Cellulose

, Volume 24, Issue 12, pp 5403–5415 | Cite as

Metal sulfates-catalyzed butanolysis of cellulose: butyl levulinate production and optimization

  • Lin Deng
  • Chun Chang
  • Ran An
  • Xiaoge Qi
  • Guizhuan Xu
Original Paper
First Online:
Received:
Accepted:

Abstract

Direct production of butyl levulinate (BL) by butanolysis of cellulose was carried out using single or combined metal sulfates catalysts. The synergetic enhancement of the ferric sulfate and aluminum sulfate can improve the conversion of cellulose to BL. Moreover, the butanolysis of cellulose was optimized by using response surface methodology. Under the optimum conditions of 194 °C, catalyst concentration 10.0 g/L and reaction time 3 h, the average cellulose conversion of 100% and BL yield of 40.3% were obtained. In addition, the analysis of liquid products and the characterization of catalyst were performed, and the reusability experiments showed that the metal sulfates can be easily recycled and be reused more than five times with high activity in the butanolysis process. This study provided an economical and feasible method for bio-based BL production from cellulose.

Keywords

Cellulose Butanolysis Butyl levulinate Metal sulfate 
This is a preview of subscription content, log in to check access.

Notes

Acknowledgments

The authors gratefully acknowledge the financial support from the Natural Science Foundation of Henan Province of China (162300410247) and the Foundation and Frontier Technology Research Project of Henan Province of China (162300410007).

Supplementary material

10570_2017_1530_MOESM1_ESM.docx (445 kb)
Supplementary material 1 (DOCX 445 kb)

