ABSTRACT
The structure of oxidic precursors of supported NiMo hydrodesulfurization catalysts has been investigated indepth by the combination of laser Raman spectroscopy and Xray absorption spectroscopy measured at the Mo and Ni K edges at the different stages of the preparation. The oxidic catalysts were prepared by incipient wetness impregnation of δ-alumina with a solution obtained by dissolving MoO3 in H2O2 and subsequently adding Ni(NO3)2·6H2O in this asprepared solution (8 wt % MoO3; 2 wt % NiO). The formation of the 6-molybdoaluminate Anderson-type heteropolyanion (AlMo6O24H6) 3− and of a mixture of oxo−hydroxo nickel species and bulk and/or surface NiAl-layered double hydroxide dispersed at the surface of the support has been identified after drying. Upon further thermal treatment at 723 K under dried air, calcined dehydrated catalyst is constituted of highly distorted isolated or partially condensed tetrahedral Mo units with terminal mono-oxo groups and of bulk and/or surface NiAl2O4-type and NiO-type species. After further exposure of the calcined catalyst to air moisture, a partial recovery of the Anderson-type molybdenum heteropolyanion and NiAl-layered double hydroxide species is evidenced by X-ray absorption spectroscopy. The nature and dispersion of active species formed after sulfidation under H2S/H2 of the different oxidic catalysts (dried-NiMo, dehydrated-calcined NiMo, and calcined-NiMo samples) are finally discussed in light of the structure of the parent oxidic precursors.
