Skip to main content
SpringerLink
Log in

Efficient dehydration of carbohydrates to 5-hydroxymethylfurfural in ionic liquids catalyzed by tin(IV) phosphonate and zirconium phosphonate

  • Articles
  • Published:
Science China Chemistry Aims and scope Submit manuscript

Abstract

In this work, we synthesized tin(IV) phosphonate (SnBPMA) and zirconium phosphonate (ZrBPMA) by the reaction of SnCl4·5H2O or ZrOCl2·8H2O with N,N-bis(phosphonomethyl)aminoacetic acid, which was synthesized from a biomaterial glycine through a Mannich-type reaction. The SnBPMA and ZrBPMA were very efficient heterogeneous catalysts for the dehydration of fructose to produce 5-hydroxymethylfurfural (HMF), and the SnBPMA had higher activity than the ZrBPMA. The effects of solvents, temperature, reaction time, and reactant/solvent weight ratio on the reaction catalyzed by SnBPMA were investigated. It was demonstrated that the yield of HMF could reach 86.5% with 1-ethyl-3-methylimidazolium bromide ([Emim] Br) as solvent, and the SnBPMA and SnBPMA/[Emim]Br catalytic system could be reused five times without considerable reduction in catalytic efficiency. Further study indicated that the SnBPMA and ZrBPMA in [Emim]Br were also effective for the dehydration of sucrose and inulin to produce HMF with satisfactory yields.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Tuck CO, Pérez E, Horváth IT, Sheldon RA, Poliakoff M. Valorization of biomass: Deriving more value from waste. Science, 2012, 337: 695–699

    Article  CAS  Google Scholar 

  2. Alonso DM, Wettstein SG, Dumesic JA. Bimetallic catalysts for upgrading of biomass to fuels and chemicals. Chem Soc Rev, 2012, 41: 8075–8098

    Article  CAS  Google Scholar 

  3. Gallezot P. Conversion of biomass to selected chemical products. Chem Soc Rev, 2012, 41: 1538–1558

    Article  CAS  Google Scholar 

  4. Long JX, Li XH, Wang LF, Zhang N. Ionic liquids: Efficient solvent and medium for the transformation of renewable lignocellulose. Sci China Chem, 2012, 55: 1500–1508

    Article  CAS  Google Scholar 

  5. Stark A, Sellin M, Ondruschka B, Massonne K. The effect of hydrogen bond acceptor properties of ionic liquids on their cellulose solubility. Sci China Chem, 2012, 55: 1663–1670

    Article  CAS  Google Scholar 

  6. Fang DW, Li M, Ge RL, Zang SL, Yang JZ, Gao YA. Density estimated physicochemical properties of alanine-based ionic liquid [C7mim][Ala] and its application in selective transesterification of soybean oil. Sci China Chem, 2012, 55: 1677–1682

    Article  CAS  Google Scholar 

  7. Deng TY, Sun JY, Liu HC. Cellulose conversion to polyols on supported ru catalysts in aqueous basic solution. Sci China Chem, 2010, 53: 1476–1480

    Article  CAS  Google Scholar 

  8. Qi XH, Watanabe M, Aida TM, Smith RL. Synergistic conversion of glucose into 5-hydroxymethylfurfural in ionic liquid-water mixtures. Bioresource Technol, 2012, 109: 224–228

    Article  CAS  Google Scholar 

  9. Zhang ZH, Liu B, Zhao ZB. Conversion of fructose into 5-HMF catalyzed by GeCl4 in DMSO and [Bmim]Cl system at room temperature. Carbohyd Polym, 2012, 88: 891–895

    Article  CAS  Google Scholar 

  10. Zhang ZH, Wang Q, Xie HB, Liu WJ, Zhao ZB. Catalytic conversion of carbohydrates into 5-hydroxymethylfurfural by germanium(IV) chloride in ionic liquids. ChemSusChem, 2011, 4: 131–138

    Article  Google Scholar 

  11. Hu SQ, Zhang ZF, Song JL, Zhou YX, Han BX. Efficient conversion of glucose into 5-hydroxymethylfurfural catalyzed by a common lewis acid SnCl4 in an ionic liquid. Green Chem, 2009, 11: 1746–1749

    Article  CAS  Google Scholar 

  12. Yang Y, Hu CW, Abu-Omar MM. Conversion of carbohydrates and lignocellulosic biomass into 5-hydroxymethylfurfural using AlCl3·6H2O catalyst in a biphasic solvent system. Green Chem, 2012, 14: 509–513

    Article  Google Scholar 

  13. Ståhlberg T, Rodriguez-Rodriguez S, Fristrup P, Riisager A. Metal-free dehydration of glucose to 5-(hydroxymethyl)furfural in ionic liquids with boric acid as a promoter. Chem Eur J, 2011, 17: 1456–1464

    Article  Google Scholar 

  14. Hansen TS, Mielby J, Riisager A. Synergy of boric acid and added salts in the catalytic dehydration of hexoses to 5-hydroxymethylfurfural in water. Green Chem, 2011, 13: 109–114

    Article  CAS  Google Scholar 

  15. Zhao S, Cheng MX, Li JZ, Tian J, Wang XH. One pot production of 5-hydroxymethylfurfural with high yield from cellulose by a bronsted-lewis-surfactant-combined heteropolyacid catalyst. Chem Commun, 2011, 47: 2176–2178

    Article  CAS  Google Scholar 

  16. Zhang YM, Degirmenci V, Li C, Hensen EJM. Phosphotungstic acid encapsulated in metal-organic framework as catalysts for carbohydrate dehydration to 5-hydroxymethylfurfural. ChemSusChem, 2011, 4: 59–64

