Hyphenation of supercritical fluid chromatography and two-dimensional gas chromatography–mass spectrometry for group type separations

• Separation between alkenes and cyclic alkanes was achieved.
• Successful hyphenation of SFC and GC × GC–TOF with reversed column configuration.
• Group type separation of saturates, unsaturates, aromatics and oxygenates achieved.
• Comprehensive analysis separation of synthetic oil.

The Fischer–Tropsch (FT) process produces a variety of compounds over a wide carbon number range and the synthetic crude oil produced by this process is rich in highly valuable olefins and oxygenates, which crude oil only contains at trace levels. The characterization of these products is very challenging even when using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC × GC–TOF-MS). The separation between cyclic paraffins and olefins is especially difficult since they elute in similar positions on the GC × GC chromatogram and since they have identical molecular masses with indistinguishable fragmentation patterns. Previously, a high performance liquid chromatography (HPLC) fractionation procedure was used prior to GC × GC–TOF-MS analysis to distinguish between alkenes and alkanes, both cyclic and non-cyclic, however, there was co-elution of the solvents used in the HPLC fractionation procedure, and the volatile components in the gasoline sample and the dilution introduced by the off-line fractionation procedure made it very difficult to investigate components present at very low concentrations. The hyphenation of supercritical fluid chromatography (SFC) to GC × GC is less complicated and the removal of the supercritical CO2 can be easily achieved without any loss of the volatile sample components, eliminating the introduction of co-eluting solvents as well as the dilution effect. This paper describes the on-line hyphenation of SFC to a GC × GC system in order to comprehensively characterize the chemical groups (saturates, unsaturates, oxygenates and aromatics) in an FT sample.