Advertisement

BioEnergy Research

, Volume 5, Issue 2, pp 380–386 | Cite as

Effect of Formic Acid on Conversion of Fructose to 5-Hydroxymethylfurfural in Aqueous/Butanol Media

  • Nan Jiang
  • Renliang Huang
  • Wei Qi
  • Rongxin Su
  • Zhimin He
Article

Abstract

Acid-catalyzed dehydration of carbohydrates into 5-hydroxymethylfurfural (HMF), a valuable biomass-derived intermediate, has received increasing attention. Efficient methods for HMF production are needed for successful commercialization of HMF in the near future. A new process for the dehydration of sugars into 5-hydroxymethylfurfural in aqueous/butanol media enhanced by using formic acid was developed. The effects of formic acid concentration, reaction temperature, and reaction time on the fructose conversion and HMF yield showed the significant influences of these process variables. The optimum conditions were found to be 2.5 mol/L formic acid concentration, 170°C and 70 min. Under such conditions, a fructose conversion of 98.3% with a HMF yield of 69.2% was achieved. The application of the butanol solvent and formic acid led to the conversion of fructose to HMF with high yield. The catalytic system in this study has prospects for commercial application due to its less corrosion and convenient downstream separation.

Keywords

5-Hydroxymethylfurfural Fructose Sugars Formic acid Dehydration 

Abbreviations

HMF

5-Hydroxymethylfurfural

HPLC

High-performance liquid chromatography

ILs

Ionic liquids

Notes

Acknowledgments

This work was supported by the National Natural Science Foundation of China (20976125, 31071509) and Tianjin (10JCYBJC05100), the National Key Technology R&D program (2007BAD42B02), the Program for New Century Excellent Talents in Chinese University (NCET-08-0386), the Program of Introducing Talents of Discipline to Universities of China (B06006), and the Key Project of Chinese Ministry of Education (108031).

Supplementary material

12155_2011_9141_MOESM1_ESM.doc (84 kb)
ESM 1 (DOC 84 kb)

References

  1. 1.
    Atsumi S et al (2008) Non-fermentative pathways for synthesis of branched-chain higher alcohols as biofuels. Nature 451:86–89PubMedCrossRefGoogle Scholar
  2. 2.
    Huber GW et al (2005) Production of liquid alkanes by aqueous-phase processing of biomass-derived carbohydrates. Science 308:1446–1450PubMedCrossRefGoogle Scholar
  3. 3.
    Chheda JN et al (2007) Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals. Angew Chem Int Edit 46:7164–7183CrossRefGoogle Scholar
  4. 4.
    Roman-Leshkov Y et al (2006) Phase modifiers promote efficient production of hydroxymethylfurfural from fructose. Science 312:1933–1937PubMedCrossRefGoogle Scholar
  5. 5.
    Chheda JN et al (2007) Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono- and poly-saccharides. Green Chem 9:342–350CrossRefGoogle Scholar
  6. 6.
    Yong G et al (2008) Efficient catalytic system for the selective production of 5-hydroxymethylfurfural from glucose and fructose. Angew Chem Int Ed 47:9345–9348CrossRefGoogle Scholar
  7. 7.
    Chan JYG et al (2009) Selective conversion of fructose to 5-hydroxymethylfurfural catalyzed by tungsten salts at low temperatures. Chemsuschem 2:731–734PubMedCrossRefGoogle Scholar
  8. 8.
    Zhao HB et al (2007) Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural. Science 316:1597–1600PubMedCrossRefGoogle Scholar
  9. 9.
    Olivier-Bourbigou H et al (2002) Ionic liquids: perspectives for organic and catalytic reactions. J Mol Catal A-Chem 181:419–437CrossRefGoogle Scholar
  10. 10.
    Tukel SS et al (2008) Catalytic efficiency of immobilized glucose isomerase in isomerization of glucose to fructose. Food Chem 111:658–662CrossRefGoogle Scholar
  11. 11.
    Huang R et al (2009) Integrating enzymatic and acid catalysis to convert glucose into 5-hydroxymethylfurfural. Chem Commun (Camb) 46:1115–1117CrossRefGoogle Scholar
  12. 12.
    Hansen TS et al (2009) Efficient microwave-assisted synthesis of 5-hydroxymethylfurfural from concentrated aqueous fructose. Carbohydr Res 344:2568–2572PubMedCrossRefGoogle Scholar
  13. 13.
    Hu SQ et al (2008) Conversion of fructose to 5-hydroxymethylfurfural using ionic liquids prepared from renewable materials. Green Chem 10:1280–1283CrossRefGoogle Scholar
  14. 14.
    Roman-Leshkov Y et al (2007) Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates. Nature 447:982–985PubMedCrossRefGoogle Scholar
  15. 15.
    Thananatthanachon T et al (2010) Efficient production of the liquid fuel 2,5-dimethylfuran from fructose using formic acid as a reagent. Angew Chem Int Ed 49:6616–6618CrossRefGoogle Scholar
  16. 16.
    Thananatthanachon T et al (2010) Efficient route to hydroxymethylfurans from sugars via transfer hydrogenation. Chemsuschem 3:1139–1141PubMedCrossRefGoogle Scholar
  17. 17.
    Vlachos DG et al (2010) The roles of catalysis and reaction engineering in overcoming the energy and the environment crisis. Chem Eng Sci 65:18–29CrossRefGoogle Scholar
  18. 18.
    Asghari FS et al (2006) Dehydration of fructose to 5-hydroxyme-thylfurfural in sub-critical water over heterogeneous zirconium phosphate catalysts. Carbohydr Res 341:2379–2387PubMedCrossRefGoogle Scholar
  19. 19.
    Bicker M et al (2005) Dehydration of d-fructose to hydroxymethylfurfural in sub- and supercritical fluids. J Supercritical Fluids 36:118–126CrossRefGoogle Scholar
  20. 20.
    Qi XH et al (2008) Catalytical conversion of fructose and glucose into 5-hydroxymethylfurfural in hot compressed water by microwave heating. Catal Commun 9:2244–2249CrossRefGoogle Scholar
  21. 21.
    Roman-Leshkov Y et al (2009) Solvent effects on fructose dehydration to 5-hydroxymethylfurfural in biphasic systems saturated with inorganic salts. Top Catal 52:297–303CrossRefGoogle Scholar
  22. 22.
    Qi XH et al (2009) Efficient process for conversion of fructose to 5-hydroxymethylfurfural with ionic liquids. Green Chem 11:1327–1331CrossRefGoogle Scholar
  23. 23.
    Li Y et al (2009) Fructose decomposition kinetics in organic acids-enriched high temperature liquid water. Biomass Bioenerg 33:1182–1187CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC. 2011

Authors and Affiliations

  • Nan Jiang
    • 1
  • Renliang Huang
    • 1
  • Wei Qi
    • 1
  • Rongxin Su
    • 1
  • Zhimin He
    • 1
  1. 1.State Key Laboratory of Chemical Engineering, Chemical Engineering Research Center, School of Chemical Engineering and TechnologyTianjin UniversityTianjinPeople’s Republic of China

Personalised recommendations