Solvent Effects on Fructose Dehydration to 5-Hydroxymethylfurfural in Biphasic Systems Saturated with Inorganic Salts

Furan derivatives, such as 5-hydroxymethylfurfural (HMF), obtained from acid-catalyzed dehydration of carbohydrates, can serve as renewable chemical platforms for the production of fuels and chemical intermediates. Addition of an inorganic salt to concentrated aqueous solutions of fructose (30 wt% fructose on salt free basis) in biphasic systems containing an organic extracting phase improves HMF yields by increasing the partitioning of HMF into the extracting phase, as measured by the partition coefficient, R, equal to the concentration of HMF in the organic phase normalized by the concentration in the aqueous phase. We have studied the impact of solvent choice on HMF yield using primary and secondary alcohols, ketones, and cyclic ethers in the C3–C6 range as extracting solvents in biphasic systems saturated with NaCl. Biphasic systems containing C4 solvents generated the highest HMF yields within each solvent class. Tetrahydrofuran demonstrated the best combination of high HMF selectivity (83%) and high extracting power (R = 7.1) at 423 K. The presence of NaCl provided the additional benefit of creating biphasic systems using solvents that are completely miscible with water in the absence of salt. We have also studied the impact of different salts on HMF yield in systems using 1-butanol as the extracting solvent. Na+ and K+ showed the best combination of extracting power and HMF selectivity of the monovalent and divalent chloride salts tested. Changing the anion of the salt from Cl− to Br− resulted in R-values and HMF selectivity values resembling the non-salt system, while changing to the SO42− divalent species generated a high R-value (8.1), but a low HMF selectivity value (71%).

[1]  C. Moreau,et al.  Development of a continuous catalytic heterogeneous column reactor with simultaneous extraction of an intermediate product by an organic solvent circulating in countercurrent manner with the aqueous phase , 1995 .

[2]  Yoshio Nakamura,et al.  The Dehydration of D-Fructose to 5-Hydroxymethyl-2-furaldehyde , 1980 .

[3]  H. V. Bekkum,et al.  The Conversion of Fructose and Glucose in Acidic Media: Formation of Hydroxymethylfurfural , 1986 .

[4]  B. Kuster,et al.  5‐Hydroxymethylfurfural (HMF). A Review Focussing on its Manufacture , 1990 .

[5]  H. Vogel,et al.  Dehydration of d-fructose to hydroxymethylfurfural in sub- and supercritical fluids , 2005 .

[6]  W. J. Groot,et al.  Continuous isopropanol-butanol-ethanol fermentation by immobilized Clostridium beijerinckii cells in a packed bed fermenter , 1983 .

[7]  Joseph Joffe,et al.  Salt Effects in Liquid-Liquid Equilibria , 1966 .

[8]  K. Héberger,et al.  Aqueous salting-out effect of inorganic cations and anions on non-electrolytes. , 2006, Chemosphere.

[9]  H. Szmant,et al.  The preparation of 5-hydroxymethylfurfuraldehyde from high fructose corn syrup and other carbohydrates: Preparation of 5-hydroxymethylfurfuraldehyde , 1981 .

[10]  Johnathan E. Holladay,et al.  Top Value Added Chemicals From Biomass. Volume 1 - Results of Screening for Potential Candidates From Sugars and Synthesis Gas , 2004 .

[11]  Bernhard Kuster,et al.  Preparation of 5‐Hydroxymethylfurfural Part I. Dehydration of Fructose in a Continuous Stirred Tank Reactor , 1977 .

[12]  Gerard Avignon,et al.  Dehydration of fructose to 5-hydroxymethylfurfural over H-mordenites , 1996 .

[13]  Alessandro Gandini,et al.  Recent Catalytic Advances in the Chemistry of Substituted Furans from Carbohydrates and in the Ensuing Polymers , 2004 .

[14]  David W. Brown,et al.  Dehydration reactions of fructose in non‐aqueous media , 2007 .

[15]  Antoine Gaset,et al.  Selective conversion of D-fructose to 5-hydroxymethyl-2-furancarboxaldehyde using a water-solvent-ion-exchange resin triphasic system , 1981 .

[16]  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 .

[17]  Jeppe Rass-Hansen,et al.  The renewable chemicals industry. , 2008, ChemSusChem.

[18]  B. Kuster,et al.  The influence of the initial and catalyst concentrations on the dehydration of d-fructose , 1977 .

[19]  Alessandro Gandini,et al.  Furans in polymer chemistry , 1997 .

[20]  Yuriy Román‐Leshkov,et al.  Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates , 2007, Nature.

[21]  Richard M. Musau,et al.  The preparation of 5-hydroxymethyl-2-furaldehyde (HMF) from d-fructose in the presence of DMSO , 1987 .

[22]  S Aravinth,et al.  Liquid–liquid equilibria of water/acetic acid/1-butanol system — effects of sodium (potassium) chloride and correlations , 1999 .

[23]  W. W. Lucasse,et al.  The Effect of Salts on the Mutual Miscibility of Normal Butyl Alcohol and Water. , 1942 .

[24]  G. Huber,et al.  Production of Liquid Alkanes by Aqueous-Phase Processing of Biomass-Derived Carbohydrates , 2005, Science.