, Volume 22, Issue 4, pp 2231–2243 | Cite as

Hydrolysis of cellulose in supercritical water: reagent concentration as a selectivity factor

  • Celia M. Martínez
  • Danilo A. CanteroEmail author
  • M. D. Bermejo
  • M. J. Cocero
Original Paper


In this work, the influence of reagent concentration on hydrolysis reactions of cellulose in supercritical water was analyzed. The hydrolysis was carried out at 400 °C and 25 MPa with reaction times between 0.07 and 1.57 s and feeding cellulose concentrations between 5 and 20 % w/w (1.5–6 % w/w at reactor inlet). Also, a flash separator was used to separate vapor in the product stream in order to increase the final concentration. The best result for sugar production (79 % w/w) was obtained working with a cellulose concentration of 5 % w/w and 0.07-s reaction time. For glycolaldehyde production, the best result (42 % w/w) was obtained with a concentration of 20 % w/w and 1.57 s. The employment of a flash separator allowed reducing the water content by 50 %. It was also observed that by increasing the cellulose concentration in the reactor up to 4 % w/w, the hydrolysis took place with a similar kinetic as that in the heterogeneous media, thus reducing the conversion rate of cellulose in supercritical water.


Biomass Glycolaldehyde Kinetics Sugars Supercritical fluids 



The authors thank the Spanish Ministry of Economy and Competitiveness for Project CTQ2011-23293, CTQ2011-27347, CQT2013-44143-R and ENE2012-33613. MDB thanks the Spanish Ministry of Economy and Competitiveness for Ramón y Cajal research fellowship RYC-2013-13976.

Conflict of interest

The authors declare that they have no conflict of interest.

Supplementary material

10570_2015_674_MOESM1_ESM.doc (221 kb)
Supplementary material 1 (DOC 221 kb)


