, Volume 26, Issue 17, pp 9035–9043 | Cite as

Heterogeneous Cr-zeolites (USY and Beta) for the conversion of glucose and cellulose to 5-hydroxymethylfurfural (HMF)

  • Esra Sezgin
  • Merve Esen Keçeci
  • Solmaz AkmazEmail author
  • Serkan Naci Koc
Original Research


For the first time, the heterogeneous calcined forms of chromium loaded USY, ZSM-5 and Beta zeolites were studied for the synthesis of HMF from glucose and cellulose in different solvents such as 1-butyl-3-methylimidazolium chloride (BMIMCl) and dimethyl sulfoxide (DMSO). Catalysts were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, inductive coupling plasma-mass spectrometry and temperature programmed desorption (NH3-TPD). It was found that calcined forms of chromium-zeolites provide better HMF yield in (BMIMCl) ionic liquid than chromium-free zeolites. The 58.8% and 54.5% HMF yields from glucose and 34.1% and 34.3% HMF yields from cellulose were obtained at 130 °C after 60 min in BMIMCl ionic liquid with Cr-Beta (SiO2/Al2O3 = 28) and Cr-USY (SiO2/Al2O3 = 6) zeolites, respectively. 35% HMF yield was achieved with heterogeneous Cr-USY (SiO2/Al2O3 = 6) zeolite at 160 °C after 90 min in DMSO. However, HMF yield from cellulose was not observed in DMSO. Although chromium leaching from catalyst occurred in BMIMCI solvent, no loss of catalytic activity and no chromium leaching from catalyst was observed in DMSO for five times recycling reactions. It can be said that DMSO is highly suitable solvent for easily separable heterogeneous Cr-USY catalyst for glucose to HMF conversion.


Glucose Cellulose HMF USY ZSM-5 Beta zeolite 



This work was supported by Scientific Research Projects Coordination Unit of Istanbul University (Project No: FYL-2016-21561) and The Scientific and Technological Research Council of Turkey (TUBITAK) (Project No: 214M149).


