed within the temperature range of 1100–1730 K, nominal pressure of 20 bar, and reaction duration of ∼ 4 ms. A kinetic model is built to simulate the results. The model explains how styrene is consumed under high-pressure pyrolytic conditions, how the secondary chemistry of intermediate products affect subsequent PAH formation, and how acetylene addition alters the reaction pathways. Throughout the temperature range, styrene breakdown is dominated by the bimolecular interaction between styrene and hydrogen atom, which produces benzene+vinyl or phenyl and ethylene through the stabilization of 2-phenylethyl and its subsequent dissociation. As a result, large amounts of phenyl accumulate, which react with styrene to form C 14 H 12 species while simultaneously releasing H atoms through addition/elimination reactions. The reactivity of fuel consumption is preserved by the regeneration of H atoms as chain carriers. Several C 14 H 10 compounds are formed as a result of the following breakdown of the C 14 H 12 isomers, particularly stilbene, 1,1-diphenyl ethylene, and 9-methyl-9H-fluorene. The presence of acetylene as a co-reactant with styrene allows the Hydrogen-Abstraction-Acetylene-Addition (HACA) pathway to proceed from phenyl radical to enhance the production of phenylacetylene at very low temperatures and acenaphthylene. This hinders the formation of C 14 H 12 isomers, exclusive products from pure styrene dissociation by competing with the styrene+phenyl routes. [ABSTRACT FROM AUTHOR]