Effect of water on HDS of DBT over a dispersed Mo catalyst using in situ generated hydrogen

A novel process was developed for the bitumen emulsion upgrading, wherein emulsion breaking and upgrading occurred in the same reactor using H₂ generated in situ from the water in the emulsion via the water gas shift reaction (WGSR). In this study, dibenzothiophene (DBT) was chosen as a model compound to investigate the effect of water and in situ H₂ on hydrodesulfurization (HDS). All the experiments were performed in a 1-L autoclave reactor at temperatures between 300 and 380 °C using in situ H₂ and ex situ H₂ (externally supplied H₂) over a dispersed Mo catalyst formed from phosphomolybdic acid (PMA). At very low water content, water was found to promote the HDS reaction in the ex situ H₂ run probably because it facilitates the formation of more active dispersed MoS_x species. At higher water content, however, water inhibits every individual reaction in the reaction network in the HDS of DBT, blocking the hydrogenation pathway more than the hydrogenolysis pathway. The relative reactivity of the in situ and ex situ H₂ depends on the water content present in the reaction system. At an optimized mole ratio of H₂O:CO (1.35), higher HDS activity was observed in the in situ H₂ run compared to ex situ H₂ run, and particularly, the hydrogenation pathway was promoted in the in situ H₂ run.