Study on Products from Fuel-rich Methane Combustion near Sooting Limit Temperature Region and Importance of Methyl Radicals for the Formation of First Aromatic Rings

Abstract

Productions of mono-/di-cyclic aromatic hydrocarbons as well as smaller stable species from extremely fuel-rich CH4/air mixtures (equivalence ratio of 1.7–6.0 and fuel-to-mixture ratio of 15–38 mol.%) near sooting limit in terms of temperature, were investigated using a micro flow reactor with a controlled temperature profile at maximum wall temperature of 1300 K. Species measurements of O2, H2, CO, CO2, CH4, C2H2, C2H4, C2H6, benzene, toluene, styrene and naphthalene were performed with GC and GC/MS analysis. One-dimensional computations were also conducted with several detailed chemical kinetics. Most of the mechanisms comparably well predicted the smaller species except C2H2 (acetylene), which was overestimated by all the mechanism especially at moderate equivalence ratio (Ø (Formula presented.) 3.0). There were large discrepancies between measured and computed mole fractions of benzene and naphthalene at high equivalence ratio (Ø (Formula presented.) 4.0). Reaction path analysis indicated that reaction pathway branched from C2H3 reacting with methyl radical, which competes with C2H2 production, showed relatively low contribution to benzene formation at moderate equivalence ratio. Therefore, improvements of chemical kinetics with further consideration of reactions with methyl radical are necessary for precise prediction of products where abundant amounts of methyl radical exist.