Catalytic Upgrading of Ethanol to 1-Butanol Biofuel Additive Using Pd/MgO-Al2O3 and Bimetallic Pd-Cu/MgO-Al2O3 Mixed Oxide Catalysts

Catalytic upgrading of bioethanol via a C–C coupling reaction is a sustainable method of producing 1-butanol, a high-performance biofuel. This reaction was studied using a flow-through microreactor system with Pd/MgO-Al2O3 and bimetallic Pd-Cu/MgO-Al2O3 mixed oxide-based catalysts in a H2 carrier gas at a pressure of 21 bar and temperatures ranging from 200 to 350 ◦C. The effect of the metal promoter(s) on the hydrogen transfer reaction steps in the overall reaction was investigated. The palladium promoter significantly improved the activity and butanol selectivity across the entire temperature range. However, the yield of liquid products decreased significantly at temperatures higher than 250 ◦C, primarily because the decarbonylation side reaction of the acetaldehyde intermediate accelerated. The promoting effect of Pd was most beneficial below 250 ◦C because the decarbonylation reaction was inhibited by the reversible poisoning effect of CO on multiple Pd sites responsible for decarbonylation. Diluting the Pd phase with Cu increased liquid yields due to gradually decreasing decarbonylation activity. However, the dehydrogenation–hydrogenation activity decreased as well, as did the promoting effect on the corresponding reaction steps in the coupling reaction. Additionally, the product distribution changed dramatically, decreasing 1-butanol selectivity, because metallic Cu can catalyze the formation of ethyl acetate and ketone products.