title: Comparison between pre-fractionation and fractionation process of heavy gas oil for determination of sulfur compounds using comprehensive two-dimensional gas chromatography.
abstract: The separation of the organic sulfur compounds (OSC) of petroleum or its heavy fractions is a critical step and is essential for the correct characterization of these compounds, especially due to similar physical and chemical properties of polycyclic aromatic sulfur heterocycles (PASH) and polycyclic aromatic hydrocarbons (PAH). This similarity results in coelutions among PAH and PASH and for this reason former steps of fractionation are required before gas chromatographic analysis. The objective of this study was to evaluate the potential of GC×GC for the separation and identification of OSC in a heavy gas oil sample without fractionation, after pre-fractionation in an alumina column and also after fractionation process. This last one was performed with a modified stationary phase manufactured and characterized in the laboratory, called Pd(II)-MPSG, where palladium is chemically linked to silica through mercaptopropyl groups. The fractions obtained from both procedures were analyzed by GC×GC/TOFMS, which was effective to separate and identify various classes of OSC. A hundred and thirty-five compounds were tentatively identified in the sample that was only pre-fractionated. However, when the fractionation was also performed with the Pd(II)-MPSG phase, a larger number of sulfur compounds were found (317). Results have shown that the analysis of a pre-fractionated sample by GC×GC/TOFMS is suitable when the goal is a general characterization of classes of compounds in the sample, while a more detailed analysis of PASH can be performed, using also the fractionation Pd(II)-MPSG phase. GC×GC/TOFMS played a major role in the comparison of samples obtained from pre-fractionation and fractionation steps due to its high peak capacity, selectivity, organized distribution of chromatographic peaks and resolution.
authors.affiliation: LAAO - Laboratório de Química Analítica Ambiental e Oleoquímica, Universidade Federal do Rio Grande do Sul, Brazil.
authors.forename: Maria Elisabete
authors.initials: ME
authors.lastname: Machado
authors.forename: Lucas Panizzi
authors.initials: LP
authors.lastname: Bregles
authors.forename: Eliana Weber
authors.initials: EW
authors.lastname: de Menezes
authors.forename: Elina Bastos
authors.initials: EB
authors.lastname: Caramão
authors.forename: Edilson Valmir
authors.initials: EV
authors.lastname: Benvenutti
authors.forename: Cláudia Alcaraz
authors.initials: CA
authors.lastname: Zini
mesh_terms: D000537:Aluminum Oxide / Q000737:chemistry; D005591:Chemical Fractionation / Q000379:methods; D002849:Chromatography, Gas / Q000379:methods*; D008024:Ligands; D010165:Palladium / Q000737:chemistry; D010578:Petroleum / Q000032:analysis*; D058428:Silica Gel / Q000737:chemistry; D013457:Sulfur Compounds / Q000032:analysis / Q000302:isolation & purification*
chemical_list: D008024:Ligands; D010578:Petroleum; D013457:Sulfur Compounds; D010165:Palladium; D058428:Silica Gel; D000537:Aluminum Oxide; C008756:palladium chloride