Solvent Effects on Fructose Dehydration to 5-Hydroxymethylfurfural in Biphasic Systems Saturated with Inorganic Salts
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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 SO4 2− divalent species generated a high R-value (8.1), but a low HMF selectivity value (71%).
KeywordsHMF Solvent Acid catalysis Biphasic Fructose
This work was supported by the National Science Foundation Chemical and Transport Systems Division of the Directorate for Engineering, the Great Lakes Bioenergy Research Center (GLBRC), and Virent Energy Systems.
- 1.Christensen CH, Rass-Hansen J, Marsden CC, Taarning E, Egeblad K (2008) Chem Sus Chem 1:283Google Scholar
- 3.Werpy T, Petersen G (2004) Top Value Added Chemicals from Biomass: Vol 1—Results of Screening for Potential Candidates from Sugars and Synthesis Gas. Tech. Report No. Report No. NREL/TP-510-35523 (National Renewable Energy Laboratory)Google Scholar
- 6.Chaabouni A et al (1999) Journal de la Societe Chimique de Tunisie 4:547Google Scholar
- 7.Rapp KM (1987) US Patent, 4,740,605 Google Scholar
- 8.Brown DW, Floyd AJ, Kinsman RG, Roshan-Ali Y (1982) J Chem Technol Biotechnol 32:920Google Scholar
- 11.Szmant HH, Chundury DD (1981) J Chem Technol and Biotechnol 31:135Google Scholar
- 14.Peniston QP (1956) U.S. Patent 2,750,394 Google Scholar
- 15.El Hajj T, MasRoua A, Martin JC, Descotes G (1987) Bulletin de la Societe Chimique de France 5:855Google Scholar
- 21.Gruter G, Maria JDF (2007) Avantis International, European Patent Office EP20060075564Google Scholar
- 22.Jain MK and Datta R (1991) US Patent Office 5063156Google Scholar
- 26.Treybal RE (1963) Liquid Extraction, 2nd edn. McGraw Hill, New YorkGoogle Scholar