Hydrodeoxygenation of Phenolic Compounds and Lignin Bio-Oil Surrogate Mixture over Ni/BEA Zeolite Catalyst and Investigation of Its Deactivation

Lignin is one of the main structural components of lignocellulosic biomass and can be utilized to produce phenolic compounds that can be converted downstream to cycloalkanes and aromatics, which are useful as drop-in road or aviation biofuels. Within this study, the hydrodeoxygenation of model phenolic/aromatic compounds and surrogate mixture simulating the light fraction of lignin fast-pyrolysis bio-oil was performed under mild reaction conditions. Ni/BEA zeolite was selected as a catalyst to investigate the conversion and the product selectivity of alkyl phenols (phenol, catechol, cresols), methoxy-phenols (guaiacol, syringol, creosol), aromatics (anisole, 1,2,3-trimethoxybenzene) and dimer (2-phenoxy-1-phenyl ethanol) compounds towards (alkyl)cycloalkanes. The hydrodeoxygenation of a surrogate mixture of eleven phenolic and aromatic compounds was then studied by investigating the effect of reaction conditions (temperature, time, H2 pressure, surrogate mixture concentration, and catalyst-to-feed ratio). The conversion of model compounds was in the range of 80-100%, towards a 37-81% (alkyl)cycloalkane yield, being strongly dependent on the complexity/side-chain group of the phenolic/aromatic ring. Regarding the hydrodeoxygenation of the surrogate mixture, 59-100% conversion was achieved, with up to a 72% yield of C6-C9 cycloalkanes. Characterization of spent catalysts showed that the hydrodeoxygenation of surrogate mixture led to carbonaceous depositions on the catalyst, which can be limited under lower temperatures and longer reaction conditions, while after regeneration, the physicochemical properties of catalysts can be partially recovered.