The Fate of Naphthalene and n-Alkylnaphthalenes During Combustion, and an Evaluation of the Sources of these Compounds in Diesel Exhaust Emissions

Abstract

The main objective of this research was to understand the fate of naphthalene and n-alkylnaphthalenes during diesel combustion, and an evaluation of their sources in diesel exhaust emissions. This was achieved by the use of a procedure which employed a [14C]radiolabelled PAH technique and a diesel enriched fuel technique (DEFT). The combustion of diesel fuel spiked with [14C]naphthalene has shown unequivocally that 0.5% of the naphthalene contained in diesel fuel survives combustion under the engine conditions studied (2500 rpm and 50 Nm). The survived naphthalene represented 22.8% of the total recovered naphthalene, the other 77.2% was presumably pyrosynthetic in nature. The sources of the pyrosynthesised naphthalene in the emissions was investigated at 2500 rpm and 50 Nm. The previously unreported input of n-methylnaphthalenes to the pyrosynthesised naphthalene was demonstrated by combusting fuel spiked with [14C]2-methylnaphthalene. Radiolabelled 2- methylnaphthalene (0.53% of the original [14C]2-methylnaphthalene) which had survived combustion, and radiolabelled naphthalene (0.02% of the original [14C]2-methylnaphthalene), were recovered in the exhaust extracts. This showed unequivocally that 2-methylnaphthalene was converted to naphthalene in the combustion chamber. The first enrichment experiments (DEFT), in which 1- and 2-methylnaphthalene were added separately to fuel prior to combustion confirmed that demethylation of both species produced naphthalene in small yields (1.9% and 6.1% respectively). The contribution of n-alkylnaphthalenes with the alkyl group greater than methyl in length, to pyrosynthesised naphthalene contained in exhaust emissions was investigated using fuel spiked with non-radiolabelled alkyl-PAH. The major product of combustion of these compounds was 2- vinylnaphthalene, with a 0.08% conversion for 2-butylnaphthalene and a 0.01% conversion for 2- ethylnaphthalene. No dealkylated products were detected in the exhaust emissions. A mechanism for the formation of 2-vinylnaphthalene was proposed. The effect of engine speed and load on the recovery of naphthalene and the contribution of pyrosynthesised and survived naphthalene to recovered naphthalene were established using [14C]naphthalene. At all speeds and loads investigated the pyrosynthesised fraction of recovered naphthalene was shown to be dominant.