Hydrodeoxygenation–Isomerization of Methyl Palmitate over SAPO-11-Supported Ni-Phosphide Catalysts

Ni-phosphide catalysts on SAPO-11 were studied in the hydrodeoxygenation–isomerization of methyl palmitate (C15H31COOCH3—MP). The catalysts were synthesized using temperature-programmed reduction (TPR) of a phosphate precursor ((NH4)2HPO4 and Ni(CH3CH2COO)2), TPR of a phosphite precursor (H3PO3 and Ni(OH)2), and using phosphidation of Ni/SAPO-11 by PPh3 in the liquid phase. The samples were characterized by ICP-AES chemical analysis, N2 physisorption, NH3-TPD, XRD, and TEM. First, the screening of the catalysts prepared by the TPR method was carried out in a semi-batch autoclave to determine the influence of the preparation method and conditions on one-pot HDO–isomerization (290–380 °C, 2–3 MPa). The precursor’s nature and the amount of phosphorus strongly influenced the activity of the catalysts and their surface area and acidity. Isomerization occurred only at a low P content (Ni/P = 2/1) and blocking of the SAPO-11 channels by unreduced phosphates at higher P contents did not allow us to obtain iso-alkanes. Experiments with liquid phosphidation samples in a continuous-flow reactor also showed the strong dependence of activity on phosphidation duration as well as on Ni content. The highest yield of isomerized products (66% iso-C15–16 hydrocarbons, at complete conversion of O-containing compounds, 340 °C, 2 MPa, and LHSV = 5.3 h−1) was obtained over 7% Ni2P/SAPO-11 prepared by the liquid phosphidation method

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

Effect of Phosphorus Precursor, Reduction Temperature, and Support on the Catalytic Properties of Nickel Phosphide Catalysts in Continuous-Flow Reductive Amination of Ethyl Levulinate

Levulinic acid and its esters (e.g., ethyl levulinate, EL) are platform chemicals derived from biomass feedstocks that can be converted to a variety of valuable compounds. Reductive amination of levulinates with primary amines and H2 over heterogeneous catalysts is an attractive method for the synthesis of N-alkyl-5-methyl-2-pyrrolidones, which are an environmentally friendly alternative to the common solvent N-methyl-2-pyrrolidone (NMP). In the present work, the catalytic properties of the different nickel phosphide catalysts supported on SiO2 and Al2O3 were studied in a reductive amination of EL with n-hexylamine to N-hexyl-5-methyl-2-pyrrolidone (HMP) in a flow reactor. The influence of the phosphorus precursor, reduction temperature, reactant ratio, and addition of acidic diluters on the catalyst performance was investigated. The Ni2P/SiO2 catalyst prepared using (NH4)2HPO4 and reduced at 600 °C provides the highest HMP yield, which reaches 98%. Although the presence of acid sites and a sufficient hydrogenating ability are important factors determining the pyrrolidone yield, the selectivity also depends on the specific features of EL adsorption on active catalytic sites

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