Characterization and thiophene hydrodesulfurization activity of amorphous-silica–alumina-supported NiW catalysts

The influence of the preparation method and sulfidation conditions on the structure and activity of ASA-supported NiW catalysts was investigated by a combination of 57Co Mössbauer emission spectroscopy (MES), transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS), and thiophene hydrodesulfurization (HDS) activity measurements. Ni is sulfided already at low temperatures. This nickel sulfide phase redisperses at higher temperatures over the edges of WS2 particles to form “Nisingle bondWsingle bondS”-type phases. The formation of such highly active phases is facilitated by the partial transformation of intermediate WOxSy phases to WS2 (W image edge XAS) at 673 K. In addition to this “Cosingle bondMosingle bondS” analogue nickel sulfide particles are present in dispersed form close to an oxysulfidic tungsten phase. It is found that the sulfidation of NiW/ASA closely resembles that of NiW/Al2O3. Trends in the HDS activity as a function of catalyst pretreatment were evaluated. A higher calcination temperature (from 673 to 823 K) decreases the HDS performance stemming from a lower W sulfidation degree and a more dominant presence of small oxysulfidic tungsten particles. Increasing the sulfidation pressure from atmospheric pressure to 15 bar leads to a strong increase of the HDS activity. Whereas sulfidation at 923 K results in a well-crystallized WS2 phase (XAS), the concomitant loss in dispersion (TEM) is detrimental to its performance. Moreover, indications are found that more complete crystallization of the WS2 phase results in a lower activity.