On the opposing effects of methanol and ethanol addition on PAH and soot formation in ethylene counterflow diffusion flames

An experimental and numerical analysis of the effects of methanol and ethanol addition on polycyclic aromatic hydrocarbon (PAH) and soot formation in non-premixed ethylene flames is reported here. Laser-induced incandescence (LII) and laser-induced fluorescence (LIF) techniques were used to measure soot volume fractions and relative PAH concentrations in counterflow diffusion flames, respectively. A comprehensive chemical kinetic analysis was performed by modeling soot with detailed gas-phase chemistry and a sectional method. The results showed that although both methanol and ethanol are typically regarded as clean fuels, their presence in ethylene diffusion flames had the opposite effects on PAH and soot formation. The LIF and LII signals decreased significantly as methanol fraction increased, suggesting a soot-inhibiting role for methanol. Apart from the fact that methanol addition reduced the carbon supply for soot thus having a fuel-dilution effect (methanol converted primarily to CO), the increased H₂ concentration from methanol decomposition was seen to chemically suppress incipient benzene ring formation and subsequent PAH and soot growth processes. In contrast, a small amount of ethanol addition enhanced soot formation, which was well captured by the numerical model. Reaction pathway analysis showed that ethanol decomposition produced a relatively large amount of methyl radicals, enhancing the chemical interaction between CH₃ and C₂ species and, thereby promoting the formation of propargyl and C₄ species. As a result, benzene formation was promoted through reactions between C₂H₂ and C₄ species and via C₃H₃ recombination reaction, leading sequentially to the enhancement of PAH growth and soot formation.