  1. Abou-Yousef H, Hassan EB (2014) A novel approach to enhance the activity of H-form zeolite catalyst for production of hydroxymethylfurfural from cellulose. J Ind Eng Chem 20:1952–1957CrossRefGoogle Scholar
  2. Almeida RM, Albuquerque NJA, Souza FTC, Meneghetti SMP (2016) Catalysts based on TiO2 anchored with MoO3 or SO4 2− for conversion of cellulose into chemicals. Catal Sci Technol 6:3137–3142CrossRefGoogle Scholar
  3. Amarasekara A, Williams L, Ebede C (2008) Mechanism of the dehydration of d-fructose to 5-hydroxymethylfurfural in dimethyl sulfoxide at 150 °C: an NMR study. Carbohydr Res 343:3021–3024CrossRefGoogle Scholar
  4. Ayari F, Mhamdi M, Hammedia T, Álvarez-Rodríguez J, Guerrero-Ruiz AR, Delahay G, Ghorbel A (2012) Influence of the parent zeolite structure on chromium speciation and catalytic properties of Cr-zeolite catalysts in the ethylene ammoxidation. Appl Catal A-Gen 439–440:88–100CrossRefGoogle Scholar
  5. Aylak AR, Akmaz S, Koc SN (2017) An efficient heterogeneous CrOx–Y zeolite catalyst for glucose to HMF conversion in ionic liquids. Particul Sci Technol 35:490–493CrossRefGoogle Scholar
  6. Binder JB, Raines RT (2009) Simple chemical transformation of lignocellulosic biomass into furans for fuels and chemicals. J Am Chem Soc 131:1979–1985CrossRefGoogle Scholar
  7. Boucetta C, Kacimi M, Ensuque A, Piquemal JY, Bozon-Verduraz F, Ziyad M (2009) Oxidative dehydrogenation of propane over chromium-loaded calcium-hydroxyapatite. Appl Catal A-Gen 356:201–210CrossRefGoogle Scholar
  8. Climent MJ, Corma A, Iborra S (2011) Converting carbohydrates to bulk chemicals and fine chemicals over heterogeneous catalysts. Green Chem 13:520–540CrossRefGoogle Scholar
  9. Cui J, Tan J, Deng T, Cui X, Zhu Y, Lia Y (2016) Conversion of carbohydrates to furfural via selective cleavage of the carbon–carbon bond: the cooperative effects of zeolite and solvent. Green Chem 18:1619–1624CrossRefGoogle Scholar
  10. De Jong E, Higson A, Walsh P, Wellisch M (2012) Bio-based chemicals value added products from bio refineries. IEA Bioenergy, Task42 BiorefineryGoogle Scholar
  11. Dutta S, De S, Alam MI, Abu-Omar MM, Saha B (2012) Direct conversion of cellulose and lignocellulosic biomass into chemicals and biofuel with metal chloride catalysts. J Catal 288:8–15CrossRefGoogle Scholar
  12. Graham BJ, Raines RT (2018) Efficient metal-free conversion of glucose to 5-hydroxymethylfurfural using a boronic acid. Biomass Conv Bioref. CrossRefGoogle Scholar
  13. Hu L, Sun Y, Lin L, Liu S (2012) 12-Tungstophosphoric acid/boric acid as synergetic catalysts for the conversion of glucose into 5-hydroxymethylfurfural in ionic liquid. Biomass Bioenergy 47:289–294CrossRefGoogle Scholar
  14. Hu L, Wu Z, Xu J, Sun Y, Lin L, Liu S (2014) Zeolite-promoted transformation of glucose into 5-hydroxymethylfurfural in ionic liquid. Chem Eng J 244:137–144CrossRefGoogle Scholar
  15. Jadhav H, Taarning E, Pedersen CM, Bols M (2012) Conversion of d-glucose into 5-hydroxymethylfurfural (HMF) using zeolite in [Bmim]Cl or tetrabutylammonium chloride (TBAC)/CrCl2. Tetrahedron Lett 53:983–985CrossRefGoogle Scholar
  16. Karinen R, Vilonen K, Niemelä M (2011) Biorefining: heterogeneously catalyzed reactions of carbohydrates for the production of furfural and hydroxymethylfurfural. ChemSusChem 4:1002–1016CrossRefGoogle Scholar
  17. Kazi FK, Patel AD, Serrano-Ruiz JC, Dumesic JA, Anex RP (2011) Techno-economic analysis of dimethylfuran (DMF) and hydroxymethylfurfural (HMF) production from pure fructose in catalytic processes. Chem Eng J 169:329–338CrossRefGoogle Scholar
  18. Lai B, Zhao Y, Yan L-f (2013) Preparation of 5-hydroxymethylfurfural from cellulose via fast depolymerization and consecutively catalytic conversion. Chin J Chem Phys 26:355–360CrossRefGoogle Scholar
