Understanding how hydrotreating oxygen-containing compounds together with nitrogen-containing compounds affects the reactivity and selectivity is relevant for processing renewable feedstocks. In this work, competitive hydrodeoxygenation (HDO) and hydrodenitrogenation (HDN) reactions were studied by co-hydrotreating palmitic acid (C16 acid) and tetradecylamine (C14 amine) over a Pt/ZrO2 catalyst in a batch reactor. HDO proceeded faster than HDN in the studied system, and the deoxygenation reactions were found to have an inhibitory effect on HDN. Co-hydrotreating the C16 acid and the C14 amine expanded the reaction network from the individual HDO and HDN networks and changed the prevailing reaction pathways, initially in favor of oxygen removal. The formation of heavy secondary amides and amines through condensation reactions became increasingly favored as the share of C16 acid in the feed increased. For a given conversion level, the condensation product selectivity was observed to increase as the reaction temperature was decreased, whereas increasing the reaction temperature promoted the formation of the desired paraffins. This work described the ease of HDO compared to HDN, the role of condensation reactions in the co-hydrotreating reaction network, and the inhibitory effect on HDN thereof.
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