Performance of Ni-rich bimetallic phosphides on simultaneous quinoline hydrodenitrogenation and dibenzothiophene hydrodesulfurization

• Ni-rich bimetallic phosphides incorporating different second metals were prepared.
• 90% HDN from quinoline and 100% HDS from dibenzothiophene were achieved over metal phosphides at 380 °C.
• Mo0.05Ni1.95P showed the highest activity and the lowest content of adsorbed N and S.
• The presence of N-containing compounds in the feed greatly inhibited complete HDS.

A series of Ni-rich bimetallic phosphides incorporating different metals were successfully prepared by initial wetness impregnation, followed by temperature-programmed reduction. Catalyst characterization indicates that the bulk structure and physical properties maintained after adding 2.5 mol% another metal on Ni2P. Electron transfer from the second metal to Ni was found on Mo0.05Ni1.95P, Co0.05Ni1.95P, and Fe0.05Ni1.95P, except on W0.05Ni1.95P. Simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene (DBT) over phosphides and a commercial metal sulfide were studied at 320–380 °C, 3 MPa, weight hourly space velocity of 6 h− 1, and H2/feed ratio of 500:1. Metal phosphides show higher HDN of quinoline and the same HDS of dibenzothiophene activities than that of a commercial catalyst at 380 °C. Mo0.05Ni1.95P shows the best performance and lowest N and S content adsorbed on the catalyst, due to the active M(2) sites. HDS conversion and product selectivities are seriously impacted by the adsorption of N-containing compounds on active sites of catalysts. Increasing temperature to 360 °C or/and decreasing N content to less than 1000 ppm quinoline in the feed are suggested to obtain simultaneous efficient removal of N and S.