Hydro(deoxygenation) Reaction Network of Lignocellulosic Oxygenates

Hydrodeoxygenation (HDO) is a key transformation step to convert lignocellulosic oxygenates into drop-in and functional high-value hydrocarbons through controlled oxygen removal. Nevertheless, the mechanistic insights of HDO chemistry have been scarcely investigated as opposed to a significant extent of hydrodesulfurization chemistry. Current requirements emphasize certain underexplored events of HDO of oxygenates, which include 1) interactions of oxygenates of varied molecular size with active sites of the catalysts, 2) determining the conformation of oxygenates on the active site at the point of interaction, and 3) effects of oxygen contents of oxygenates on the reaction rate of HDO. It is realized that the molecular interactions of oxygenates with the surface of the catalyst dominates the degree and nature of deoxygenation to derive products with desired selectivity by overcoming complex separation processes in a biorefinery. Those oxygenates with high carbon numbers (>C10), multiple furan rings, and branched architectures are even more complex to understand. This article aims to focus on concise mechanistic analysis of biorefinery oxygenates (C10-35) for their deoxygenation processes, with a special emphasis on their interactions with active sites in a complex chemical environment. This article also addresses differentiation of the mode of interactions based on the molecular size of oxygenates. Deoxygenation processes coupled with or without ring opening of furan-based oxygenates and site-substrate cooperativity dictate the formation of diverse value-added products. Oxygen removal has been the key step for microbial deoxygenation by the use of oxygen-removing decarbonylase enzymes. However, challenges to obtain branched and long-chain hydrocarbons remain, which require special attention, including the invention of newer techniques to upgrade the process for combined depolymerization-HDO from real biomass.