Polycyclic aromatic hydrocarbons production from the supercritical pyrolysis of n-decane, ethylcyclohexane, and n-decane/ethylcyclohexane blends

Abstract

To investigate the effects of fuel composition on the production and growth of polycyclic aromatic hydrocarbons (PAH) at conditions relevant to the pre-combustion environment of fuels in future high-speed aircraft, we have conducted supercritical pyrolysis experiments in an isothermal, silica-lined stainless-steel flow reactor at 568 °C, 94.6 atm, and 133 s, with the model fuels n-decane and ethylcyclohexane—as well as n-decane/ethylcyclohexane blends in which the fraction of fuel carbon coming from ethylcyclohexane is 0.25, 0.50, and 0.75. High-pressure liquid-chromatographic analyses of the reaction products have led to the isomer-specific identification and quantification of 169 three- to nine-ring PAH—159 of which have never before been reported as products of a cyclic-alkane fuel. Quantification of the aliphatic products by gas chromatographic techniques reveals that n-decane produces mostly 1-alkenes and n-alkanes, whose radicals generate more radicals; whereas ethylcyclohexane produces mostly C5-ring and C6-ring alkanes and alkenes, whose radicals show a propensity for ring dehydrogenation. These contrasts in the aliphatic-product distributions have major impacts on PAH growth, which, in this reaction environment, occurs chiefly through the reactions of resonance-stabilized arylmethyl radicals with the C2-C4 1-alkenes. For fuel compositions rich in n-decane, all the ingredients necessary for these PAH-growth reactions to thrive are in place: methyl-substituted PAH, as sources of arylmethyl radicals; a radical-rich environment that fosters H abstraction and arylmethyl-radical formation; and C2-C4 1-alkenes, as growth species. However, an increase in the level of ethylcyclohexane in the fuel brings about substantial reductions in the levels of H-abstracting radicals and C2-C4 1-alkenes as well as an increase in the supply of “donated” hydrogen for stabilizing radicals. These factors combine to bring about marked reductions in PAH growth at fuel compositions rich in ethylcyclohexane, resulting in much lower production of the high-ring-number PAH that are the precursors to solids in the supercritical fuel-pyrolysis environment.