Effect of 2,6-Bis-(1-hydroxy-1,1-diphenyl-methyl) Pyridine as Organic Additive in Sulfide NiMoP/γ-Al2O3 Catalyst for Hydrodesulfurization of Straight-Run Gas Oil.

The effect of 2,6-bis-(1-hydroxy-1,1-diphenyl-methyl) pyridine (BDPHP) in the preparation of NiMoP/γ-Al2O3 catalysts have been investigated in the hydrodesulfurization (HDS) of straight-run gas oil. The γ-Al2O3 support was modified by surface impregnation of a solution of BDPHP to afford BDPHP/Ni molar ratios (0.5 and 1.0) in the final composition. The highest activity for NiMoP materials was found when the molar ratio of BDPHP/Ni was of 0.5. X-ray diffraction (XRD) results revealed that NiMoP (0.5) showed better dispersion of MoO3 than the NiMoP (1.0). Fourier transform infrared spectroscopy (FT-IR) results indicated that the organic additive interacts with the γ-Al2O3 surface and therefore discards the presence of Mo or Ni complexes. Raman spectroscopy suggested a high Raman ratio for the NiMoP (0.5) sample. The increment of the Mo=O species is related to a major availability of Mo species in the formation of MoS2. The temperature programmed reduction (TPR) results showed that the NiMoP (0.5) displayed moderate metal-support interaction. Likewise, X-ray photoelectron spectroscopy (XPS) exhibited higher sulfurization degree for NiMoP (0.5) compared with NiMoP (1.0). The increment of the MoO3 dispersion, the moderate metal-support interaction, the increase of sulfurization degree and the increment of Mo=O species provoked by the BDPHP incorporation resulted in a higher gas oil HDS activity.

In situ Raman studies during sulfidation, and operando Raman-GC during ammoxidation reaction using nickel-containing catalysts: a valuable tool to identify the transformations of catalytic species.

Ni-containing catalysts are investigated under reaction conditions for two different cases, during sulfidation, with Ni-Mo based catalysts, and during ammoxidation reaction, with the Ni-Nb catalysts. It is shown how Raman spectroscopy can follow some of the transformations of these catalysts upon different treatments. For the NiMo/Al(2)O(3)-SiO(2) system it was possible to identify some of the sulfided Mo species formed during the sulfidation of the oxide precursors, while for the bulk Ni-Nb oxide catalysts the simultaneous reaction-Raman results strongly suggest that the incipient interaction between niobium and nickel oxides at low Nb/Ni atomic ratios is directly related to catalytic activity, and that a larger size well-defined NiNb(2)O(6) mixed oxide phase is not active for this reaction. Moreover, the promotion by niobium doping appears to be limited to a moderate niobium loading. It was found that in situ and operando Raman are valuable techniques that allowed the identification of active Mo-S and Ni-Nb species under reaction conditions, and that are not stable under air atmospheres.