Conversion of Sawdust into 5-Hydroxymethylfurfura by Using 1,3-Dimethyl-2-Imidazolidinone as the Solvent

Document Type: Research Article


School of Chemical Engineering, Changchun University of Technology, Changchun 130012, P.R. CHINA


The conversion of the cellulose into 5-HMF would experience three steps, cellulose to glycose, glycose to fructose and fructose to 5-HMF. Chloride ion can break down the hydrogen bond in cellucose, chromium can catalyze the isomerization of glycose to fructose, and the high temperature is helpful to cyclohydration of fructose to 5-HMF. In this paper, the sawdust has been directly degraded into 5-HMF in 1,3-dimethyl-2-imidazolidinone (DMI) solvent containing alkali halides or ionic liquid with chromium(III) as the catalyst. The factors including the reaction temperature, reaction time, amount of catalyst and liquid-solid ratio, are investigated. The results indicate that the additive —— alkali halides plays an important role in the degradation of sawdust, for example that NaCl and KCl give rise to 28% (140°C) and 25.5% (120°C) of the final yield calculated on m(5-HMF)/m(sawdust), respectively.  


Main Subjects

[1] Kamm B., Gruber P.R., Kamm M., (Eds.), "Biorefineriess Industrial Processes and Products", Wiley-VCH: Weinheim, Germany, (2006).

[2] Lansalot-Matras C., Moreau C., Dehydration of Fructose into 5-Hydroxymethylfurfural in the Presence of Ionic Liquids, Catal. Commun., 4, p. 517 (2003).

[3] Gandini A., Belgacem M.N., Furans in Polymer Chemistry, Prog. Polym. Sci., 22, p. 1203 (1997).

[4] Gandini A., Belgacem M.N., Furfural and Furanic Polymers, L’Actualite Chim., 11/12, p. 56 (2002).

[5] Gandini A.,. Belgacem M.N, Recent Contributions to the Preparation of Polymers Derived from Renewable Resources, J. Polym. Environ., 10, p. 105 (2002).

[6] Moreaua C., Belgacemb M.N., Gandini A., Recent Catalytic Advances in the Chemistry of Substituted Furans from Carbohydrates and in the Ensuing Polymers, Top. Catal., 7, p. 11 (2004).

[7] Zhao H.B., Holladay J.E., Brown H., Zhang Z.C., Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural, Science, 316, p. 1597 (2007).

[8] Moreau C., Durand R., Roux A., Tichit D., Production of Liquid Alkanes by Aqueous-Phase Processing of Biomassderived Carbohydrates, Appl. Catal. A: Gen., 193, p. 257 (2000).

[9] Moreau C., Finiels A., Vanoye L., Dehydration of Fructose and Sucrose Into 5-Hydroxymethylfurfural in the Presence of 1-H-3-Methylimidazolium Chloride Acting Both as Solvent and Catalyst, J. Mol. Catal. A: Chem., 253, p. 165 (2006).

[10] Guo F., Fang Z., Zhou T.J., Conversion of Fructose and Glucose Into 5-Hydroxymethylfurfural with Lignin-Derived Carbonaceous Catalyst under Microwave Irradiation in Dimethyl Sulfoxide-Ionic Liquid Mixtures, Bioresource Technology, 112, p. 313 (2012).

[11] Asghari F.S., Yoshida H., Acid-Catalyzed Production of 5-Hydroxymethyl Furfural from D-Fructose in Subcritical Water, Ind. Eng. Chem. Res., 45, p. 2163 (2006).

[12] Bicker M., Hirth J., Vogel H., Dehydration of Fructose to 5-Hydroxymethylfurfural in Sub- and Supercritical Acetone, Green Chem., 5, p. 280 (2003).

[13] Huber G.W., Cheda J.N., Barrett C.J., Production of Liquid Alkanes by Aqueous-Phase Processing of Biomassderived Carbohydrates, Science, 308, p. 1446 (2005).

[14] Seri K., Inoue Y., Ishida H., Catalytic Activity of Lanthanide(III) Ions for the Dehydration of Hexose to 5-Hydroxymethyl-2-Furaldehyde in Water, Bull. Chem. Soc. Jpn., 74, p. 1145 (2001).

[15] Asghari F.S., Yoshida H., “Kinetics of the Decomposition of Fructose Catalyzed by Hydrochloric Acid in Subcritical Water: Formation of 5-Hydroxymethylfurfural, Levulinic, and Formic Acids, Ind. Eng. Chem. Res., 46, p. 7703 (2007).

[16] Seri K., Inoue Y., Ishida H., Highly Efficient Catalytic Activity of Lanthanide(III) Ions for Conversion of Saccharides to 5-Hydroxymethyl-2-Furfural in Organic Solvent, Chem. Lett., 29, p. 22 (2000).

[17] Qi X.H., Watanabe M., Aida T.M., Jr. Smith R.L., Selective Conversion of D-Fructose to 5-Hydroxymethylfurfural by Ion-Exchange Resin in Acetone/Dimethyl Sulfoxide Solvent Mixtures, Ind. Eng. Chem. Res., 47, p. 9234 (2008).

[18] Binder  J.B.,  Raines  R.T.,  Simple  Chemical Transformation of Lignocellulosic Biomass into Furans for Fuels and Chemicals, J. Am. Chem. Soc., 131, p. 1979 (2009).

[19] Ren Q., Wu J., Zhang J., He J.S., Guo M.L., Synthesis of 1-Allyl,3-Methyle Mazolium-Based Roomtemperature Ionic Liquid and Preluviinary Study of its Dissolving Cellulose, Acta Polym. Sci., 3, p. 448 (2003).