REVIEW OF 5-HMF SYNTHESIS: CATALYSIS AND TECHNOLOGIES
Article Sidebar
Main Article Content
Abstract
5-Hydroxymethylfurfural (5-HMF) is recognized as a key platform molecule in the bioeconomy, serving as a precursor for the production of biofuels (2,5-dimethylfuran, 5-ethoxymethylfurfuryl ether), biopolymers (2,5-furandicarboxylic acid), and pharmaceutical intermediates. This review systematizes modern approaches to the synthesis of 5-HMF from carbohydrate feedstocks of varying complexity – from monosaccharides (fructose, glucose) to cellulose and lignocellulosic biomass (rice straw). Catalytic systems (homogeneous acids, ionic liquids, heterogeneous catalysts, including functionalized silica gel SiO₂-Imi-SO₃H and sulfated zeolite HSO₃-ZSM-5), solvent effects (dimethyl sulfoxide, biphasic water/organic solvent systems, including dichloromethane/tetrahydrofuran), process intensification methods (ultrasound, microwaves), and strategies for suppressing side reactions are analyzed in detail. The main pathways of 5-HMF chemical transformation are discussed, along with techno-economic and environmental aspects of production based on life cycle assessment (LCA) and bibliometric analysis. Key challenges (catalyst and separation costs, stability) and promising research directions (low-cost bifunctional catalysts, deep eutectic solvents, process integration, electrochemical methods, use of non-food biomass) are identified.
Downloads
Article Details
Issue
Section
This work is licensed under a Creative Commons Attribution 4.0 International License.
Public License Terms
(For Open Journal Systems (OJS))
-
Copyright:
The copyright of the published article remains with the author(s). However, after publication, the article is distributed on the OJS platform under the Creative Commons (CC BY) license. -
License Type:
This article is distributed under the Creative Commons Attribution 4.0 International (CC BY 4.0) license. This means users can utilize the article under the following conditions:- Copy and distribute: The text of the article or its parts can be freely distributed.
- Quote and analyze: Parts of the article can be used for quoting and analysis.
- Free use: The article can be freely used for research and educational purposes.
- Attribution: Users must provide proper attribution and reference to the original source.
-
Commercial use:
The article can be used for commercial purposes, provided that authorship and source are properly cited. -
Document modification:
The text or content of the article can be modified or adapted, as long as it does not harm the authorship. -
Liability disclaimer:
The author(s) are responsible for the accuracy of the information contained in the article. The editorial team of the platform is not liable for any damages resulting from the use of this information. -
Public usage obligations:
The content of the article must be used only in accordance with legal and ethical standards. Unauthorized use is strictly prohibited.
Note:
These license terms are designed to ensure transparency and openness in material usage. By accepting these terms, you agree to the adaptation and distribution of the article content under the terms of the Creative Commons license.
Link: Creative Commons Attribution 4.0 International (CC BY 4.0)
How to Cite
References
[1] Jiang, Z., Zeng, Y., Hu, D., et al. (2023). Chemical transformations of 5-hydroxymethylfurfural into highly added value products: Present and future. Green Chemistry, 25, 871–892. https://doi.org/10.1039/D2GC03444A DOI: https://doi.org/10.1039/D2GC03444A
[2] Wang, H., Zhu, C., Li, D., et al. (2019). Recent advances in catalytic conversion of biomass to 5-hydroxymethylfurfural and 2,5-dimethylfuran. Renewable and Sustainable Energy Reviews, 103, 227–247. https://doi.org/10.1016/j.rser.2018.12.010 DOI: https://doi.org/10.1016/j.rser.2018.12.010
