Modeling of Aromatic and Polycyclic Aromatic Hydrocarbon Formation in Premixed Methane and Ethane Flames

TLDR

A detailed kinetic model of aromatic and polyaromatic formation was developed and validated against experimental data from an atmospheric‑pressure, laminar flat methane and ethane flame at equivalence ratio 2.5, with gas composition measured by online GC/MS across flame and post‑flame zones for species ranging from two to five‑ring PAHs. The model identifies that aromatic and polycyclic aromatic hydrocarbons form mainly through resonantly stabilized radical combinations, with propargyl and I‑methylallenyl yielding benzene and methyl‑benzene, cyclopentadienyl self‑combination producing naphthalene, and indenyl–cyclopentadienyl coupling forming phenanthrene, while O₂‑mediated phenyl removal to cyclopentadienyl is key to PAH and soot precursor growth.

Abstract

Detailed chemical kinetic modeling has been performed to investigate aromatic and polyaromatic hydrocarbon formation pathways in rich, sooting, methane and ethane premixed flames. An atmospheric pressure, laminar flat flame operated at an equivalence ratio of 2.5 was used to acquire experimental data for model validation. Gas composition analysis was conducted by an on-line gas chromatograph / mass spectrometer technique. Measurements were made in the flame and post-flame zone for a number of low molecular weight species, aliphatics, aromatics, and polycyclic aromatic hydrocarbons (PAHs) ranging from two to five-aromatic fused rings. The modeling results show the key reaction sequences leading to aromatic and polycyclic aromatic hydrocarbon formation primarily involve the combination of resonantly stabilized radicals. In particular, propargyl and I-methylallenyl combination reactions lead to benzene and methyl substituted benzene formation, while polycyclic aromatics are formed from cyclopentadienyl and fused rings that have a shared C3, side structure. Naphthalene production through the reaction step of cyclopentadienyl self-combination, and phenanthrene formation from indenyl and cyclopentadienyl combination were shown to be important in the flame modeling study. The removal of phenyl by O2leading to cyclopentadienyl formation isexpccted to playa pivotal role in the PAH or soot precursor growth process under fuel-rich oxidation conditions.