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Cellulose

, Volume 19, Issue 6, pp 2033–2047 | Cite as

Approaching zero cellulose loss in cellulose nanocrystal (CNC) production: recovery and characterization of cellulosic solid residues (CSR) and CNC

  • Q. Q. Wang
  • J. Y. Zhu
  • R. S. Reiner
  • S. P. Verrill
  • U. Baxa
  • S. E. McNeil
Original Paper

Abstract

This study demonstrated the potential of simultaneously recovering cellulosic solid residues (CSR) and producing cellulose nanocrystals (CNCs) by strong sulfuric acid hydrolysis to minimize cellulose loss to near zero. A set of slightly milder acid hydrolysis conditions than that considered as “optimal” were used to significantly minimize the degradation of cellulose into soluble sugars that cannot be economically recovered, but resulted in CSR that is easily recoverable through conventional centrifuge. It was found that the window for simultaneous recoveries of CSR and producing high yield CNC in strong acid hydrolysis was extremely narrow. However, we achieved significant CSR yield with near zero cellulose loss but without sacrificing CNC yield compared with that obtained at “optimal condition”. The resultant CSR contains sulfate ester groups that facilitated subsequent mechanical nano-fibrillation to cellulose nanofibrils (CNFs), a potential high value nanocellulosic material for a variety of applications.

Keywords

Nanocellulose materials/composites Cellulose nanocrystals (CNCs) Cellulose nanofibrils (CNFs) Cellulose nanowhiskers (CNWs) Acid hydrolysis 

Notes

Acknowledgments

Financial support for this work included USDA Agriculture and Food Research Initiative (AFRI) Competitive Grant (No. 2011-67009-20056) and Chinese Scholarship Council (CSC). The funding from these two programs made the visiting appointment of Wang at the USDA Forest Products Laboratory (FPL) possible. We would like to acknowledge Fred Matt and Kolby Hirth (Both FPL) for conducting carbohydrate and sulfur content measurements, respectively, Thomas Kuster (FPL) for SEM image analysis, Debby Sherman of DSimaging and Life Science Microscopy Facility at Purdue University for TEM analysis of the mechanically fibrillated CSR samples. We also would like to thank Anne Kamata, SAIC-Frederick, Inc. for electron microscopy imaging. The TEM imaging work has been funded in whole or in part with federal funds from the National Cancer Institute, National Institutes of Health, under Contract No. HHSN261200800001E. The content of this publication does not necessarily reflect the views or policies of the Department of Health and Human Services, nor does mention of trade names, commercial products, or organizations imply endorsement by the U.S. Government.

