Upgrading of biomass-derived 2-hexanol to liquid transportation fuels on Cu–Mg–Al mixed oxides. Effect of Cu content

• Cu–Mg–Al mixed oxides promote 2-hexanol upgrading to liquid fuels.
• C9–C24 oxygenates and hydrocarbons are main products.
• ∼70% of the products are C9–C15 compounds for jet fuel applications.
• Product quality depends on the Cu content.
• Reaction mechanism changes with the base/metal site ratio.

The gas-phase synthesis of high molecular weight compounds of application as liquid transportation fuels from 2-hexanol was studied on Cu–Mg–Al mixed oxides with different copper content (0.3–61.2%) and a Mg/Al = 1.5 M ratio. Catalysts were prepared by coprecipitation and characterized by several techniques such as BET surface area, XRD, TPD of CO2, TPR and N2O decomposition. Yields of up to 87% were obtained for compounds in the C9–C24 range, ≈80% of which were suitable as jet fuels and the rest as diesel substitutes. This product pool was a hydrophobic mixture of ketones, alcohols and hydrocarbons with 160–200 g/mol average molecular weight and an O/C atomic ratio as low as 0.04. Because low copper content catalysts are hard to reduce, on these materials the reaction occurs via a base-catalyzed mechanism involving consecutive dehydrogenation, CC bond formation, dehydration and hydrogenation steps, that forms mainly even carbon atom number products. Partially reduced Cun+ atoms contribute to promote a distinct pathway toward odd products. In contrast, on high copper content oxides the reaction yields similar amounts of even and odd products and proceeds by a bifunctional Cu0-base mechanism in which the CC coupling is rate-limiting.

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