  19. Lei H, Geng Z, Xing T, Zhen W, Jiaxing X, Lu L, Shijie L (2013) Catalytic conversion of carbohydrates into 5-hydroxymethylfurfural over cellulose-derived carbonaceous catalyst in ionic liquid. Bioresour Technol 148:501–507CrossRefGoogle Scholar
  20. Marianou AA, Michailof CM, Pineda A, Iliopoulou EF, Triantafyllidis KS, Lappas AA (2018) Effect of Lewis and Brønsted acidity on glucose conversion to 5-HMF and lactic acid in aqueous and organic media. Appl Catal A Gen 555:75–87CrossRefGoogle Scholar
  21. Mirzaei HM, Karimi B (2016) Sulphanilic acid as a recyclable bifunctional organocatalyst in the selective conversion of lignocellulosic biomass to 5-HMF. Green Chem 18:2282–2286CrossRefGoogle Scholar
  22. Roman-Leshkov Y, Chheda J, Dumesic J (2006) Phase modifiers promote efficient production of hydroxymethylfurfural from fructose. Science 312:1933–1937CrossRefGoogle Scholar
  23. Shen Y, Sun J, Yi Y, Li M, Wang B, Xu F, Sun R (2014) InCl3-catalyzed conversion of carbohydrates into 5-hydroxymethylfurfural in biphasic system. Bioresour Technol 172:457–460CrossRefGoogle Scholar
  24. Silva B, Figueiredo H, Santos VP, Pereira MFR, Figueiredo JL, Lewandowska AE, Banares MA, Nevesd IC, Tavares T (2011) Reutilization of Cr-Y zeolite obtained by biosorption in the catalytic oxidation of volatile organic compounds. J Hazard Mater 192:545–553CrossRefGoogle Scholar
  25. Tan MX, Zhao L, Zhang Y (2011) Production of 5-hydroxymethyl furfural from cellulose n in CrCl2/zeolite/BMIMCl system. Biomass Bioenergy 35:1367–1370CrossRefGoogle Scholar
  26. Tong X, Ma Y, Li Y (2010) Biomass into chemicals: conversion of sugars to furan derivatives by catalytic processes. Appl Catal A Gen 385:1–13CrossRefGoogle Scholar
  27. Veronque J, Flora C, Frank R, Amandine C, Catherine P, Emmanuelle G (2009) Non-catalyzed and Pt/γ-Al2O3-catalyzed hydrothermal cellulose dissolution–conversion: influence of the reaction parameters and analysis of the unreacted cellulose. Green Chem 12:2052–2060Google Scholar
  28. Wang JJ, Xu WJ, Ren JW, Liu XH, Lu GZ, Wang YQ (2011) Efficient catalytic conversion of fructose into hydroxymethylfurfural by a novel carbon-based solid acid. Green Chem 13:2678–2681CrossRefGoogle Scholar
  29. Xiao S, Liu B, Wang Y, Fang Z, Zhang Z (2014) Efficient conversion of cellulose into biofuel precursor 5-hydroxymethylfurfural in dimethyl sulfoxide–ionic liquid mixtures. Bioresour Technol 151:361–366CrossRefGoogle Scholar
  30. Yang F, Li Y, Zhang Q, Sun X, Fan H, Xu N, Li G (2015) Selective conversion of cotton cellulose to glucose and 5-hydroxymethyl furfural with SO4 2−/MxOy solid superacid catalyst. Carbohydr Polym 131:9–14CrossRefGoogle Scholar
  31. Zhang Z, Zhao Z (2011) Production of 5-hydroxymethylfurfural from glucose catalyzed by hydroxyapatite supported chromium chloride. Bioresour Technol 102:3970–3972CrossRefGoogle Scholar
  32. Zhang J, Cao Y, Li H, Ma X (2014) Kinetic studies on chromium-catalyzed conversion of glucose into 5-hydroxymethylfurfural in alkylimidazolium chloride ionic liquid. Chem Eng J 237:55–61CrossRefGoogle Scholar
  33. Zhang YR, Li N, Li MF, Fan YM (2016) Highly efficient conversion of microcrystalline cellulose to 5-hydroxymethyl furfural in a homogeneous reaction system. RSC Adv 6:21347–21351CrossRefGoogle Scholar
  34. Zhao HB, Holladay JE, Brown H, Zhang ZC (2007) Metal chlorides ionic liquid solvents convert sugars to 5-hydroxymethylfurfural. Science 316:1597–1600CrossRefGoogle Scholar
  35. Zhou L, He Y, Ma Z, Liang R, Wua Y (2015) Sulfonated hierarchical H-USY zeolite for efficient hydrolysis of hemicellulose/cellulose. Carbohydr Polym 117:694–700CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2019

Authors and Affiliations

  • Esra Sezgin
    • 1
  • Merve Esen Keçeci
    • 1
  • Solmaz Akmaz
    • 1
    Email author
  • Serkan Naci Koc
    • 1
  1. 1.Department of Chemical EngineeringIstanbul University-CerrahpaşaIstanbulTurkey

Personalised recommendations