This paper describes the identification of nitrogen-containing compounds in a typical feed for
diesel oil hydrotreating and how their individual concentrations change upon hydrotreating over
a conventional sulfided CoMo/Al2O3 catalyst at commercial conditions. A preconcentration
procedure followed by gas chromatographic (GC) analysis utilizing a highly sensitive nitrogen-specific detector (atomic emission detector) allowed the quantitative analysis of individual
nitrogen-containing compounds (N compounds) at levels as low as 0.05 μg N/mL. The nitrogen
compounds in the feed and products were identified by comparison with reference compounds
as well as by high-resolution GC/mass spectrometric characterization. The relative reactivities
of individual compounds in the diesel fuel feed were determined and the most refractory
compounds identified. Alkyl-substituted carbazoles were found to be the major compound class
in the feed and to be among the least reactive N compounds in the feed. Just as in the case of
alkyldibenzothiophene hydrodesulfurization, carbazoles having alkyl substituents at positions
adjacent to the nitrogen atom were found to be the least reactive N compounds in the diesel
fuel feed for hydrodenitrogenation.
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11 Catalytic hydropyrolysis of beech wood was conducted in a fluid bed reactor at 450°C and a total pressure 12 of 26 bar. The differences in hydrodeoxygenation activity, selectivity and the resulting product composition 13 between sulfided Mo/MgAl 2 O 4 , CoMo/MgAl 2 O 4 or NiMo/MgAl 2 O 4 catalysts have been investigated. The 14 acidity and molybdate species in the oxide catalyst precursors were characterized with ammonia 15 temperature programmed desorption (NH 3-TPD) and Raman spectroscopy. The spent sulfided catalysts 16 were also extensively characterized by scanning electron microscopy (SEM) and by scanning transmission 17 electron microscopy (STEM) coupled with energy dispersive X-ray spectroscopy (EDS). The catalytic 18 hydropyrolysis of beech wood produced four kinds of products: Liquid organic and aqueous phases, solid 19 char and gases. The solid char and aqueous phase yields were not affected by the type of catalyst. The sum 20 of condensed organics and C 4+ gas yield varied between 24.3 and 26.4 wt.% on dry, ash free basis (daf) and 21 was highest for the Mo catalyst and lowest for the NiMo catalyst. The NiMo catalyst had the highest 22 hydrogenation, cracking, and de-carbonylation activity. The oxygen content in the condensed organic phase 23 was between 9.0 and 12 wt.% on dry basis (db) and was lowest for the CoMo catalyst and highest for the
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