On-line analysis of complex hydrocarbon mixtures using comprehensive two-dimensional gas chromatography

This paper discusses the first setup for on-line qualitative and quantitative comprehensive two-dimensional gas chromatography (GC × GC) of complex hydrocarbon mixtures. A built-in 4-port 2-way valve allows switching between flame ionization detection (FID) and time-of-flight mass spectrometry (TOF-MS) between runs, without the need to cool down and vent the MS. Proper selection of GC carrier gas flow rates enables maximal agreement between the obtained chromatograms in both configurations. For on-line analysis of reactor effluents, a dedicated sampling system allows automatic sampling of the hot reactor effluent gases and immediate injection of the sample on the GC × GC. To determine a complete effluent composition in a single run of the GC × GC, a subzero oven starting temperature was employed. Modulation is started when the oven temperature reaches 40°C, thus dividing the chromatogram in a conventional 1D and a comprehensive 2D part. This work illustrates the mature and robust character of GC × GC, extending its capabilities from mere laboratory use to on-line routine analysis for industrial processes in the (petro-)chemical industry.