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Transition metal nitrides, carbides and phosphides have the potential to replace the expensive and hazardous catalysts typically used for the conversion of fatty acids. However, there has been little research on the influence of treatment conditions and precursor nature on the properties of such catalytic systems. To better understand these dependencies, we synthesized a number of Mo catalysts by temperature‐programmed reduction (700‐900 °C; CH4/N2, N2/H2) using ammonium heptamolybdate, diammonium phosphate and hexamethylenetetramine (HMT) as Mo, C, N and P sources. The presence of HMT in the precursor mixtures ensured the synthesis of pure phase Mo2C, Mo2N and MoP. Catalytic activity in the (hydro)deoxygenation of stearic acid (240 min; 360 °C; 50 bar of H2) decreased in the following order: Mo2C>Mo2N>MoP. However, all of the studied Mo‐based catalysts showed good deoxygenation efficiency and, thus, represent excellent alternatives to traditional noble and sulfur‐containing catalysts. [ABSTRACT FROM AUTHOR]

• Nitridation temperature play a crucial role in catalyst properties and activity. • At the optimised conditions, Co-Mo nitride catalyst show a HDS efficiency up to 99.0%. • At the optimised conditions, Co-Mo nitride catalyst show a HDN efficiency up to 84.0%. Sulfur-free transition metal carbide and nitride catalysts have been shown to be reasonable substitutes for sulfidic catalysts for the hydrotreating middle distillates and vegetable oils. However, their catalyst activity is still lower than commercial catalysts. In this paper, we build on our previous research by studying the synthesis and testing of nine sulfur-free Al 2 O 3 -supported Co-Mo nitride catalysts for the hydrotreating of atmospheric gasoil and its blends with rapeseed oil (25 wt.%) under industrial conditions (330–350 °C, 5.5 MPa, WHSV 1–2 h−1). Nitration temperatures play the most significant role in the synthesis and activity of the catalyst, obtaining a CoMoNx catalyst whose catalytic behaviour competes with the current commercial sulfidic Ni-Mo or Co-Mo catalysts (reduction of sulfur and nitrogen content up to 99.0 and 84.0%, respectively). Thus, our results allow us to evaluate and define the most suitable synthesis conditions for preparing high activity sulfur-free Al 2 O 3 -supported Co-Mo nitride catalysts. [Display omitted] [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]