[3] van Putten, R.-J., van der Waal, J. C., de Jong, E., et al. (2013). Hydroxymethylfurfural: A versatile platform chemical made from renewable resources. Chemical Reviews, 113(3), 1499–1597. https://doi.org/10.1021/cr300182k DOI: https://doi.org/10.1021/cr300182k
[4] Zhang, Z., & Huber, G. W. (2018). Catalytic oxidation of carbohydrates into organic acids and furan chemicals. Chemical Society Reviews, 47(4), 1351–1390. https://doi.org/10.1039/C7CS00213K DOI: https://doi.org/10.1039/C7CS00213K
[5] Dutta, S., De, S., & Saha, B. (2012). A brief summary of the synthesis of polyester building-block chemicals and biofuels from 5-hydroxymethylfurfural. ChemPlusChem, 77(4). https://doi.org/10.1002/cplu.201100035 DOI: https://doi.org/10.1002/cplu.201100035
[6] Thananatthanachon, T., & Rauchfuss, T. B. (2010). Efficient production of the liquid fuel 2,5-dimethylfuran from fructose using formic acid as a reagent. Angewandte Chemie International Edition, 49(37), 6616–6618. https://doi.org/10.1002/anie.201002267 DOI: https://doi.org/10.1002/anie.201002267
[7] Dutta, S., Wu, L., & Mascal, M. (2015). Efficient, green, and scalable production of 5-ethoxymethylfurfural from fructose catalyzed by sulfuric acid. ChemSusChem, 8(10), 1711–1715. https://doi.org/10.1002/cssc.201403481 DOI: https://doi.org/10.1002/cssc.201403481
[8] Sajid, M., Zhao, X., & Liu, D. (2018). Production of 2,5-furandicarboxylic acid (FDCA) from 5-hydroxymethylfurfural (HMF): Recent progress focusing on chemical catalytic routes. Green Chemistry, 20(24), 5427–5453. https://doi.org/10.1039/C8GC02680G DOI: https://doi.org/10.1039/C8GC02680G
[9] Kröger, M., Prüße, U., & Vorlop, K.-D. (2012). A new approach for the production of 2,5-furandicarboxylic acid by in situ oxidation of 5-hydroxymethylfurfural starting from fructose. Topics in Catalysis, 13(3), 237–242. https://doi.org/10.1023/A:1009017929727 DOI: https://doi.org/10.1023/A:1009017929727
[10] Davis, S. E., Houk, L. R., Tamargo, E. C., et al. (2011). Oxidation of 5-hydroxymethylfurfural over supported Pt, Pd, and Au catalysts. Catalysis Today, 160(1), 55–60. https://doi.org/10.1016/j.cattod.2010.06.004 DOI: https://doi.org/10.1016/j.cattod.2010.06.004
[11] Ромашов, Л. В. (2017). Исследование свойств 5-(гидроксиметил)фурфурола и его применение в синтезе биологически активных соединений и их аналогов (Канд. диссертация).
[12] Kuster, B. F. M. (1990). 5-Hydroxymethylfurfural (HMF): A review focusing on its manufacture. Starch – Stärke, 42(8), 314–321. https://doi.org/10.1002/star.19900420808 DOI: https://doi.org/10.1002/star.19900420808
[13] Girisuta, B., Janssen, L. P. B. M., & Heeres, H. J. (2006). A kinetic study on the decomposition of 5-hydroxymethylfurfural into levulinic acid. Green Chemistry, 8(8), 701–709. https://doi.org/10.1039/B518176C DOI: https://doi.org/10.1039/b518176c
[14] Antal, M. J., Mok, W. S. L., & Richards, G. N. (1990). Mechanism of formation of 5-(hydroxymethyl)-2-furaldehyde from D-fructose and sucrose. Carbohydrate Research, 199(1), 91–109. https://doi.org/10.1016/0008-6215(90)84096-D
[15] Jung, D., Körner, P., & Kruse, A. (2021). Kinetic study on the impact of acidity and acid concentration on the formation of 5-hydroxymethylfurfural (HMF), humins, and levulinic acid in the hydrothermal conversion of fructose. Biomass and Bioenergy, 154, 106231. https://doi.org/10.1007/s13399-019-00507-0 DOI: https://doi.org/10.1007/s13399-019-00507-0
[16] Sorokina, K. N., Taran, O. P., Medvedeva, T. B., & Parmon, V. N. (2017). Method for producing 5-hydroxymethylfurfural and ethanol from cellulose (Russian Patent RU2636004C1, November 17, 2017).
