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To obtain direct evidence of the formation of the Ni-Mo-S phase on NiMo/Al(2)O(3) catalysts under high-pressure hydrodesulfurization conditions, a high-pressure EXAFS chamber has been constructed and used to investigate the coordination structure of Ni and Mo species on the catalysts sulfided at high pressure. The high-pressure chamber was designed to have a low dead volume and was equipped with polybenzimidazole X-ray windows. Ni K-edge k(3)chi(k) spectra with high signal-to-noise ratio were obtained using this high-pressure chamber for the NiMo/Al(2)O(3) catalyst sulfided at 613 K and 1.1 MPa over a wide k range (39.5-146 nm(-1)). The formation of Ni-Mo and Mo-Ni coordination shells was successfully proved by Ni and Mo K-edge EXAFS measurement using this chamber. Interatomic distances of these coordination shells were almost identical to those calculated from Ni K-edge EXAFS of NiMo/C catalysts sulfided at atmospheric pressure. These results support the hypothesis that the Ni-Mo-S phase is formed on the Al(2)O(3)-supported NiMo catalyst sulfided under high-pressure hydrodesulfurization conditions.

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Ni species on the spent NiMo catalyst from ultra-deep hydrodesulfurization of gas oil in a commercial plant were studied by Ni K-edge EXAFS and TEM measurement without contact of the catalysts with air. The Ni-Mo coordination shell related to the Ni-Mo-S phase was observed in the spent catalyst by quasi in situ Ni K-edge EXAFS measurement with a newly constructed high-pressure chamber. The coordination number of this shell was almost identical to that obtained by in situ Ni K-edge EXAFS measurement of the fresh catalyst sulfided at 1.1 MPa. On the other hand, large agglomerates of Ni(3)S(2) were observed only in the spent catalyst by quasi in situ TEM/EDX measurement. MoS(2)-like slabs were sintered slightly on the spent catalyst, where they were destacked to form monolayer slabs. These results suggest that the Ni-Mo-S phase is preserved on the spent catalyst and Ni(3)S(2) agglomerates are formed by sintering of Ni(3)S(2) species originally present on the fresh catalyst.

In situ Co K-edge quick-EXAFS (QEXAFS) coupled with temperature-programmed oxidation as well as ex situ XAFS was applied to investigating the mechanism for enhancing the dispersion of Co(3)O(4) nanoparticles in a calcined Co/SiO(2) Fischer-Tropsch synthesis catalyst prepared by adding triethylene glycol (TEG) to a Co(NO(3))(2).6H(2)O impregnating solution. Ex situ Co K-edge XAFS indicated that, regardless of whether the catalysts were prepared with or without using TEG, the hexaaqua Co (II) complex was formed in impregnated samples which then underwent the dehydration process to some extent during the subsequent drying step at 393 K. In situ QEXAFS and ex situ EXAFS results also indicated that small oxide clusters were formed in the TEG-modified catalyst calcined at ~400-470 K which interacted with polymer species derived from TEG. Since the Fischer-Tropsch synthesis activity of the TEG-modified catalyst increased with an increase in the calcination temperature in a similar temperature range [Koizumi et al. (2011), Appl. Catal. A, 395, 138-145], it was suggested that such an interaction enables the clusters to be distributed over the support surface uniformly, resulting in enhancing their dispersion. After combustion of polymer species, Co(3)O(4)-like species were formed, and agglomeration of the Co(3)O(4)-like species at high calcination temperatures was suppressed by the addition of TEG to the impregnating solution. It was speculated that the addition of TEG induced the formation of some surface silicate which worked as an anchoring site for Co(3)O(4) and Co(0) nanoparticles during calcination and H(2) reduction, respectively.