Catalytic activity of unsupported (Mo-W)S2 catalysts in hydrodesulfurization

PETR 15

Amelia Olivas, aolivas@ccmc.unam.mx1, G. Alonso2, and Sergio Fuentes, fuentes@ccmc.unam.mx1. (1) Departamento de Catálisis, Centro de Ciencias de la Materia Condensada, Universidad Nacional Autónoma de México, Apdo. Postal 2681, Ensenada, Baja California, Mexico, (2) Centro de Investigación en Materiales Avanzados, Miguel de Cervantes No 120, Chihuahua, Chih. C.P. 3, Mexico
Unsupported (Mo-W)S2 sulfide catalyst derived from (NH4)2 (Mox-W1-x) S4 (ATMW) bimetallic thiosalts precursors were prepared. The ATMW complexes were obtained from ammonium heptamolybdate and ammonium metatungstate in ammonia solutions in contact with flowing H2S gas. Bimetallic thiosalts with Mo/ (Mo+W) atomic ratios (R1) = 0.75, 0.85 and 0.95 (experimental values) were prepared. Activation of precursors as catalysts was made ex situ by treating the ATMW bimetallic precursor in 15% H2S/H2 gas mixtures at 400 °C four hours. The catalytic activity in the HDS of DBT was evaluated in a batch reactor at 623 K and 3.1 MPa. The (Mo-W)S2 bimetallic samples showed similar catalytic properties (5 - 5.8 x 10-7 mol/s.g) among them but higher activity and selectivity for hydrogenation than MoS2 (4 - 4.5 x 10-7 mol/s.g). Comparing these samples against the NiMoW trimetallic catalysts (23 x 10-7 mol/s.g), reported not long ago, we observed a lower activity but higher selectivity to hydrogenation. We conclude that a small synergistic effect due to addition of W in MoS2 occurred, however it is much smaller than the effect obtained when Ni is added as in the case of trimetallics.