[17] Wanninayake, P., Rathnayake, M., Thushara, D., & Gunawardena, S. (2022). Conversion of rice straw into 5-hydroxymethylfurfural: Review and comparative process evaluation. Biomass Conversion and Biorefinery, 12, 1013–1047. https://doi.org/10.1007/s13399-021-01351-x DOI: https://doi.org/10.1007/s13399-021-01351-x
[18] Food and Agriculture Organization of the United Nations (FAO). (2022). Global assessment of biomass resources for 5-HMF production: Technical potential and sustainability.
[19] Dutta, S., De, S., Saha, B., et al. (2012). Advances in conversion of hemicellulosic biomass to furfural and upgrading to biofuels. Catalysis Science & Technology, 2(10), 2025–2036. https://doi.org/10.1039/C2CY20235B DOI: https://doi.org/10.1039/c2cy20235b
[20] Avalon Industries AG. (2019). Method for the extraction of (5-hydroxymethylfurfural, 5-HMF) (European Patent EP3424914A1, January 9, 2019).
[21] Binder, J. B., & Raines, R. T. (2009). Simple chemical transformation of lignocellulosic biomass into furans for fuels and chemicals. Journal of the American Chemical Society, 131(5), 1979–1985. https://doi.org/10.1021/ja808537j DOI: https://doi.org/10.1021/ja808537j
[22] Román-Leshkov, Y., Chheda, J. N., & Dumesic, J. A. (2006). Phase modifiers promote efficient production of hydroxymethylfurfural from fructose. Science, 312(5782), 1933–1937. https://doi.org/10.1126/science.1126337 DOI: https://doi.org/10.1126/science.1126337
[23] Wang, F.-F., Liu, C.-L., & Dong, W.-S. (2013). Highly efficient production of lactic acid from cellulose using lanthanide triflate catalysts. Green Chemistry, 15(8), 2091–2095. https://doi.org/10.1039/C3GC40836A DOI: https://doi.org/10.1039/c3gc40836a
[24] IEA Bioenergy Task 42. (2021). Techno-economic assessment (TEA) and life cycle assessment (LCA) of 5-HMF production routes.
[25] Tunç, E., Hoşgün, E. Z., Hoşgün, H. L., & Bozan, B. (2023). Direct conversion of cellulose into 5-HMF by transition-metal doped montmorillonite catalyst in water. Clays and Clay Minerals, 71(1), 14–24. https://doi.org/10.1007/s42860-023-00232-w DOI: https://doi.org/10.1007/s42860-023-00232-w
[26] Cao, Q., Guo, X., Guan, J., et al. (2011). A process for efficient conversion of fructose into 5-hydroxymethylfurfural in ammonium salts. Applied Catalysis A: General, 403(1–2), 98–103. https://doi.org/10.1016/j.apcata.2011.06.018 DOI: https://doi.org/10.1016/j.apcata.2011.06.018
[27] Chheda, J. N., Román-Leshkov, Y., & Dumesic, J. A. (2007). Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and polysaccharides. Green Chemistry, 9(4), 342–350. https://doi.org/10.1039/B611568C DOI: https://doi.org/10.1039/B611568C
[28] Qi, X., Watanabe, M., Aida, T. M., et al. (2009). Efficient process for conversion of fructose to 5-hydroxymethylfurfural with ionic liquids. Green Chemistry, 11(9), 1327–1331. https://doi.org/10.1039/B905975J DOI: https://doi.org/10.1039/b905975j
[29] Tao, F., Song, H., & Chou, L. (2011). Catalytic conversion of cellulose to chemicals in ionic liquid. Carbohydrate Research, 346(1), 58–63. https://doi.org/10.1016/j.carres.2010.10.022 DOI: https://doi.org/10.1016/j.carres.2010.10.022
[30] Amarasekara, A. S., Williams, L. D., & Ebede, C. C. (2008). Mechanism of the dehydration of D-fructose to 5-hydroxymethylfurfural in dimethyl sulfoxide at 150 °C: An NMR study. Carbohydrate Research, 343(18), 3021–3024. https://doi.org/10.1016/j.carres.2008.09.008 DOI: https://doi.org/10.1016/j.carres.2008.09.008
[31] Тарабанко, В. Е., Смирнова, М. А., Челбина, Ю. В., & Черняк, М. Ю. (2011). Low-temperature synthesis of 5-hydroxymethylfurfural. Khimiya rastitel’nogo syr’ya [Chemistry of Plant Materials], 9, 87–92.
