Synergetic Effect of Ni2P/SiO2 and γ-Al2O3 Physical Mixture in Hydrodeoxygenation of Methyl Palmitate

The Ni2P/SiO2 catalyst, which was prepared by in situ temperature-programmed reduction and in the mixture with the inert (SiC, SiO2) or acidic (γ-Al2O3) material was studied in methyl palmitate hydrodeoxygenation (HDO). Methyl palmitate HDO was carried out at temperatures of 270–330 °C, H2/feed volume ratio of 600 Nm3/m3, and H2 pressure of 3.0 MPa. Ni2P/SiO2 catalyst, diluted with γ-Al2O3 showed a higher activity than Ni2P/SiO2 catalyst diluted with SiC or SiO2. The conversion of methyl palmitate increased significantly in the presence of γ-Al2O3 most probably due to the acceleration of the acid-catalyzed reaction of ester hydrolysis. The synergism of Ni2P/SiO2 and γ-Al2O3 in methyl palmitate HDO can be explained by the cooperation of the metal sites of Ni2P/SiO2 and the acid sites of γ-Al2O3 in consecutive metal-catalyzed and acid-catalyzed reactions of HDO. The obtained results let us conclude that the balancing of metal and acid sites plays an important role in the development of the efficient catalyst for the HDO of fatty acid esters over supported phosphide catalysts

HDO of Methyl Palmitate over Silica-Supported Ni Phosphides: Insight into Ni/P Effect

Two sets of silica-supported nickel phosphide catalysts with a nickel content of about 2.5 and 10 wt % and Ni/P molar ratio 2/1, 1/1 and 1/2 in each set, were prepared by way of a temperature-programmed reduction method using (Ni(CH3COO)2) and ((NH4)2HPO4) as a precursor. The NixPy/SiO2 catalysts were characterized using chemical analysis N2 physisorption, XRD, TEM, 31P MAS NMR. Methyl palmitate hydrodeoxygenation (HDO) was performed in a trickle-bed reactor at 3 MPa and 290 °C with LHSV ranging from 0.3 to 16 h−1. The Ni/P ratio was found to affect the nickel phosphide phase composition, POx groups content and catalytic properties in methyl palmitate HDO with the TOF increased along with a decline of Ni/P ratio and a growth of POx groups’ content. Taking into account the possible routes of methyl palmitate conversion (metal-catalyzed hydrogenolysis or acid-catalyzed hydrolysis), we proposed that the enhancement of acid POx groups’ content with the Ni/P ratio decrease provides an enhancement of the rate of methyl palmitate conversion through the acceleration of acid-catalyzed hydrolysis

Support Effect on the Performance of Ni2P Catalysts in the Hydrodeoxygenation of Methyl Palmitate

The effect of support nature, SiO2 and γ-Al2O3, on physicochemical and catalytic properties of nickel phosphide catalysts in methyl palmitate hydrodeoxygenation (HDO) has been considered. Firstly, alumina-supported nickel phosphide catalysts prepared by temperature-programmed reduction method starting from different precursors (phosphate–Ni(NO3)2 and (NH4)2HPO4 or phosphite–Ni(OH)2 and H3PO3) were compared using elemental analysis, N2 physisorption, H2-TPR, XRD, TEM, NH3-TPD, 27Al and 31P MAS NMR techniques and catalytic experiments. The mixture of nickel phosphide phases was produced from phosphate precursor on alumina while using of phosphite precursor provides Ni2P formation with the higher activity in methyl palmitate HDO. Besides, the comparative study of the performances of Ni2P/SiO2 and Ni2P/Al2O3 catalysts demonstrates the apparent superiority of alumina-supported Ni2P in the methyl palmitate hydrodeoxygenation. Considering the tentative scheme of methyl palmitate transformation, we proposed that cooperation of Ni2P and acid sites on the surface of alumina provides the enhanced activity of alumina-supported Ni2P through the acceleration of acid-catalysed hydrolysis

Effect of Mono-, Di-, and Triethylene Glycol on the Activity of Phosphate-Doped NiMo/Al2O3 Hydrotreating Catalysts

The effect of glycols on the catalytic properties of phosphate-doped NiMo/Al2O3 catalysts in the hydrotreating of straight-run gas oil (SRGO) was studied. The NiMo(P)/Al2O3 catalysts were prepared using ethylene glycol (EG), diethylene glycol (DEG), and triethylene glycol (TEG) as additives. The organic agent was introduced into the aqueous impregnation solution obtained by the dissolving of MoO3 in H3PO4 solution, followed by Ni(OH)2 addition. The Raman and UV–Vis studies show that the impregnation solution contains diphosphopentamolybdate HxP2Mo5O23(6−x)− and Ni(H2O)62+, and that these ions are not affected by the presence of glycols. When the impregnation solution comes in contact with the γ-Al2O3 surface, HxP2Mo5O23(6−x)− is decomposed completely. The catalysts were characterized by Raman spectroscopy, low-temperature N2 adsorption, X-ray photoelectron spectroscopy, and transmission electron microscopy. It is shown that the sulfide catalysts prepared with glycols display higher activity in the hydrotreating of straight-run gas oil than the NiMoP/Al2O3 catalyst prepared without the additive. The hydrodesulfurization and hydrodenitrogenation activities depend on the glycol type and are decreased in the following order: NiMoP-DEG/Al2O3 > NiMoP-EG/Al2O3 > NiMoP-TEG/Al2O3 > NiMoP/Al2O3. The higher activity of NiMoP-DEG/Al2O3 can be explained with the higher dispersion of molybdenum on the surface of the catalyst in the sulfide state