The formation of polycyclic aromatic hydrocarbons from the supercritical pyrolysis of 1-methylnaphthalene

Abstract

In order to better understand the pyrolytic reactions leading to the formation of polycyclic aromatic hydrocarbons (PAH) and carbonaceous solids under supercritical conditions, we have pyrolyzed the model fuel 1-methylnaphthalene (critical temperature, 499 °C; critical pressure, 36 atm) in an isothermal silica-lined stainless-steel reactor coil at 585 °C, 110 atm, and 140 s. Analysis of the reaction products by high-pressure liquid chromatography with diode-array ultraviolet-visible absorbance detection and mass spectrometric detection has led to the identification of 37 individual 2- to 7-ring PAH—fifteen of which have never before been reported as products of 1-methylnaphthalene pyrolysis. The absence, among the reaction products, of single-ring aromatics and acetylene indicates that there is no aromatic ring rupture in this reaction environment, and the structures of each of the 5- to 7-ring PAH products reveal the intactness of the two 2-ring naphthalene units required in their construction. Proposed reaction pathways involving species plentiful in the reaction environment—1-naphthylmethyl radical, methyl radical, 1-methylnaphthalene, naphthalene, and 2-methylnaphthalene—account for the formation of the observed 5- to 7-ring PAH products. These reaction pathways, along with consideration of bond dissociation energies and relative abundances of reactant species, account for the extremely high product selectivity exhibited by the observed product PAH. The detection of seven 8- and 9-ring PAH, each requiring construction from three naphthalene or methylnaphthalene units, provides evidence that the types of reaction mechanisms outlined here—for the combination of two naphthalene entities to form 5- to 7-ring PAH—are also likely to apply to the combination of three and more such entities in the formation of larger-ring-number PAH and eventually carbonaceous solids.