Synthesis of etheric ester based biofuel additive over bifunctional metal/zeolite catalysts comprising NiRe nanoparticles and Beta zeolite

Biomass derived etheric ester compounds show promising applications as renewable fuel additives and solvents. In this study, we reported the preparation of bifunctional transition metal/zeolite catalysts comprising Ni-Re bimetal nanoparticles and Beta zeolites prepared via conventional wet-impregnation method. The bifunctional nature makes it possible for the synthesis of ethyl-4-ethoxy pentanoate (EEP) as etheric ester starting from ethyl levulinate (EL) in presence of H2 with good performance. The textural properties and acidity of the catalysts were characterized by several techniques: XRD, TEM, STEM-Mapping, H2-TPR and XPS. The addition of ReOx increased the dispersion and reducibility of NiO·NH3-TPD and in-situ FT-IR of pyridine adsorption confirmed that the NiReOx/Beta catalyst affords large amount of Lewis acid sites and certain amount of Bronsted acid sites. The attained Bronsted acid sites in BEA topology may be the key sites contributing to the etherification. Under optimized reaction conditions, namely 160 °C, 1 MPa H2 and reaction time of 2 h, almost full conversion of EL with 83% yield of EEP could be achieved in ethanol.