Precursor-Driven Catalytic Performances of Al2O3-Supported Earth-Abundant Ni Catalysts in the Hydrogenation of Levulinic Acid and Hydroxymethylfurfural into Added-Value Chemicals.

It has been shown that the nature of the metal precursor and the thermal effects during calcination determine the physicochemical properties of the catalysts and their catalytic activity in the levulinic acid (LA) and 5-hydroxymethylfurfural (HMF) hydrogenation reactions. The endothermic effect during calcination of the inorganic nickel precursor promoted higher metal dispersion and stronger interaction with the alumina surface. In contrast, the exothermic effects during the calcination of organic nickel precursors resulted in smaller metal dispersion and lower interaction with the support surface. A clear relationship was found between the size of the metal crystallites and the yield of LA hydrogenation reaction. The smaller crystallites were more active in the LA hydrogenation reaction. In turn, the size of the metal particles and their nature of interaction with the surface of the alumina influence the hydrogenation pathways of the HMF.

Biodiesel Production by Methanolysis of Rapeseed Oil-Influence of SiO2/Al2O3 Ratio in BEA Zeolite Structure on Physicochemical and Catalytic Properties of Zeolite Systems with Alkaline Earth Oxides (MgO, CaO, SrO).

Alkaline earth metal oxide (MgO, CaO, SrO) catalysts supported on BEA zeolite were prepared by a wet impregnation method and tested in the transesterification reaction of rapeseed oil with methanol towards the formation of biodiesel (FAMEs-fatty acid methyl esters). To assess the influence of the SiO2/Al2O3 ratio on the catalytic activity in the tested reaction, a BEA zeolite carrier material with different Si/Al ratios was used. The prepared catalysts were tested in the transesterification reaction at temperatures of 180 °C and 220 °C using a molar ratio of methanol/oil reagents of 9:1. The transesterification process was carried out for 2 h with the catalyst mass of 0.5 g. The oil conversion value and efficiency towards FAME formation were determined using the HPLC technique. The physicochemical properties of the catalysts were determined using the following research techniques: CO2-TPD, XRD, BET, FTIR, and SEM-EDS. The results of the catalytic activity showed that higher activity in the tested process was confirmed for the catalysts supported on the BEA zeolite characterized by the highest silica/alumina ratio for the reaction carried out at a temperature of 220 °C. The most active zeolite catalyst was the 10% CaO/BEA system (Si/Al = 300), which showed the highest triglyceride (TG) conversion of 90.5% and the second highest FAME yield of 94.6% in the transesterification reaction carried out at 220 °C. The high activity of this system is associated with its alkalinity, high value of the specific surface area, the size of the active phase crystallites, and its characteristic sorption properties in relation to methanol.