5-Hydroxymethylfurfural (5-HMF) Production from Hexoses: Limits of Heterogeneous Catalysis in Hydrothermal Conditions and Potential of Concentrated Aqueous Organic Acids as Reactive Solvent System

5-Hydroxymethylfurfural (5-HMF) is an important bio-sourced intermediate, formed from carbohydrates such as glucose or fructose. The treatment at 150–250 °C of glucose or fructose in pure water and batch conditions, with catalytic amounts of most of the usual acid-basic solid catalysts, gave limited yields in 5-HMF, due mainly to the fast formation of soluble oligomers. Niobic acid, which possesses both Lewis and Bronsted acid sites, gave the highest 5-HMF yield, 28%, when high catalyst/glucose ratio is used. By contrast, we disclose in this work that the reaction of fructose in concentrated aqueous solutions of carboxylic acids, formic, acetic or lactic acids, used as reactive solvent media, leads to the selective dehydration of fructose in 5-HMF with yields up to 64% after 2 hours at 150 °C. This shows the potential of such solvent systems for the clean and easy production of 5-HMF from carbohydrates. The influence of adding solid catalysts to the carboxylic acid media was also reported, starting from glucose.

[1]  B. Kuster,et al.  The influence of pH and weak-acid anions on the dehydration of d-fructose , 1977 .

[2]  Susanne Rugh,et al.  [33] Industrial-scale production and application of immobilized glucose isomerase , 1987 .

[3]  G. N. Richards,et al.  Mechanism of formation of 5-(hydroxymethyl)-2-furaldehyde from D-fructose an sucrose. , 1990, Carbohydrate research.

[4]  G. Busca,et al.  Selective saccharides dehydration to 5-hydroxymethyl-2-furaldehyde by heterogeneous niobium catalysts , 1999 .

[5]  A. R. Raspolli Galletti,et al.  Heterogeneous zirconium and titanium catalysts for the selective synthesis of 5-hydroxymethyl-2-furaldehyde from carbohydrates , 2000 .

[6]  Claude Moreau,et al.  Isomerization of glucose into fructose in the presence of cation-exchanged zeolites and hydrotalcites ☆ , 2000 .

[7]  G. Busca,et al.  Acid sites characterization of niobium phosphate catalysts and their activity in fructose dehydration to 5-hydroxymethyl-2-furaldehyde , 2000 .

[8]  H. Vogel,et al.  Dehydration of fructose to 5-hydroxymethylfurfural in sub- and supercritical acetone , 2003 .

[9]  A. R. Galletti,et al.  Heterogeneous catalysts based on vanadyl phosphate for fructose dehydration to 5-hydroxymethyl-2-furaldehyde , 2004 .

[10]  Masaru Watanabe,et al.  Catalytic glucose and fructose conversions with TiO2 and ZrO2 in water at 473 K: Relationship between reactivity and acid–base property determined by TPD measurement , 2005 .

[11]  C. Moreau,et al.  Determination of the basic strength of solid catalysts in water by means of a kinetic tracer , 2006 .

[12]  A. Auroux,et al.  Niobic acid and niobium phosphate as highly acidic viable catalysts in aqueous medium: Fructose dehydration reaction , 2006 .

[13]  C. Moreau,et al.  Dehydration of fructose and sucrose into 5-hydroxymethylfurfural in the presence of 1-H-3-methyl imidazolium chloride acting both as solvent and catalyst , 2006 .

[14]  Johnathan E. Holladay,et al.  Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural , 2007, Science.

[15]  James A. Dumesic,et al.  An overview of dehydration, aldol-condensation and hydrogenation processes for production of liquid alkanes from biomass-derived carbohydrates , 2007 .

[16]  P. Brandão,et al.  Isomerization of d-glucose to d-fructose over metallosilicate solid bases , 2008 .

[17]  R. Smith,et al.  Catalytical conversion of fructose and glucose into 5-hydroxymethylfurfural in hot compressed water by microwave heating , 2008 .

[18]  K. Buchholz,et al.  Industrial carbohydrate biotransformations. , 2008, Carbohydrate research.

[19]  Jinliang Song,et al.  Efficient conversion of glucose into 5-hydroxymethylfurfural catalyzed by a common Lewis acid SnCl4 in an ionic liquid , 2009 .

[20]  Atsushi Takagaki,et al.  Syntheses of 5-hydroxymethylfurfural and levoglucosan by selective dehydration of glucose using solid acid and base catalysts , 2010 .

[21]  Xinli Tong,et al.  Biomass into chemicals: Conversion of sugars to furan derivatives by catalytic processes , 2010 .

[22]  Manuel Moliner,et al.  Mechanism of glucose isomerization using a solid Lewis acid catalyst in water. , 2010, Angewandte Chemie.

[23]  B. Hamad,et al.  Basic properties of MgLaO mixed oxides as determined by microcalorimetry and kinetics , 2010 .

[24]  Volkan Degirmenci,et al.  Glucose activation by transient Cr2+ dimers. , 2010, Angewandte Chemie.

[25]  Michikazu Hara,et al.  Protonated titanate nanotubes as solid acid catalyst. , 2010, Journal of the American Chemical Society.

[26]  Catherine Pinel,et al.  Cellulose hydrothermal conversion promoted by heterogeneous Bronsted and Lewis acids: Remarkable efficiency of solid Lewis acids to produce lactic acid , 2011 .

[27]  A. Riisager,et al.  Synergy of boric acid and added salts in the catalytic dehydration of hexoses to 5-hydroxymethylfurfural in water , 2011 .

[28]  Yuguang Du,et al.  Tantalum compounds as heterogeneous catalysts for saccharide dehydration to 5-hydroxymethylfurfural. , 2011, Chemical communications.

[29]  P. Carniti,et al.  Absence of expected side-reactions in the dehydration reaction of fructose to HMF in water over niobic acid catalyst , 2011 .

[30]  C. Afonso,et al.  5-Hydroxymethylfurfural (HMF) as a building block platform: Biological properties, synthesis and synthetic applications , 2011 .

[31]  F. Jérôme,et al.  Heterogeneously Catalyzed Conversion of Carbohydrates , 2011 .

[32]  Wenjing Fu,et al.  Synthesis of 5-(hydroxymethyl)furfural in ionic liquids: paving the way to renewable chemicals. , 2011, ChemSusChem.

[33]  A. K. Patra,et al.  Microwave assisted rapid conversion of carbohydrates into 5-hydroxymethylfurfural catalyzed by mesoporous TiO2 nanoparticles , 2011 .

[34]  Michikazu Hara,et al.  Nb2O5·nH2O as a heterogeneous catalyst with water-tolerant Lewis acid sites. , 2011, Journal of the American Chemical Society.

[35]  R. L. D. Souza,et al.  Glucose–fructose isomerisation promoted by basic hybrid catalysts , 2012 .

[36]  W. Chung,et al.  Facile catalytic dehydration of fructose to 5-hydroxymethylfurfural by Niobium pentachloride , 2012 .