    Article  Google Scholar 

  17. Qu YS, Huang CP, Song YL, Zhang J, Chen BH. Efficient dehydration of glucose to 5-hydroxymethylfurfural catalyzed by the ionic liquid, 1-hydroxyethyl-3-methylimidazolium tetrafluoroborate. Bioresource Technol, 2012, 121: 462–466

    Article  CAS  Google Scholar 

  18. Tong XL, Ma Y, Li YD. An efficient catalytic dehydration of fructose and sucrose to 5-hydroxymethylfurfural with protic ionic liquids. Carbohyd Res, 2010, 345: 1698–1701

    Article  CAS  Google Scholar 

  19. Zhang Y, Wang JJ, Ren JW, Liu XH, Li XC, Xia YJ, Lu GZ, Wang YQ. Mesoporous niobium phosphate: An excellent solid acid for the dehydration of fructose to 5-hydroxymethylfurfural in water. Catal Sci Technol, 2012, 2: 2485–2491

    Article  CAS  Google Scholar 

  20. Qi XH, Guo HX, Li LY, Smith RL. Acid-catalyzed dehydration of fructose into 5-hydroxymethylfurfural by cellulose-derived amorphous carbon. ChemSusChem, 2012, 5: 2215–2220

    Article  CAS  Google Scholar 

  21. Wang JJ, Xu WJ, Ren JW, Liu XH, Lu GZ, Wang YQ. Efficient catalytic conversion of fructose into hydroxymethylfurfural by a novel carbon-based solid acid. Green Chem, 2011, 13: 2678–2681

    Article  CAS  Google Scholar 

  22. Sidhpuria KB, Daniel-da-Silva AL, Trindade T, Coutinho JAP. Supported ionic liquid silica nanoparticles (SILnPs) as an efficient and recyclable heterogeneous catalyst for the dehydration of fructose to 5-hydroxymethylfurfural. Green Chem, 2011, 13: 340–349

    Article  CAS  Google Scholar 

  23. Iremonger SS, Liang JM, Vaidhyanathan R, Martens I, Shimizu GKH, Daff TD, Aghaji MZ, Yeganegi S, Woo TK. Phosphonate monoesters as carboxylate-like linkers for metal organic frameworks. J Am Chem Soc, 2011, 133: 20048–20051

    Article  CAS  Google Scholar 

  24. Ma TY, Lin XZ, Zhang XJ, Yuan ZY. High surface area titanium phosphonate materials with hierarchical porosity for multi-phase adsorption. New J Chem, 2010, 34: 1209–1216

    Article  CAS  Google Scholar 

  25. Dutta A, Pramanik M, Patra AK, Nandi M, Uyama H, Bhaumik A. Hybrid porous tin(IV) phosphonate: An efficient catalyst for adipic acid synthesis and a very good adsorbent for CO2 uptake. Chem Commun, 2012, 48: 6738–6740

    Article  CAS  Google Scholar 

  26. Jiménez-Morales I, Santamaría-González J, Maireles-Torres P, Jiménez-López A. Mesoporous tantalum phosphate as acidic catalyst for the methanolysis of sunflower oil. Appl Catal B-Environ, 2012, 123-124: 316–323

    Article  Google Scholar 

  27. Pramanik M, Nandi M, Uyama H, Bhaumik A. Organic-inorganic hybrid porous sulfonated zinc phosphonate material: Efficient catalyst for biodiesel synthesis at room temperature. Green Chem, 2012, 14: 2273–2281

    Article  CAS  Google Scholar 

  28. Song JL, Mao JG, Sun YQ, Clearfield A. Novel hybrid porous 3d networks of Lead(II) diphosphonate and triphosphonate containing 1,3,5-benzenetricarboxylate. Eur J Inorg Chem, 2003, 2003: 4218–4226

    Article  Google Scholar 

  29. Mao JG, Wang ZK, Clearfield A. Building layered structures from hydrogen bonded molecular units and 1D metal phosphonate chains: Synthesis, characterization and crystal structures of N,N’-dimethyl-N,N′-ethylenediamine-bis(methylenephosphonic acid), its Ni(II) and Pb(II) complexes. J Chem Soc, Dalton T, 2002, 2: 4541–4546

    Article  Google Scholar 

  30. Lai LK, Zhang YG. The effect of imidazolium ionic liquid on the dehydration of fructose to 5-hydroxymethylfurfural, and a room temperature catalytic system. ChemSusChem, 2010, 3: 1257–1259

    Article  CAS  Google Scholar 

  31. Tong XL, Li YD. Efficient and selective dehydration of fructose to 5-hydroxymethylfurfural catalyzed by brønsted-acidic ionic liquids. ChemSusChem, 2010, 3: 350–355

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Beijing National Laboratory for Molecular Sciences; Institute of Chemistry, Chinese Academy of Sciences, Beijing, 100190, China

    Hui Ning, JinLiang Song, MinQiang Hou, DeZhong Yang, HongLei Fan & BuXing Han

Authors
  1. Hui Ning
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. JinLiang Song
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. MinQiang Hou
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. DeZhong Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. HongLei Fan
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. BuXing Han
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to BuXing Han.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Ning, H., Song, J., Hou, M. et al. Efficient dehydration of carbohydrates to 5-hydroxymethylfurfural in ionic liquids catalyzed by tin(IV) phosphonate and zirconium phosphonate. Sci. China Chem. 56, 1578–1585 (2013). https://doi.org/10.1007/s11426-013-4944-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11426-013-4944-3

Keywords

Search

Navigation