Application of Magnetic Resonance Imaging and Raman Imaging to study the impact of phosphorus in impregnation of hydrotreatment catalysts
Résumé
Magnetic Resonance Imaging is applied, for the first time, to monitor in-situ the impregnation step of hydrotreatment catalysts with an aqueous solution composed simultaneously of molybdenum, cobalt and phosphorus. This technique provides information about spatial distribution of all metal precursors inside the catalyst pellet with a significantly improved spatial resolution of 39 μm × 39 μm compared to the literature. Streamline Raman Imaging yields complementary information about molybdenum speciation at equilibrium. For a molybdenum based catalyst, a slow transport of molybdenum complexes through γ-alumina is observed by Magnetic Resonance Imaging, which suggests a strong interaction between metal precursor and the support. Presence of polymeric molybdenum ions is found near the edges as well as the formation of an Anderson-type heteropolyanion. In the presence of phosphorus, interaction between molybdenum and γ-alumina is weaken since a preferential adsorption to phopshorus is observed. This phenomenon results in an increase in the transport rate of molybdenum complexes. When phosphorus is added to a molybdenum based catalysts promoted by cobalt, preferential interactions between metal promotor and the support are observed rather than with molybdenum species. This innovative Magnetic Resonance Imaging −Streamline Raman Imaging methodology allows a better control of the deposition process during impregnation and to identify the descriptors that most influence this preparation step. Finally, this methodology can be applied to other type of supported catalysts.