Abstract
As a key renewable chemical for plastics and fine chemicals, the preparation of 5-hydroxymethylfurfural (5-HMF) from biomass is an important research topic. Cellulose, although abundant in nature, is difficult to convert to 5-HMF in good yields due to its recalcitrant and heterogeneous nature. In this work, we show an efficient two-step process for converting microcrystalline cellulose into 5-HMF with ionic liquids under mild conditions. In the first step, high glucose yields of above 80% could be obtained from the cellulose hydrolysis by a strong acidic cation exchange resin in 1-ethyl-3-methyl imidazolium chloride ([EMIM][Cl]) with gradual addition of water. In the second step, the resin was separated from the reaction mixture and CrCl3 was added which lead to a 5-HMF yield of 73% based on cellulose substrate. The strategy can allow practical conversion of biomass into bio-derived products.
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References
Corma A, Iborra S, Velty A (2007) Chemical routes for the transformation of biomass into chemicals. Chem Rev 107(6):2411–2502
Harmer MA, Fan A, Liauw A, Kumar RK (2009) A new route to high yield sugars from biomass: phosphoric-sulfuric acid. Chem Commun 45(43):6610–6612
Hu SQ, Zhang ZF, Song JL, Zhou YX, Han BX (2009) Efficient conversion of glucose into 5-hydroxymethylfurfural catalyzed by a common Lewis acid SnCl4 in an ionic liquid. Green Chem 11(11):1746–1749
Ishikawa Y, Saka S (2001) Chemical conversion of cellulose as treated in supercritical methanol. Cellulose 8(3):189–195
James OO, Maity S, Usman LA, Ajanaku KO, Ajani OO, Siyanbola TO, Sahu S, Chaubey R (2010) Towards the conversion of carbohydrate biomass feedstocks to biofuels via hydroxylmethylfurfural. Energy Environ Sci 3(12):1833–1850
Li CZ, Zhao ZK (2007) Efficient acid-catalyzed hydrolysis of cellulose in ionic liquid. Adv Synth Catal 349:1847–1850
Li CZ, Wang Q, Zhao ZK (2008) Acid in ionic liquid: an efficient system for hydrolysis of lignocellulose. Green Chem 10(2):177–182
Lima S, Neves P, Antunes MM, Pillinger M, Ignatyev K, Valente AA (2009) Conversion of mono/di/polysaccharides into fruran compounds using 1-alkyl-3-methylimidazolium ionic liquids. Appl Catal A Gen 363(1–2):93–99
Onda A, Ochi T, Yanagisawa K (2008) Selective hydrolysis of cellulose into glucose over solid acid catalysts. Green Chem 10(10):1033–1037
Qi XH, Watanabe M, Aida TM, Smith RL Jr (2008a) Catalytic dehydration of fructose into 5-hydroxymethylfurfural by ion-exchange resin in mixed-aqueous system by microwave heating. Green Chem 10(7):799–805
Qi XH, Watanabe M, Aida TM, Smith RL Jr (2008b) Selective conversion of d-fructose to 5-hydroxymethylfurfural by ion-exchange resin in acetone/dimethyl sulfoxide solvent mixtures. Ind Eng Chem Res 47(23):9234–9239
Qi XH, Watanabe M, Aida TM, Smith RL Jr (2009) Efficient process for conversion of fructose to 5-hydroxymethylfurfural with ionic liquids. Green Chem 11(9):1327–1331
Qi XH, Watanabe M, Aida TM, Smith RL Jr (2010) Fast transformation of glucose and di-/polysaccharides into 5-hydroxymethylfurfural by microwave heating in an ionic liquid/catalyst system. Chemsuschem 3(9):1071–1077
Rinaldi R, Schuth F (2009) Acid hydrolysis of cellulose as the entry point into biorefinery schemes. Chemsuschem 2(12):1096–1107
Roman-Leshkov Y, Chheda JN, Dumesic JA (2006) Phase modifiers promote efficient production of hydroxymethylfurfural from fructose. Science 312(5782):1933–1937
Roman-Leshkov Y, Barrett CJ, Liu ZY, Dumesic JA (2007) Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates. Nature 447(7147):982–985
Saka S, Ueno T (1999) Chemical conversion of various celluloses to glucose and its derivatives in supercritical water. Cellulose 6(3):177–191
Swatloski RP, Spear SK, Holbrey JD, Rogers RD (2002) Dissolution of cellose with ionic liquids. J Am Chem Soc 124(18):4974–4975
Tian J, Wang JH, Zhao S, Jiang CY, Zhang X, Wang XH (2010) Hydrolysis of cellulose by the heteropoly acid H3PW12O40. Cellulose 17(3):587–594
Wu YY, Fu ZH, Yin DL, Xu Q, Liu FL, Lu CL, Mao LQ (2010) Microwave-assisted hydrolysis of crystalline cellulose catalyzed by biomass char sulfonic acids. Green Chem 12(4):696–700
Yu S, Brown HM, Huang XW, Zhou XD, Amonette JE, Zhang ZC (2009) Single-step conversion of cellulose to 5-hydroxymethylfurfural (HMF), a versatile platform chemical. Appl Catal A Gen 361(1–2):117–122
Zhang ZH, Zhao ZBK (2010) Microwave-assisted conversion of lignocellulosic biomass into furans in ionic liquid. Bioresour Technol 101(3):1111–1114
Zhao HB, Holladay JE, Brown H, Zhang ZC (2007) Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural. Science 316(5831):1597–1600
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The authors gratefully acknowledge the financial supports by the National Natural Science Foundation of China (NSFC, No. 20806041) and the Japan Society for the Promotion of Science.
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Qi, X., Watanabe, M., Aida, T.M. et al. Catalytic conversion of cellulose into 5-hydroxymethylfurfural in high yields via a two-step process. Cellulose 18, 1327–1333 (2011). https://doi.org/10.1007/s10570-011-9568-1
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DOI: https://doi.org/10.1007/s10570-011-9568-1