[32] Nikolla, E., Román-Leshkov, Y., Moliner, M., et al. (2011). “One-pot” synthesis of 5-(hydroxymethyl)furfural from carbohydrates using tin-beta zeolite. ACS Catalysis, 1(4), 408–410. https://doi.org/10.1021/cs2000544 DOI: https://doi.org/10.1021/cs2000544
[33] Hu, S., Zhang, Z., Song, J., et al. (2009). Efficient conversion of glucose into 5-hydroxymethylfurfural catalyzed by a common Lewis acid SnCl₄ in an ionic liquid. Green Chemistry, 11, 1746–1749. https://doi.org/10.1039/B914601F DOI: https://doi.org/10.1039/b914601f
[34] Yan, H., Yang, Y., Tong, D., et al. (2009). Catalytic conversion of glucose to 5-hydroxymethylfurfural over SO₄²⁻/ZrO₂ and SO₄²⁻/ZrO₂–Al₂O₃ solid acid catalysts. Catalysis Communications, 10(11), 1558–1563. https://doi.org/10.1016/j.catcom.2009.04.020 DOI: https://doi.org/10.1016/j.catcom.2009.04.020
[35] Eminov, S., Filippousi, P., Brandt, A., et al. (2016). Direct catalytic conversion of cellulose to 5-hydroxymethylfurfural using ionic liquids. Inorganics, 4(4), 32. https://doi.org/10.3390/inorganics4040032 DOI: https://doi.org/10.3390/inorganics4040032
[36] Zhao, H., Holladay, J. E., Brown, H., et al. (2007). Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural. Science, 316(5831), 1597–1600. https://doi.org/10.1126/science.1141199 DOI: https://doi.org/10.1126/science.1141199
[37] Wang, T., Nolte, M. W., & Shanks, B. H. (2014). Catalytic dehydration of C6 carbohydrates for the production of hydroxymethylfurfural (HMF) as a versatile platform chemical. Green Chemistry, 16(2), 548–572. https://doi.org/10.1039/C3GC41365A DOI: https://doi.org/10.1039/C3GC41365A
[38] Deng, W., Liu, M., Zhang, Q., et al. (2010). Acid-catalysed direct transformation of cellulose into methyl glucosides in methanol at moderate temperatures. Chemical Communications, 46(15), 2668–2670. https://doi.org/10.1039/B925723C DOI: https://doi.org/10.1039/b925723c
[39] Gallo, J. M. R., Trapp, M. A., Alonso, D. M., et al. (2013). Direct conversion of cellulose to levulinic acid and gamma-valerolactone using solid acid catalysts. Catalysis Science & Technology, 3(1), 306–309. https://doi.org/10.1039/C2CY20689G DOI: https://doi.org/10.1039/C2CY20689G
[40] Amarasekara, A. S., & Owereh, O. S. (2009). Hydrolysis and decomposition of cellulose in Brønsted acidic ionic liquids under mild conditions. Industrial & Engineering Chemistry Research, 48(22), 10152–10155. https://doi.org/10.1021/ie901047u DOI: https://doi.org/10.1021/ie901047u
[41] Hu, L., Zhao, G., Tang, X., et al. (2013). Catalytic conversion of carbohydrates into 5-hydroxymethylfurfural over cellulose-derived carbonaceous catalyst in ionic liquid. Bioresource Technology, 148, 501–507. https://doi.org/10.1016/j.biortech.2013.09.016 DOI: https://doi.org/10.1016/j.biortech.2013.09.016
