Novel, High Activity Hydroprocessing Catalysts: Iron Group Phosphides

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Virginia Tech

A series of iron, cobalt and nickel transition metal phosphides was synthesized by means of temperature-programmed reduction (TPR) of the corresponding phosphates. The same materials, Fe₂P, CoP and Ni₂P, were also prepared on a silica (SiO₂) support. The phase purity of these catalysts was established by x-ray diffraction (XRD), and the surface properties were determined by N₂ BET specific surface area (Sg) measurements and CO chemisorption. The activities of the silica-supported catalysts were tested in a three-phase trickle bed reactor for the simultaneous hydrodenitrogenation (HDN) of quinoline and hydrodesulfurization (HDS) of dibenzothiophene using a model liquid feed at realistic conditions (30 atm, 370 °C). The reactivity studies showed that the nickel phosphide (Ni₂P/SiO₂) was the most active of the catalysts. Compared with a commercial Ni-Mo-S/g-Al₂O₃ catalyst at the same conditions, Ni₂P/silica had a substantially higher HDS activity (100 % vs. 76 %) and HDN activity (82 % vs. 38 %).

Because of their good hydrotreating activity, an extensive study of the preparation of silica supported nickel phosphides, Ni₂P/SiO₂, was carried out. The parameters investigated were the phosphorus content and the weight loading of the active phase. The most active composition was found to have a starting synthesis Ni/P ratio close to 1/2, and the best loading of this sample on silica was observed to be 18 wt.%.

Extended x-ray absorption fine structure (EXAFS) and x-ray absorption near edge spectroscopy (XANES) measurements were employed to determine the structures of the supported samples. The main phase before and after reaction was found to be Ni₂P, but some sulfur was found to be retained after reaction.

A comprehensive scrutiny of the HDN reaction mechanism was also made over the Ni₂P/SiO₂ sample (Ni/P = 1/2) by comparing the HDN activity of a series of piperidine derivatives of different structure. It was found that piperidine adsorption involved an a-H activation and nitrogen removal proceeded mainly by means of a b-H activation though an elimination (E2) mechanism. The relative elimination rates depended on the type and number of b-hydrogen atoms. Elimination of b-H atoms attached to tertiary carbon atoms occurred faster than those attached to secondary carbon atoms. Also, the greater the number of the b-H atoms, the higher the elimination rates. The nature of the adsorbed intermediates was probed by Fourier transform infrared spectroscopy (FTIR) and temperature-programmed desorption (TPD) of the probe molecule, ethylamine. This measurement allowed the determination of the likely steps in the hydrodenitrogenation reaction.

Hydrodenitrogenation mechanism, Hydrodenitrogenation, Hydrodesulfurization, Phosphorus effect, Iron group phosphide, EXAFS, Structure-sensitivity