References

  1. Araki J, Wada M, Kuga S, Okano T (1998) Flow properties of microcrystalline cellulose suspension prepared by acid treatment of native cellulose. Colloids Surf A 142:75–82CrossRefGoogle Scholar
  2. Battista OA (1950) Hydrolysis and crystallization of cellulose. Ind Eng Chem 42(3):502–507CrossRefGoogle Scholar
  3. Beck-Candanedo S, Roman M, Gray DG (2006) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromolecules 6:1048–1054CrossRefGoogle Scholar
  4. Bondeson DAM, Oksman K (2006) Optimization of the isolation of manocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose 13:171–180CrossRefGoogle Scholar
  5. Chen Y, Liu C, Chang PR, Cao X, Anderson DP (2009) Bionanocomposites based on pea starch and cellulose nanowhiskers hydrolyzed from pea hull fibre: effect of hydrolysis time. Carbohydr Polym 76(4):607–615CrossRefGoogle Scholar
  6. Chum HL, Johnson DK, Black SK, Overend RP (1990) Pretreatment-catalyst effects of the combined severity parameter. Appl Biochem Biotechnol 24(25):1–14CrossRefGoogle Scholar
  7. Dong XM, Revol JF, Gray DG (1998) Effect of microcrystallite preparation conditions on the formation of colloid crystals of cellulose. Cellulose 5:19–32CrossRefGoogle Scholar
  8. Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Capadona JR, Rowan SJ, Weder C, Thielemans W, Roman M, Renneckar S (2010) Review: current international research into cellulose nanofibres and nanocomposites. J Mater Sci 45(1):1–33CrossRefGoogle Scholar
  9. Franson MH (1985) Standard Methods for the Examination of Water and Wastewater. 16th Ed. American Public Health Association (APHA), Washington, pp 532–537Google Scholar
  10. Hamad WY (2011) Development and properties of nanocrystalline cellulose (NCC). In: Zhu JY, Zhang X, Pan XJ (eds) Sustainable production of fuels, chemicals, and fibers from forest biomass. American Chemical Society, Washington, DC, pp 301–321CrossRefGoogle Scholar
  11. Hamad WY, Hu TQ (2010) Structure–process–yield interrelations in nanocrystalline cellulose extraction. Can J Chem Eng 88:392–402Google Scholar
  12. Klemm D, Kramer F, Moritz S, Lindstrom T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed 50(24):5438–5466CrossRefGoogle Scholar
  13. Marchessault RH, Morehead FF, Koch MJ (1961) Some hydrodynamic properties of neutral suspensions of cellulose crystallites as realted to size and shape. J Colloid Sci 16:327–344CrossRefGoogle Scholar
  14. Moran JL, Alvarez VA, Cyras VP, Vazquez A (2008) Extraction of cellulose and preparation of nanocellulose from sisal fibers. Cellulose 15:149–159CrossRefGoogle Scholar
  15. Mukherjee SM, Woods HJ (1953) X-ray and electron microscope studies of the degradation of cellulose by sulphuric acid. Biochim Biophys Acta 10:499–511CrossRefGoogle Scholar
  16. Nickerson RF, Habrle JA (1947) Cellulose intercrystalline structure. Ind Eng Chem 39:1507–1512CrossRefGoogle Scholar
  17. Rånby BG (1951) The colloidal properties of cellulose micelles. Discuss Faraday Soc 11:158–164CrossRefGoogle Scholar
  18. Revol J-F, Bradford H, Giasson J, Marchessault RH, Gray DG (1992) Helicoidal self-ordering of cellulose microfibrils in squeous suspension. Int J Biol Macromol 14:170–172CrossRefGoogle Scholar
  19. Saito T, Okita Y, Nge TT, Sugiyama J, Isogai A (2006) TEMPO-mediated oxidation of native cellulose: microscopic analysis of fibrous fractions in the oxidized products. Carbohydr Polym 65:435–440CrossRefGoogle Scholar
  20. Stamm AJ (1964) Wood and cellulose science. The Ronald Press Company, New York, p 549Google Scholar
  21. Wegner TH, Jones EP (2009) A fundamental review of the relationships between nanotechnology and lignocellulosic biomass. In: Lucia LA, Rojas OJ (eds) The Nanoscience and Technology of Renewable Biomaterials. 1 st ed. John Wiley and Sons, USA, pp 1–41CrossRefGoogle Scholar
  22. Zhu JY, Sabo R, Luo X (2011) Integrated production of nano-fibrillated cellulose and cellulosic biofuel (ethanol) by enzymatic fractionation of wood fibers. Green Chem 13(5):1339–1344CrossRefGoogle Scholar
  23. Zhu W, Houtman CJ, Zhu JY, Gleisner R, Chen KF (2012) Quantitative predictions of bioconversion of aspen by dilute acid and SPORL pretreatments using a unified combined hydrolysis factor (CHF). Process Biochem 47:785–791CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. (outside the USA)  2012

Authors and Affiliations

  • Q. Q. Wang
    • 1
    • 2
  • J. Y. Zhu
    • 2
  • R. S. Reiner
    • 2
  • S. P. Verrill
    • 2
  • U. Baxa
    • 3
  • S. E. McNeil
    • 4
  1. 1.State Key Lab of Pulp and Paper EngineeringSouth China University of TechnologyGuangzhouChina
  2. 2.USDA Forest ServiceForest Products LaboratoryMadisonUSA
  3. 3.Electron Microscopy LaboratorySAIC-Frederick, Inc., NCI-FrederickFrederickUSA
  4. 4.Nanotechnology Characterization Laboratory, Advanced Technology ProgramSAIC-Frederick, Inc., NCI-FrederickFrederickUSA

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