Hydroconversion of 5‐Hydroxymethylfurfural to 2,5‐Dimethylfuran and 2,5‐Dimethyltetrahydrofuran over Non‐promoted Ni/SBA‐15

Abstract

The selective hydroconversion of 5‐hydroxymethylfurfural (HMF) to biofuels is currently highly sought‐for. While the literature has demonstrated that this reaction is possible on promoted Ni catalysts, we show here that a monometallic, non‐promoted Ni/SBA‐15 catalyst, prepared by incipient wetness impregnation, can convert HMF to 2,5‐dimethylfuran (DMF) and to 2,5‐dimethyltetrahydrofuran (DMTHF) at 180 °C, in a consecutive way. Through a control over reaction time, high yields to DMF (71 %, at conversion of 93 %) or DMTHF (97 %, at conversion of 100 %) can be achieved. Kinetic modelling suggests a preferential route to DMF via 5‐methylfurfural (MFFR) as intermediate, though the route via 2,5‐bis(hydroxylmethyl)furan (BHMF) is also present. The favored route in the experimental conditions involves the hydrogenolysis of the hydroxyl group of HMF as first step, followed by the hydrogenation of the aldehyde function, to methylfurfuryl alcohol (MFOL). It is suggested a higher reaction rate of hydrogenation or hydrogenolysis of the side group is linked to the presence of a methyl group in the molecule. No hydrogenation of the furan ring is detected on the intermediates.

Dual Metal–Acid Pd-Br Catalyst for Selective Hydrodeoxygenation of 5-Hydroxymethylfurfural (HMF) to 2,5-Dimethylfuran at Ambient Temperature

“…There are two groups of catalysts which have been proposed for conversion of HMF to DMF: 1) Pd, Pt, Ru, Ir, Co, Ni and Cu-based monometallic or bimetallic catalysts, which perform hydrogenolysis of C-O bond at the temperatures in the range of 150~250 o C. [14,[18][19][20][21][22][23] and 2) bifunctional metal-acid catalysts for hydrodeoxygenation through protonation of the hydroxyl groups and dehydration at milder reaction conditions (60~130 o C) [24][25][26][27][28][29][30][31][32][33] . The disadvantage of the first route is that the high reaction temperature induces polymerization of highly reactive HMF to humins [34] .…”

Preparation of 1-Hydroxy-2,5-hexanedione from HMF by the Combination of Commercial Pd/C and Acetic Acid

“…As a result, the conversion of HMF to valuable products has attracted much attention. Up to now, it has been reported that many chemicals such as 2,5-dimethylfuran (DMF) [18][19][20][21], furan-2,5-diyldimethanol (DHMF) [22,23], furan-2,5-dicarbaldehyde [24][25][26], furan-2,5-dicarboxylic acid [27][28][29][30][31], cyclopentanone derivatives [32][33][34][35][36][37][38], acyclic 2,5-diketones [39][40][41] and so on [42][43][44][45][46][47] can be obtained from HMF through hydrogenation, oxidation and other catalytic processes. The acyclic 2,5-diketones, derived from the hydrogenation of HMF, are valuable intermediates with widespread applications in polymers, surfactants, medicine and solvents.…”

Chemocatalytic value addition of glucose without carbon–carbon bond cleavage/formation reactions: an overview

“…Many of the critical derivatives of HMF involve redox chemistry, where the existing functional groups in HMF (i.e., hydroxymethyl, aldehyde, furan ring) are selectively oxidized/ reduced to other functional groups. 236,237 The sequential reduction of HMF under catalytic hydrogenation conditions leads to a series of furanic and non-furanic derivatives (Scheme 6). For example, selective hydrogenolysis of the C-OH bond in HMF forms 5-methylfurfural (MF).…”