The effects of oxygen on the yields of polycyclic aromatic hydrocarbons formed during the pyrolysis and fuel-rich oxidation of catechol

To better understand the effects of oxygen on the formation and destruction of polycyclic aromatic hydrocarbons (PAH) during the burning of complex solid fuels, we have performed pyrolysis and fuel-rich oxidation experiments in an isothermal laminar-flow reactor, using the model fuel catechol (ortho-dihydroxybenzene), a phenol-type compound representative of structural entities in coal, wood, and biomass. The catechol pyrolysis experiments are conducted at a fixed residence time of 0.3 s, at nine temperatures spanning the range of 500–1000 °C, and under varying oxygen ratios ranging from 0 (pure pyrolysis) to 0.92 (near stoichiometric oxidation). The PAH products, ranging in size from two to nine fused aromatic rings, have been analyzed by gas chromatography with flame-ionization and mass spectrometric detection, and by high-pressure liquid chromatography with diode-array ultraviolet-visible absorbance detection. The quantified PAH products fall into six structural classes: benzenoid PAH, indene benzologues, fluoranthene benzologues, cyclopenta-fused PAH, ethynyl-substituted PAH, and methyl-substituted PAH. A comparison of product yields from pyrolysis and fuel-rich oxidation of catechol reveals that at temperatures <800 °C, where only two-ring PAH are produced in significant quantities, increases in oxygen concentration bring about increases in yields of the two-ring aromatics indene and naphthalene. At temperatures >800 °C, increases in oxygen concentration bring about dramatic decreases in the yields of all PAH products, due to oxidative destruction reactions. The smaller-ring-number PAH are produced in higher abundance under all conditions studied, and the oxygen-induced decreases in the yields of PAH are increasingly more pronounced as the PAH ring number is increased. These observations regarding PAH ring number, from the fuel-rich oxidation experiments with catechol, fully support our finding from catechol pyrolysis in the absence of oxygen: that PAH formation and growth occur by successive ring-buildup reactions involving the C1–C5 and single-ring aromatic products of catechol’s thermal decomposition. The yield/temperature data reported here represent one of the most extensive quantifications of the effects of oxygen on PAH produced during the pyrolysis of any fuel.