The selective hydrogenation of biomass-derived 5-hydroxymethylfurfural using heterogeneous catalysts

Abstract

The products produced by hydrogenation of biomass-derived 5-hydroxymethylfurfural (HMF) are potential sustainable substitutes for petroleum-based building blocks used in the production of chemicals. We have studied the hydrogenation of HMF over supported Ru, Pd, and Pt catalysts in monophasic and biphasic reactor systems to determine the effects of the metal, support, solution phase acidity, and the solvent to elucidate the factors that determine the selectivity for hydrogenation of HMF to its fully hydrogenated form of 2,5-di-hydroxy-methyl-tetrahydrofuran (DHMTHF). We show that the selectivity to DHMTHF is affected by the acidity of the aqueous solution containing HMF. The major by-products observed are C 6 -polyols formed from the acid-catalyzed degradation and subsequent hydrogenation of 2,5-dihydroxymethylfuran (DHMF), an intermediate hydrogenation product of HMF to DHMTHF. The highest yields (88-91%) to DHMTHF are achieved using Ru supported on materials with high isoelectric points, such as ceria, magnesia-zirconia, and γ-alumina. Supported catalysts containing Pt and Pd at the same weight percent as Ru are not as active for the selective hydrogenation to DHMTHF. † Electronic supplementary information (ESI) available: Full quantitative data for hydrogenation procedures.

Supported Metal Catalysts for Total Hydrogenation of Furfural and 5-Hydroxymethylfurfural

“…Alamillo et al reported that Ru particles on oxide supports with isoelectric point 7 such as CeO2 catalyzed total hydrogenation of HMF to BHTHF in 1-butanol/water biphasic solvent at 403 K (maximum yield 91 %; Table 1) 28) . Ru catalysts on carbon or non-basic support gave significant amount of 1,2,5-and 1,2,6-hexanetriols, 1,2,5,6-hexanetetraol and unidentified products in addition to BHTHF.…”

Oxidant free one-pot transformation of bio-based 2,5-bis-hydroxymethylfuran into α-6-hydroxy-6-methyl-4-enyl-2H-pyran-3-one in water

“…Based on the nature of the reaction products and on what reported for furan hydrolysis [25,81] and for Achmatowicz reaction [42,76,79] a tentative reaction mechanism has been depicted (Scheme 4). It consists of an hydration of one C C double bond of BHMF followed by a dehydration that involve the hydroxymethyl group on the other side of the ring.…”

“…In particular, furans (e.g., 5-hydroxymethylfurfural HMF) are important biomass-derived molecules which can be used as starting materials for the synthesis of a variety of potentially useful compounds [15]. The structural moieties present in HMF, allow synthetic transformations to other target molecules by means of selective reactions such as: oxidation of the formyl group [16][17][18][19][20][21][22][23], reduction of the formyl group and/or the furan ring [24][25], deoxygenation of the hydroxyl groups to 2,5-dimethylfuran [26][27][28][29], etherification and carbonylation [30][31][32][33][34][35], and hydrogenolysis transformations [36][37]. In particular, selective reduction of 5-hydroxymethylfurfural (HMF) provides access to the diol 2,5-bishydroxymethylfuran (BHMF), a valuable building block for the production of polymers and polyurethane foams [18,38,39].…”

金属担持触媒を用いたバイオマス由来アルコールの選択的酸化反応

“…Therefore, selective transformations of these two functional groups with conventional reactions such as oxidation, reduction, hydrogenolysis and condensation have been widely investigated to produce chemicals and fuels 13) . For example, HMFbased diols of 2,5-bis(hydroxymethyl)furan (BHMF) 14), 15) a n d 2,5-b i s ( h y d r o x y m e t h y l ) t e t r a h y d r o f u r a n (BHMTHF) 16), 17) are candidates for biomass-derived monomer sources. HMF can also be oxidized into 2,5-diformylfuran (DFF) and/or 2,5-furandicarboxylic acid (FDCA) (Scheme 1).…”