References

  1. An R, Xu G, Chang C et al (2017) Efficient one-pot synthesis of n-butyl levulinate from carbohydrates catalyzed by Fe2(SO4)3. J Energy Chem 26:556–563CrossRefGoogle Scholar
  2. Badgujar KC, Bhanage BM (2015) Thermo-chemical energy assessment for production of energy-rich fuel additive compounds by using levulinic acid and immobilized lipase. Fuel Process Technol 138:139–146CrossRefGoogle Scholar
  3. Demmacarà P, Ciriminna R, Shiju NR et al (2014) Enhanced heterogeneous catalytic conversion of furfuryl alcohol into butyl levulinate. Chemsuschem 7:835–840CrossRefGoogle Scholar
  4. Démolis A, Essayem N, Rataboul F et al (2014) Synthesis and applications of alkyl levulinates. ACS Sustain Chem Eng 2:1338–1352CrossRefGoogle Scholar
  5. Démolis A, Eternot M, Essayem N, Rataboul F (2016) Influence of butanol isomers on the reactivity of cellulose towards the synthesis of butyl levulinates catalyzed by liquid and solid acid catalysts. New J Chem 40:3747–3754CrossRefGoogle Scholar
  6. Elumalai S, Agarwal B, Runge TM, Sangwan RS (2016) Integrated two-stage chemically processing of rice straw cellulose to butyl levulinate. Carbohydr Polym 150:286–298CrossRefGoogle Scholar
  7. Hishikawa Y, Yamaguchi M, Kubo S, Yamada T (2013) Direct preparation of butyl levulinate by a single solvolysis process of cellulose. J Wood Sci 59:179–182CrossRefGoogle Scholar
  8. Huang YB, Yang T, Zhou MC et al (2016) Microwave-assisted alcoholysis of furfural alcohol into alkyl levulinates catalyzed by metal salts. Green Chem 18:1516–1523CrossRefGoogle Scholar
  9. Joshi H, Moser BR, Toler J et al (2011) Ethyl levulinate: a potential bio-based diluent for biodiesel which improves cold flow properties. Biomass Bioenergy 35:3262–3266CrossRefGoogle Scholar
  10. Kean JR, Graham AE (2015) Indium(III) triflate promoted synthesis of alkyl levulinates from furyl alcohols and furyl aldehydes. Catal Commun 59:175–179CrossRefGoogle Scholar
  11. Lincai P, Hui Li, Keli C (2015) Effect of metal salts existence during the acid-catalyzed conversion of glucose in methanol medium. Catal Commun 59:10–13CrossRefGoogle Scholar
  12. Liu Y, Liu CL, Wu HZ, Dong WS (2013) An efficient catalyst for the conversion of fructose into methyl levulinate. Catal Letters 143:1346–1353CrossRefGoogle Scholar
  13. Ma H, Long JX, Wang FR et al (2015) Conversion of cellulose to butyl levulinate in bio-butanol medium catalyzed by acidic ionic liquids. Acta Phys Chim Sin 31:973–979Google Scholar
  14. Neves P, Lima S, Pillinger M et al (2013) Conversion of furfuryl alcohol to ethyl levulinate using porous aluminosilicate acid catalysts. Catal Today 218–219:76–84CrossRefGoogle Scholar
  15. Neves P, Russo PA, Fernandes A et al (2014) Mesoporous zirconia-based mixed oxides as versatile acid catalysts for producing bio-additives from furfuryl alcohol and glycerol. Appl Catal A Gen 487:148–157CrossRefGoogle Scholar
  16. Okić M, Kesić Ž, Krstić J et al (2012) Decrease of free fatty acid content in vegetable oil using silica supported ferric sulfate catalyst. Fuel 97:595–602CrossRefGoogle Scholar
  17. Peng L, Tao R, Wu Y (2016) Catalytic upgrading of biomass-derived furfuryl alcohol to butyl levulinate biofuel over common metal salts. Catalysts 6:1–12CrossRefGoogle Scholar
  18. Ren D, Fu J, Li L et al (2016) Efficient conversion of biomass-derived furfuryl alcohol to levulinate esters over commercial α-Fe2O3. RSC Adv 6:22174–22178CrossRefGoogle Scholar
  19. Tejero MAA, Ramírez E, Fité C et al (2016) Esterification of levulinic acid with butanol over ion exchange resins. Appl Catal A Gen 517:56–66CrossRefGoogle Scholar
  20. Tominaga K, Mori A, Fukushima Y et al (2011) Mixed-acid systems for the catalytic synthesis of methyl levulinate from cellulose. Green Chem 13:810CrossRefGoogle Scholar
  21. Wang Z, Hu X, Käll P-O, Helmersson U (2001) High Li+ ion storage capacity and double-electrochromic behavior of sol–gel-derived iron oxide thin films with sulfate residues. Chem Mater 13:1976–1983CrossRefGoogle Scholar
  22. Yamada T, Yamaguchi M, Kubo S, Hishikawa Y (2015) Direct production of alkyl levulinates from cellulosic biomass by a single-step acidic solvolysis system at ambient atmospheric pressure. BioResources 10:4961–4969CrossRefGoogle Scholar
  23. Zhang Z, Dong K, Zhao Z (2011) Efficient conversion of furfuryl alcohol into alkyl levulinates catalyzed by an organic-inorganic hybrid solid acid catalyst. Chemsuschem 4:112–118CrossRefGoogle Scholar
  24. Zhao S, Xu G, Chang C et al (2015) Direct conversion of carbohydrates into ethyl levulinate with potassium phosphotungstate as an efficient catalyst. Catalysts 5:1897–1910CrossRefGoogle Scholar
  25. Zhong C, Wang C, Huang F et al (2015) Selective hydrolysis of hemicellulose from wheat straw by a nanoscale solid acid catalyst. Carbohydr Polym 131:384–391CrossRefGoogle Scholar
  26. Zhou L, Zou H, Nan J et al (2014) Conversion of carbohydrate biomass to methyl levulinate with Al2(SO4)3 as a simple, cheap and efficient catalyst. Catal Commun 50:13–16CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2017

Authors and Affiliations

  • Lin Deng
    • 1
  • Chun Chang
    • 1
  • Ran An
    • 1
  • Xiaoge Qi
    • 1
  • Guizhuan Xu
    • 2
  1. 1.School of Chemical Engineering and EnergyZhengzhou UniversityZhengzhouChina
  2. 2.College of Mechanical and Electrical EngineeringHenan Agricultural UniversityZhengzhouChina

Personalised recommendations