[42] Tao, F., Song, H., & Chou, L. (2010). Hydrolysis of cellulose by using catalytic amounts of FeCl₂ in ionic liquids. ChemSusChem, 3(11), 1298–1303. https://doi.org/10.1002/cssc.201000184 DOI: https://doi.org/10.1002/cssc.201000184
[43] Antal, M. J., Mok, W. S. L., & Richards, G. N. (1990). Mechanism of formation of 5-(hydroxymethyl)-2-furaldehyde from D-fructose and sucrose. Carbohydrate Research, 199(1), 91–109. https://doi.org/10.1016/0008-6215(90)84096-D DOI: https://doi.org/10.1016/0008-6215(90)84096-D
[44] Faradis, R., Suryanto, A. B., Murwani, I. K. (2023). Conversion of cellulose to 5-hydroxymethylfurfural as sustainable energy: A bibliometric analysis by VOSviewer. Journal of Environmental Science and Sustainable Development, 6(2), 345–366. https://doi.org/10.7454/jessd.v6i2.1158 DOI: https://doi.org/10.7454/jessd.v6i2.1158
[45] Yemiş, O., & Mazza, G. (2011). Acid-catalyzed conversion of xylose, xylan and straw into furfural by microwave-assisted reaction. Bioresource Technology, 102(15), 7371–7378. https://doi.org/10.1016/j.biortech.2011.04.050 DOI: https://doi.org/10.1016/j.biortech.2011.04.050
[46] Vinh, T. Ch. D., Thong, M. D., Thu, A. H., et al. (2024). A simple and efficient synthesis of 5-hydroxymethylfurfural from carbohydrates using acidic ionic liquid grafted on silica gel. RSC Advances, 14, 17480–17490. https://doi.org/10.1039/D4RA02487G DOI: https://doi.org/10.1039/D4RA02487G
[47] Yan, L., Liu, N., Wang, Y., Machida, H., & Qi, X. (2014). Production of 5-hydroxymethylfurfural from corn stalk catalyzed by corn stalk-derived carbonaceous solid acid catalyst. Bioresource Technology, 173, 462–466. https://doi.org/10.1016/j.biortech.2014.09.148 DOI: https://doi.org/10.1016/j.biortech.2014.09.148
[48] Kuster, B. F. M., & Temmink, H. M. G. (1977). The influence of pH and weak-acid anions on the dehydration of D-fructose. Carbohydrate Research, 54, 185–191. https://doi.org/10.1016/S0008-6215(00)84810-7 DOI: https://doi.org/10.1016/S0008-6215(00)84808-9
[49] Qi, X., Watanabe, M., Aida, T. M., et al. (2008). Selective conversion of D-fructose to 5-hydroxymethylfurfural by ion-exchange resin in acetone/dimethyl sulfoxide solvent mixtures. Industrial & Engineering Chemistry Research, 47(23), 9234–9239. https://doi.org/10.1021/ie801016s DOI: https://doi.org/10.1021/ie801016s
[50] Zhang, Z., & Zhao, Z. K. (2011). Production of 5-hydroxymethylfurfural from glucose catalyzed by hydroxyapatite supported chromium chloride. Bioresource Technology, 102(4), 3970–3972. https://doi.org/10.1016/j.biortech.2010.11.098 DOI: https://doi.org/10.1016/j.biortech.2010.11.098
[51] Smith, S. M. (2020). Heterogeneous catalysis for the conversion of sugars to 5-hydroxymethylfurfural (PhD thesis). University of Wisconsin–Madison.
