Hydroxymethylfurfural

China Suppliers


Production

Related to the production of furfural, HMF can be produced from sugars. It arises via the dehydration of fructose, a technology that is evolving through new extraction methods. In this new method, fructose is treated with aqueous hydrochloric acid and the HMF (very water-soluble) is continuously extracted into methyl isobutyl ketone as an organic phase at 180 C. The aqueous phase is modified with DMSO and PVP, which minimizes the formation of side product. The organic phase is modified with 2-butanol in order to improve the yield of HMF in the organic phase. In an optimized system for fructose (but not raw biomass), conversion is 77%, with half the HMF ending up in the organic phase. Removing the (high boiling) solvents remains an issue.

In the image above are displayed in a series of chemical equilibria: fructopyranose 1, fructofuranose 2, two intermediate stages of dehydration (not isolated) 3,4 and finally HMF 5. stool softener

In June 2007, researchers at Pacific Northwest National Laboratory reported a process (using chromium chloride as catalyst) to directly convert both fructose (yielding 90%+) and glucose (yielding 70%+) into an HMF, leaving very little residual impurities. In April 2009, a single-step process for converting cellulose directly into HMF (yielding 55% at 96% purity) was outlined by researchers from the same laboratory. The chromium chloride catalyzes the conversion of glucose into fructose. krill oil

Uses agave nectar

HMF can be converted to 2,5-dimethylfuran (DMF), which is a liquid biofuel that in certain ways is superior to ethanol. Oxidation of HMF also gives 2,5-furandicarboxylic acid, which has been proposed as a replacement terephthalic acid for the production of plastics.

5-Hydroxymethyl-2-furfural (5HMF) has been found to bind specifically with intracellular sickle hemoglobin (HbS). Preliminary in vivo studies using transgenic sickle mice showed that orally administered 5HMF inhibits the formation of sickled cells in the blood.

As a contaminant

HMF can form in honey and high-fructose corn syrup (HFCS) when heated. This is a problem for American beekeepers because they use HFCS as a source of sugar when there are not enough nectar sources to feed the honeybees, and HMF is toxic to them. Adding bases such as soda ash or potash to neutralize the HFCS slows down the formation of HMF.

History

This organic compound was studied by French chemist Louis Maillard in 1912 in studies on non-enzymatic reactions of glucose.

References

^ Huber, G. W.; Iborra, S.; Corma, A. Chem. Rev. 2006, 106, 4044 - 4098. doi:10.1021/cr068360d

^ MIT Technology Review

^ terradaily.com News Article

^ Yuriy Romn-Leshkov, Juben N. Chheda, James A. Dumesic (2006). "Phase Modifiers Promote Efficient Production of Hydroxymethylfurfural from Fructose". Science 312 (5782): 19331937. doi:10.1126/science.1126337. PMID 16809536. 

^ Pacific Northwest National Laboratory (2007-06-14). "Plastic that grows on trees". Press release. http://www.pnl.gov/news/release.asp?id=255. 

^ Haibo Zhao, Johnathan E. Holladay, Heather Brown, Z. Conrad Zhang (2007). "Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural". Science 316 (5782): 15971600. doi:10.1126/science.1141199. PMID 17569858. 

^ ScienceDirect

^ Antisickling activityPMID : 15686467

^ Leblanc et al. Formation of Hydroxymethylfurfural in Domestic High-Fructose Corn Syrup and Its Toxicity to the Honey Bee (Apis mellifera). J. Agric. Food Chem., 2009, 57 (16), pp 73697376. DOI: 10.1021/jf9014526

Categories: Aldehydes | Furans