Determination of sulfur heterocycles in coal liquids and shale oils

Abstract

Sulfur heterocycles are found in low concentrations in most coalderived liquids and shale oils, and therefore, isolation of the heterocyclic sulfur fraction is necessary for individual compound Identification. In this report, a new methodology for the isolation and subsequent separation and identification of sulfur heterocycles is described and applied to selected coal liquids and shale oils. Identification was accomplished by sulfur-selective flame photometrk detection and comparison of mass spectral and chromatographic retention data of mixture components with standard reference compounds. Chromatographic retention data for 32 standard sulfur heterocycles were determined.

Retention behavior of isomeric polycyclic aromatic sulfur heterocycles in reversed-phase liquid chromatography

“…In recent decades, PAHs are one of the most studied groups of environmental contaminants because of their high carcinogenic and mutagenic potential [1–4]. However, their sulfur analogues, polycyclic aromatic sulfur heterocycles (PASHs), have received far less attention although their presence has been confirmed in air particulate matter [5, 6], sediments [7–9], coal liquids [10], diesel [9], heavy oil [11], crude oil [9, 11–17], shale oil [10, 12, 15, 18], coal tar [12–15, 19–21], mussels [7, 8], and fish [7, 8]. In addition, their carcinogenic and mutagenic potential have been reported [22, 23].…”

Biotransformation of benzothiophene by isopropylbenzene-degrading bacteria

“…The sequence of events that occurs following attack at the 2,3 position of the thiophene ring is less clear, but it is proposed that 2,3 dioxygenation yields a product that is both a cis-dihydrodiol and a thiohemiacetal, which as a result of this structure undergoes two competing reactions: either spontaneous opening of the ring, yielding 2'-mercaptomandelaldehyde, or oxidation by the dihydrodiol dehydrogenase to another thiohemiacetal, 2-hydroxy-3-oxo-2,3-dihydrobenzothiophene, which is not a substrate for the ring cleavage dioxygenase but which spontaneously opens to form 2-mercaptophenylglyoxaldehyde and subsequently 2-mercaptophenylglyoxalate. The yellow product, trans4[3-hydroxy-2-thienylJ-2-oxobut-3-enoate, is a structural analog of nins-o-hydroxybenzylidenepyruvate, an intermediate of the naphthalene catabolic pathway; extracts of recombinant bacteria containing zns-o-hydroxybenzylidenepyruvate hydratase-aldolase catalyzed the conversion of ans-4-[3-hydroxy-2-thienyl]-2-oxobut-3-enoate to 3-hydroxythiophene-2-carboxaldehyde, which could then be further acted on, in the presence of NAD+, by extracts of recombinant bacteria containing the subsequent enzyme of the naphthalene pathway, salicylaldehyde dehydrogenase.Sulfur-containing heterocyclic chemicals, including benzothiophene (benzo-[b]-thiophene, thianaphthene), comprise a relatively small but significant fraction of petroleum, coal, and shale (5,9,26,30,42). …”

“…Sulfur-containing heterocyclic chemicals, including benzothiophene (benzo-[b]-thiophene, thianaphthene), comprise a relatively small but significant fraction of petroleum, coal, and shale (5,9,26,30,42).…”

Geochemical Characterization of Organic Pollutants in Effluents Discharged from Various Industrial Sources to Riverine Systems

“…Two isomers of ethylbenzo(b) thiophene, a typical component of crude oil and gasoline (Brunet et al 2005;Freitas et al 2009) appeared in the effluent in relatively high content. 5-Ethylbenzo(b)thiophene has been previously determined in the USA shale oils (Willey et al 1981). 2-Ethylbenzo(b)thiophene was found as a constituent in creosote-contaminated groundwater in Norway.…”