[52] Roldugina, E. A., Boronoev, M. P., Shakirov, I. I., & Kardasheva, Y. S. (2024). Hydrogenation of furfural, 5-hydroxymethylfurfural, and levulinic acid in the presence of a Pd catalyst supported on mesoporous zirconosilicate. Journal of Applied Chemistry, 97(1), 63–69. https://doi.org/10.1134/S1070427224010080
[53] Zhang, H., Yu, Z., Tian, G., et al. (2020). Continuous synthesis of 5-hydroxymethylfurfural using deep eutectic solvents and its kinetic study in microreactors. Chemical Engineering Journal, 391, 123580. https://doi.org/10.1016/j.cej.2019.123580 DOI: https://doi.org/10.1016/j.cej.2019.123580
[54] Сахаютдинова, Г. Ф., Маликова, Р. Н., & Мустафин, А. Г. (2021). Efficient synthesis of 5-(hydroxymethyl)furan-2-enones via the Wittig reaction. Bulletin of Bashkir University, 26(3), 655–658. DOI: https://doi.org/10.33184/bulletin-bsu-2021.3.21
[55] Клушин, В. А., Болдырева, Е. В., Кашпарова, В. П., et al. (2017). Synthesis of 2,5-furandicarboxylic acid by selective oxidation of crude 5-hydroxymethylfurfural obtained from plant raw materials. Proceedings of Higher Educational Institutions. North Caucasus Region. Technical Sciences, 4(196). DOI: https://doi.org/10.17213/0321-2653-2017-4-96-101
[56] Chernyshev, V. M., Kravchenko, O. A., & Ananikov, V. P. (2017). Conversion of plant biomass into furan derivatives and sustainable access to a new generation of polymers, functional materials, and fuels. Russian Chemical Reviews, 86(5), 357–387. https://doi.org/10.1070/RCR4700 DOI: https://doi.org/10.1070/RCR4700
[57] Smirnova, M. A., Tarabanko, V. E., Chernyak, M. Yu., & Morozov, A. L. (2012). Synthesis of 5-fluoromethylfurfural from halogen derivatives of hydroxymethylfurfural. In Forest and Chemical Complexes — Problems and Solutions (Proc. All-Russian Scientific and Practical Conf., Krasnoyarsk, Oct. 25–26, 2012), Vol. 2, pp. 13–16. Krasnoyarsk: SibSTU Publishing.
[58] Tivas, N. S., Chetvertneva, I. A., et al. (2024). Synthesis and biocidal properties of systems based on hydrocarbons and carbohydrates. Russian Chemical Journal, 68(2), 21–30. https://doi.org/10.6060/rcj.2024682.3
[59] Moreau, C., Belgacem, M. N., & Gandini, A. (2004). Recent catalytic advances in the chemistry of substituted furans from carbohydrates and in the ensuing polymers. Topics in Catalysis, 27(1–4), 11–30. https://doi.org/10.1023/B:TOCA.0000013537.13540.0e DOI: https://doi.org/10.1023/B:TOCA.0000013537.13540.0e
[60] Lansalot-Matras, C., & Moreau, C. (2003). Dehydration of fructose into 5-hydroxymethylfurfural in the presence of ionic liquids. Catalysis Communications, 4(10), 517–520. https://doi.org/10.1016/S1566-7367(03)00133-6 DOI: https://doi.org/10.1016/S1566-7367(03)00133-X
[61] Mercadier, D., Rigal, L., Gaset, A., et al. (1981). Synthesis of 5-hydroxymethyl-2-furancarboxaldehyde catalysed by cationic exchange resins. Part II. Kinetic studies. Journal of Chemical Technology & Biotechnology, 31(1), 503–508. https://doi.org/10.1002/jctb.5030310155 DOI: https://doi.org/10.1002/jctb.280310167
[62] Rackemann, D. W., & Doherty, W. O. S. (2011). The conversion of lignocellulosics to levulinic acid. Biofuels, Bioproducts and Biorefining, 5(2), 198–214. https://doi.org/10.1002/bbb.267 DOI: https://doi.org/10.1002/bbb.267
[63] Li, H., Yang, S., Saravanamurugan, S., et al. (2017). Glucose isomerization by enzymes and chemo-catalysts: Status and current advances. ACS Catalysis, 7(4), 3010–3029. https://doi.org/10.1021/acscatal.6b03625 DOI: https://doi.org/10.1021/acscatal.6b03625
[64] Kılıç, E., & Yılmaz, S. (2015). Fructose dehydration to 5-hydroxymethylfurfural over sulfated TiO₂–SiO₂, Ti-SBA-15, ZrO₂, SiO₂, and activated carbon catalysts. Industrial & Engineering Chemistry Research, 54(19), 5220–5225. https://doi.org/10.1021/acs.iecr.5b00628 DOI: https://doi.org/10.1021/acs.iecr.5b00628
[65] Modak, A., Mankar, A., Sonde, R. R., & Pant, K. K. (2023). One-pot conversion of glucose to 5-hydroxymethylfurfural under aqueous conditions using acid/base bifunctional mesoporous silica catalyst. Renewable Energy, 212, 97–111. https://doi.org/10.1016/j.renene.2023.05.058 DOI: https://doi.org/10.1016/j.renene.2023.05.058