Three different multiphase systems (MP 1-3) comprised of two immiscible liquids, with or without an ionic liquid (IL: methyltrioctyl ammonium chloride), were investigated for the oxidation of 5-hydroxymethyl-furfural (HMF) over 5 % Ru/C as a catalyst and air (8 bar) as an oxidant. These conditions proved versatile for an excellent control of the reaction selectivity to 4 distinct products derived from full or partial oxidation of the carbonyl and alcohol functions of HMF, and each one achieved in 87-96 % isolated yield at complete conversion. MP1 based on water and isooctane, yielded 2,5-furandicarboxylic acid (FDCA, 91 % yield). In MP2, obtained by adding the IL to MP1, the oxidation proceeded towards the formation of 5-formyl-2-furancarboxylic acid (FFCA, 87-89 % yield). MP2 also proved successful in the design of a one pot-two step oxidation/reduction sequence to prepare 5-hydroxymethyl-2-furancarboxylic acid (HMFCA, 85 % yield). In MP3, the use of an acetonitrile/cyclooctane biphase yielded 2,5-diformylfuran (DFF, 96 % yield). All the multiphase systems MP 1-3 allowed a perfect segregation of the catalyst in a single phase (either the hydrocarbon or the IL) distinct from the one containing HMF and its oxidation products. This was crucial not only for the catalyst/product separation but also for the recycle of Ru/C that was possible under all the tested conditions. Accordingly, MP-reaction were run in a semicontinuous mode without removing the catalyst from the reactor nor resorting to conventional separation and activation techniques. Negligible Ru leaching, less than 0.96 ppb, was measured in all cases.
Keywords: HMF; Ru/C catalyst; multiphase systems; oxidation; selectivity control.
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