Comprehensive two-dimensional gas chromatography for basic and neutral nitrogen speciation in middle distillates

Abstract The molecular knowledge of nitrogen compounds in diesel feedstocks has become a key issue in the development of hydrotreatment processes, especially for ultra-low sulfur diesel production. Indeed, nitrogen species have a strong impact on the hydrodesulfurization (HDS) pathway, since basic nitrogen is known to poison acidic sites of HDS catalysts. Since conventional methods only allow a poor degree of information, the increased separation power of comprehensive two-dimensional gas chromatography (GC × GC-NCD) was used in this study to obtain a detailed overview of nitrogen compounds by type (basic/neutral), by family and by carbon breakdown in diesel and liquefied coal samples. Partially hydrogenated compounds such as tetrahydrocarbazole and tetrahydroquinoline derivatives could even be detected in liquefied coal samples as well as diesel from ebullated bed conversion units. Comparison of GC-NCD with GC × GC-NCD for quantitative determination of nitrogen compounds by family was achieved in a first step. These results demonstrate the superiority of GC × GC to allow for a comprehensive characterization of nitrogen compounds in diesel and related samples in one injection. Furthermore, nitrogen speciation by GC × GC-NCD technique allows identifying most nitrogen species in conventional diesel or liquefied coal samples, with no use of mass spectrometry. GC × GC-NCD was also applied to a wide range of diesel feedstocks obtained from distillation, cokefaction, FCC, ebullated bed hydroconversion units to correlate nitrogen species to the origin of the feedstocks or distillation end points, giving interesting indications on reaction mechanisms involved in the processes.