Stable and selective multi-porous nickel nanoparticles catalysts for hydrocracking of dibenzyl ether supported by DFT studies

Abstract

Preparation of clean fuel from biomass has a crucial significance on the development and utilization of renewable clean energy. In this study, a multi-stage porous mordenite supported nickel nanoparticles catalyst (Nix%/HMOR) was prepared, which showed that its acid content, acidity, porosity, specific surface area and metal dispersion were significantly improved while the crystallization strength was basically the same compared with microporous mordenite. In order to study the conversion mechanism of biomass energy, dibenzyl ether was selected as a typical lignin model compound. Under the condition of Ni10%/HMOR in n-hexane at 160 °C for 2 h under 5 MPa of initial hydrogen pressure, the conversion of dibenzyl ether was 100 % and the selectivity of methyl cyclohexane was 84.4 %, which manifested that Ni10%/HMOR had good activity in the selective hydrocracking process under mild conditions. Furthermore, density functional theory (DFT) was selected to study the activation energies of different reaction sites on dibenzyl ether bridge bonds and the recombination process of free radicals in the reaction process. It comes to a conclusion that the O atom on the C-O bridge bond is easier to be attacked by H*, and the C-O bond of the unsaturated aromatic ring is easier to break. During the recombination of free radicals, the two C-O bond breaking energy barriers of OMD are different, and H free radicals are more likely to attack the O atom in cyclohexane-methanol. It is conducive to the formation of stable compound 1 - (cyclohexylmethyl) − 1-methylcyclohexane and its isomers.

Keywords

• Ni-nanoparticles catalysts
• Dibenzyl ether
• Hydrogenolysis
• Computational studies