The successful implementation of catalytic biomass upgrading processes requires the formation of new C-C bonds between platform molecules. In this work, we present a homogeneous and a heterogeneous system for the tandem dehydrogenation-aldol condensation reaction of furfural with aliphatic alcohols. In the Ni-based homogeneous system, we investigate the effects of the ligand and the Ni precursor on the rate of transfer hydrogenation of furfural and on the subsequent aldol condensation reaction. We show that phosphine-based ligands hinder the formation of the active O-coordinated Ni complex from the initial Ni(PR3)2Cl2precursors. In the heterogeneous system, which is based on an MgAlOx mixed oxide, we show that the transfer of the alpha hydrogen from a bound alkoxide to a furfural is kinetically relevant. This conclusion is based on kinetic isotope effect measurements and on the effects of reactant concentration on the reaction rates. We further show that the surface is mostly covered by alkoxides derived from the aliphatic alcohols and, consistent with literature, that the surface coverage of oxygenates is related to their acid strength, with aldehydes binding more strongly than alcohols. Finally, we discuss engineering aspects of the potential use of this catalytic system for the production of chemicals (especially detergent precursors) and fuels. We present possible solutions to mass transfer limitation and deactivation challenges under industrially relevant conditions and discuss potential separation and hydrodeoxygenation processes downstream of the C-C bond formation step.

Homogeneous and heterogeneous catalysis for aldol condensation of furfural with aliphatic alcohols

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.