title: Liquid chromatographic properties of aromatic sulfur heterocycles on a Pd(II)-containing stationary phase for petroleum analysis.
abstract: Polycyclic aromatic sulfur heterocycles (PASHs) can show very poor reactivities in catalytic hydrodesulfurization processes in refineries, especially those in high-boiling fractions and distillation residues. An insight into the structural features of the most recalcitrant PASHs is essential for developing more efficient catalysts and improving refinery processes. The very high complexities of such mixtures necessitate fractionation of the samples into smaller subsets according to defined criteria. A stationary phase containing a palladium(II)-complex was previously shown to be efficient for separating PASHs in lighter petroleum fractions. Here we characterize this ligand exchange chromatographic phase using a large number of sulfur aromatic model compounds that were synthesized for the purpose. In general, compounds containing thiophene rings that are not condensed with other aromatic systems are weakly retained and elute in a first fraction with the polycyclic aromatic hydrocarbons. Thiophene rings condensed with other aromatic rings are more strongly retained and elute in a later fraction with a more polar eluent. If the sulfur is in a non-aromatic ring, the compound is irreversibly retained by the Pd(II) ions. Some steric effects are seen in compounds with alkyl or aryl substituents close to the sulfur atom but in general they do not interfere strongly with the complexation. Thus it seems possible to separate groups of aromatic sulfur compounds according to their complexation properties. For instance, such fractionated samples can be studied much more easily by mass spectrometric techniques.
authors.affiliation: Institute of Inorganic and Analytical Chemistry, NRW International Graduate School of Chemistry, University of Münster, Corrensstrasse 30, 48149 Muenster, Germany.
authors.forename: Kishore
authors.initials: K
authors.lastname: Sripada
authors.forename: Jan T
authors.initials: JT
authors.lastname: Andersson
mesh_terms: D002853:Chromatography, Liquid / Q000379:methods; D005782:Gels / Q000138:chemical synthesis / Q000737:chemistry; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006841:Hydrocarbons, Aromatic / Q000737:chemistry*; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010578:Petroleum / Q000032:analysis*; D012680:Sensitivity and Specificity; D012822:Silicon Dioxide / Q000138:chemical synthesis / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry*
chemical_list: D005782:Gels; D006571:Heterocyclic Compounds; D006841:Hydrocarbons, Aromatic; D009942:Organometallic Compounds; D010578:Petroleum; D010165:Palladium; D013455:Sulfur; D012822:Silicon Dioxide