title: Investigating comprehensive two-dimensional gas chromatography conditions to optimize the separation of oxygenated compounds in a direct coal liquefaction middle distillate.
abstract: Considering the global energetic context, diversifying fuels is of growing importance and many new alternatives are promising. Coal liquefaction products definitely appear among the new generation substitutes. These product's characteristics are very far from fuel specifications as they are mainly composed of naphthenes, aromatics, polycondensed naphthenic and aromatic structures and heteroatomic compounds (nitrogen and oxygen), with a very low paraffin content. Identification and quantification of oxygen-containing species in coal-derived liquids are of considerable importance to understand their behaviors in further processing. However, these species have not been characterized as fully as the predominant hydrocarbon components. Literature shows that these compounds consist mainly in alkylated phenolic and furanic structures. Therefore, comprehensive two-dimensional gas chromatography has been investigated to provide enhanced molecular characterization of these complex samples. Several different configurations involving innovative column configurations were tested. Each of them was optimized by testing different column lengths, modulation periods, and oven conditions. A comparison of the contribution of each column configuration was carried out regarding four main criteria: individual separation of oxygenates, group type separation, resolution, and space occupation. One of them enabled an outstanding separation of paraffins, naphthenes, monoaromatics, diaromatics and targeted O-compounds in a direct coal liquefaction product. It was therefore subjected to further experimentations using a time-of-flight mass spectrometer to validate the identification and unravel more than fifty oxygenated molecular structures. A group-type quantification was also established for four column arrangements and gives the distribution of paraffins, naphthenes and aromatics. It can be concluded from this study that a non-orthogonal arrangement involving a highly polar column in the first dimension was the most adapted one.
authors.affiliation: IFP Energies Nouvelles, Physics and Analysis, Rond Point de l'échangeue de Solaize, 69360 Solaize, France. badaoui.omais@ifp.fr
authors.forename: Badaoui
authors.initials: B
authors.lastname: Omais
authors.forename: Marion
authors.initials: M
authors.lastname: Courtiade
authors.forename: Nadège
authors.initials: N
authors.lastname: Charon
authors.forename: Didier
authors.initials: D
authors.lastname: Thiébaut
authors.forename: Alain
authors.initials: A
authors.lastname: Quignard
authors.forename: Marie-Claire
authors.initials: MC
authors.lastname: Hennion
mesh_terms: D001572:Benzofurans / Q000032:analysis / Q000737:chemistry; D002849:Chromatography, Gas / Q000295:instrumentation / Q000379:methods*; D003031:Coal / Q000032:analysis*; D057168:Distillation; D013058:Mass Spectrometry; D009930:Organic Chemicals / Q000032:analysis* / Q000737:chemistry; D010084:Oxidation-Reduction; D010636:Phenols / Q000032:analysis / Q000737:chemistry; D015203:Reproducibility of Results
chemical_list: D001572:Benzofurans; D003031:Coal; D009930:Organic Chemicals; D010636:Phenols