Furfural is a biomass-derived chemical that is commercially produced at quantities greater than 300,000 tons/year and can serve as a good model compound for many species produced from pyrolysis oils. Through hydrogenation and hydrogenolysis, furfuryl alcohol and 2-methyl furan can be formed, respectively. Traditionally, the hydrogenation and hydrogenolysis is performed thermochemically using externally-supplied high pressure hydrogen gas. To decarbonize the process by eliminating externally-supplied hydrogen and steam or direct-fired reactors, the electrochemical hydrogenolysis and hydrogenation (ECH) can be performed at ambient conditions with aqueous electrolytes as the proton source. ECH can also be more amenable to the distributed, small scales needed for biorefineries. Before furfural ECH can be realized commercially, the reaction mechanism and kinetics need to be better understood. To be able to produce 2-methyl furan, a biofuel candidate, acidic electrolytes and copper catalysts are necessary. The acidic electrolytes also promote side reactions with the furanic species leading to formation of humins and fouling of the electrocatalyst. Through detailed electrolysis studies, the ECH towards furfuryl alcohol and 2-methyl furan was found to follow a non-competitive Langmuir-Hinshelwood-type mechanism with the key intermediates differing for the hydrogenation and hydrogenolysis products. To further understand the wholistic kinetics of the reaction system, the kinetics of the humin formation in the electrolyte and fouling of the electrode were also investigated and found to be pH-dependent.

Kinetics of electrochemical hydrogenation and hydrogenolysis of furfural and its side reactions in acidic electrolytes on copper catalysts

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