  1. Aida TM, Sato Y, Watanabe M, Tajima K, Nonaka T, Hattori H, Arai K (2007a) Dehydration of d-glucose in high temperature water at pressures up to 80Mpa. J Supercrit Fluids 40:381–388CrossRefGoogle Scholar
  2. Aida TM et al (2007b) Reactions of d-fructose in water at temperatures up to 400 °C and pressures up to 100Mpa. J Supercrit Fluids 42:110–119CrossRefGoogle Scholar
  3. Akiya N, Savage PE (2002) Roles of water for chemical reactions in high-temperature water. Chem Rev 102:2725–2750CrossRefGoogle Scholar
  4. Arai K, Smith RL, Aida TM (2009) Decentralized chemical processes with supercritical fluid technology for sustainable society. J Supercrit Fluids 47:628–636CrossRefGoogle Scholar
  5. Cantero DA, Bermejo MD, Cocero MJ (2013a) Kinetic analysis of cellulose depolymerization reactions in near critical water. J Supercrit Fluids 75:48–57CrossRefGoogle Scholar
  6. Cantero DA, Bermejo MD, Cocero MJ (2013b) High glucose selectivity in pressurized water hydrolysis of cellulose using ultra-fast reactors. Bioresour. Technol. 135:697–703Google Scholar
  7. Cantero DA, Bermejo MD, Cocero MJ (2015a) Reaction engineering for process intensification of supercritical water biomass refining. J Supercrit Fluids 96:21–35CrossRefGoogle Scholar
  8. Cantero DA, Bermejo MD, Cocero MJ (2015b) Simultaneous and selective recovery of cellulose and hemicellulose fractions from wheat bran by supercritical water hydrolysis. Green Chem 17:610–618CrossRefGoogle Scholar
  9. Ehara K, Saka S (2002) A comparative study on chemical conversion of cellulose between the batch-type and flow-type systems in supercritical water. Cellulose 9:301–311CrossRefGoogle Scholar
  10. Ehara K, Saka S (2005) Decomposition behavior of cellulose in supercritical water, subcritical water, and their combined treatments. J. Wood Sci 51:148–153CrossRefGoogle Scholar
  11. Esposito D, Antonietti M (2013) Chemical conversion of sugars to lactic acid by alkaline hydrothermal processes. ChemSusChem 6:989–992CrossRefGoogle Scholar
  12. Fang Z, Xu C (2014) Near-critical and supercritical water and their applications for biorefineries. Springer, Dordrecht, p 71Google Scholar
  13. Goyal HB, Seal D, Saxena RC (2008) Bio-fuels from thermochemical conversion of renewable resources: a review. Renew Sustain Energy Rev 12:504–517CrossRefGoogle Scholar
  14. Griggs AJ, Kuhn EM, Chen X, Lischeske JJ, Tucker MP, Stickel JJ (2010) Mechanistic models for high-solids loading pretreatment and enzymatic hydrolysis of lignocellulosic biomass. 10AIChE-2010 AIChE Ann Meet Conf Proc, Salt Lake City, p 669aGoogle Scholar
  15. Kumar S, Gupta R, Lee YY, Gupta RB (2010) Cellulose pretreatment in subcritical water: effect of temperature on molecular structure and enzymatic reactivity. Bioresour Technol 101:1337–1347CrossRefGoogle Scholar
  16. Onda A, Ochi T, Yanagisawa K (2009) Hydrolysis of cellulose selectively into glucose over sulfonated activated-carbon catalyst under hydrothermal conditions. Top Catal 52:801–807CrossRefGoogle Scholar
  17. Peterson AA, Vogel F, Lachance RP, Fröling M, Antal JMJ, Tester JW (2008) Thermochemical biofuel production in hydrothermal media: a review of sub- and supercritical water technologies. Energy Environ Sci 1:32CrossRefGoogle Scholar
  18. Rearden P, Sajonz P, Guiochon G (1998) Detailed study of the mass transfer kinetics of Tröger’s base on cellulose triacetate. J Chromatogr A 813:1–9CrossRefGoogle Scholar
  19. Rinaldi R, Schüth F (2009) Acid hydrolysis of cellulose as the entry point into biorefinery schemes. ChemSusChem 2:1096–1107CrossRefGoogle Scholar
  20. Rogalinski T, Ingram T, Brunner G (2008) Hydrolysis of lignocellulosic biomass in water under elevated temperatures and pressures. J Supercrit Fluids 47:54–63CrossRefGoogle Scholar
  21. Sasaki M, Goto K, Tajima K, Adschiri T, Arai K (2002) Rapid and selective retro-aldol condensation of glucose to glycolaldehyde in supercritical water. Green Chem 4:285–287CrossRefGoogle Scholar
  22. Sasaki M, Adschiri T, Arai K (2003a) Fractionation of sugarcane bagasse by hydrothermal treatment Bioresour. Bioresour Technol 86:301–304CrossRefGoogle Scholar
  23. Sasaki M, Adschiri T, Arai K (2003b) Production of cellulose II from native cellulose by near- and supercritical water solubilization. J Agric Food Chem 51:5376–5381CrossRefGoogle Scholar
  24. Sasaki M, Adschiri T, Arai K (2004) Kinetics of cellulose conversion at 25 MPa in sub- and supercritical water. AIChE J 50:192–202CrossRefGoogle Scholar
  25. Sierra-Pallares J, Marchisio DL, Alonso E, Teresa Parra-Santos M, Castro F, José Cocero M (2011) Quantification of mixing efficiency in turbulent supercritical water hydrothermal reactors Chem. Eng. Sci. 66:1576–1589CrossRefGoogle Scholar
  26. Sluiter JB, Ruiz RO, Scarlata CJ, Sluiter AD, Templeton DW (2010) Compositional analysis of lignocellulosic feedstocks. 1. Review and description of methods. J Agric Food Chem 58:9043–9053CrossRefGoogle Scholar
  27. Tollefson J (2008) Energy: not your father’s biofuels. Nat News 451:880–883CrossRefGoogle Scholar
  28. Wang A, Zhang T (2013) One-pot conversion of cellulose to ethylene glycol with multifunctional tungsten-based catalysts. Acc Chem Res 46:1377–1386CrossRefGoogle Scholar
  29. Yu Y, Wu H (2010a) Understanding the primary liquid products of cellulose hydrolysis in hot-compressed water at various reaction temperatures. Energy Fuels 24:1963–1971CrossRefGoogle Scholar
  30. Yu Y, Wu H (2010b) Significant differences in the hydrolysis behavior of amorphous and crystalline portions within microcrystalline cellulose in hot-compressed water. Ind Eng Chem Res 49:3902–3909CrossRefGoogle Scholar
  31. Yu Y, Wu H (2010c) Evolution of primary liquid products and evidence of in situ structural changes in cellulose with conversion during hydrolysis in hot-compressed water. Ind Eng Chem Res 49:3919–3925CrossRefGoogle Scholar
  32. Zhang L, Xu C, Champagne P (2010) Overview of recent advances in thermo-chemical conversion of biomass. Energy Convers Manag 51:969–982CrossRefGoogle Scholar
  33. Zhao Y, Lu W-J, Wang H-T (2009) Supercritical hydrolysis of cellulose for oligosaccharide production in combined technology Chem. Eng J 150:411–417Google Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  • Celia M. Martínez
    • 1
  • Danilo A. Cantero
    • 1
    • 2
    Email author
  • M. D. Bermejo
    • 1
  • M. J. Cocero
    • 1
  1. 1.High Pressure Processes Group, Department of Chemical Engineering and Environmental TechnologyUniversity of ValladolidValladolidSpain
  2. 2.Department of Applied and Industrial Chemistry, Faculty of Exact, Physical and Natural SciencesNational University of CordobaCórdobaArgentina

Personalised recommendations