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Sulfur-free molybdenum carbides have the potential to replace the conventional sulfided catalysts used for hydrotreating. For these catalysts, it is not necessary to add sulfur to maintain their activity. This fact makes it worthwhile to continue working on improving their hydrotreating efficiency. According to our previous studies, the addition of Co or Ni promotes the hydrotreating activity, but only significant in the case of hydrodesulfurization efficiency (up to 30%). To increase the hydrodenitrogenation efficiency, other promoters, such as phosphorus, can be added. However, most of the published studies do not focus on co-processing or only on hydrotreating of gas oil model molecules at a laboratory scale. In this paper, we build on our previous research by studying five sulfur-free phosphorus-modified MoCx/Al 2 O 3 catalysts (0.5, 1.5, 2.5, 3.5, and 4.5 wt %) for the hydrotreating of atmospheric gas oil and co-processing with rapeseed oil (5, 10, and 25 wt %) under industrial conditions (330-350 °C, 5.5 MPa, WHSV 1-2 h -1 ). A phosphorus content up to 1.5 wt % promoted the hydrodesulfurization (5-10%) and the hydrodenitrogenation (10-25%) efficiencies of catalysts. Moreover, the triglycerides addition did not significantly decrease the catalyst activity during co-processing. Therefore, our results enable us to define the range of phosphorus addition that enhances MoCx activity using industrial conditions and commercial feedstocks, pointing the way to develop a suitable and sulfur-free alternative to conventional hydrotreating catalysts., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

In this work, we studied the effect of molybdenum precursors and the synthesis conditions on the final phase composition of bulk and supported molybdenum carbides and nitrides. Ammonium heptamolybdate, its mixture with hexamethylenetetramine, and their complex were used as the precursors at different temperatures. It was investigated that the synthesis of the target molybdenum nitrides strongly depended on the structure of the precursor and temperature conditions, while the synthesis of carbide samples always led to the target phase composition. Unlike the carbide samples, where the α-Mo₂C phase was predominant, the mixture of β-Mo₂N, MoO₂ with a small amount of metal molybdenum was generally formed during the nitridation. All supported samples showed a very good dispersion of the carbide or nitride phases., Competing Interests: The authors declare no conflict of interest.