Khan, Zuhaib Ali; Hellier, Paul; Ladommatos, Nicos; Almaleki, Ahmad; (2022) Influence of Fuel Bound Oxygen on Soot Mass and Polyaromatic Hydrocarbons during Pyrolysis of Ethanol, Methyl Acetate, Acetone and Diethyl Ether. In: Margot, Xandra and Payri, Raúl and José, Ramón Serrano, (eds.) Proceedings –Thiesel 2022 Conference on Thermo- and Fluid Dynamics of Clean Propulsion Powerplants. (pp. pp. 1-14). Editorial Universitat Politècnica de València: València, Spain.

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Abstract

Air pollution has reached critical levels in many major industrial cities, endangering public health, deteriorating the environment, and causing harm to property and landscape. The particulate emissions (PM) from propulsion which contribute to air pollution vary greatly in size and composition, conveying carcinogenic polyaromatic hydrocarbons (PAHs) present on the particle surface. Although it has been found that replacing fossil fuels with renewable oxygen-bearing fuels reduces the mass of PM released, not much is known on how this change in fuel composition affects soot levels, PAH production, and toxicity during the pyrolysis processes that occur in combustion engines. Biofuels such as alcohols, esters, ethers, and ketones are considered to be potentially sustainable alternatives fuels and can be produced by various biological and thermochemical processes from a range of renewable feedstocks. The effects of these oxygenated functional groups on the soot mass and PAHs produced during pyrolysis in a laminar flow reactor were investigated quantitatively in this study. The 16 PAHs identified as priority pollutants by the US Environmental Protection Agency (EPA) were investigated in this research, with particular focus on the probable mechanisms for production of the most carcinogenic PAHs (group B). The oxygenated fuels were pyrolyzed at temperatures ranging from 1050 to 1350 0C under oxygenfree conditions with a constant carbon atom content in nitrogen of 10,000 ppm and at a consistent residence period. Both soot bound PAH collected on filter papers and gaseous PAHs collected on XAD resin were extracted using accelerated solvent extraction (ASE), with PAH identification and quantification carried out using gas chromatography combined with mass spectroscopy (GCMS). An effect of the oxygenated functional groups on soot mass was readily apparent, with consistently lower production of soot by methyl acetate, and which has a higher oxygen to carbon ratio than ethanol, acetone, and diethyl ether. At all temperatures except 1350 0C, methyl acetate pyrolysis yielded much lower GP PAH levels than acetone and diethyl ether, but somewhat higher than that from ethanol pyrolysis. The concentration of PP PAH per unit volume of gas is much lower than the corresponding GP PAH, which suggests that PP PAH that condensed onto particulate surface, subsequently experienced surface reaction and were therefore not recoverable during the extraction process. The production of pyrene via acenaphthylene was found to dominate at higher temperatures for all fuels, regardless of molecular structure. At 11500C the relative abundance of the soot particles was low, however, the toxicity of the soot particles formed was substantially higher at lower temperatures, particularly in the case of pyrolysis of methyl acetate soot.

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