Cellulose

, Volume 23, Issue 6, pp 3463–3473 | Cite as

Rapid dissolution of spruce cellulose in H2SO4 aqueous solution at low temperature

  • Weijuan Huang
  • Yixiang Wang
  • Lina Zhang
  • Lingyun Chen
Original Paper
First Online:
Received:
Accepted:
  • 513 Downloads

Abstract

Dissolution of cellulose is the key challenge in its applications. It has been discovered that spruce cellulose with high molecular weight (4.10 × 105 g mol−1) can be dissolved in 64 wt% H2SO4 aqueous solution at low temperature within 2 min, and the cellulose concentration in solution can reach as high as 5 % (w/v). FT-IR spectra and XRD spectra proved that it is a direct solvent for cellulose rather than a derivative aqueous solution system. The cold H2SO4 aqueous solution broke the hydrogen bonds among cellulose molecules and the low temperature dramatically slowed down the hydrolysis, which led to the dissolution of cellulose. The resultant cellulose solution was relatively stable, and the molecular weight of cellulose only slightly decreased after storage at −20 °C for 1 h. Due to the high molecular weight of cellulose, cellulose solution could form regenerated films with good mechanical properties and transparency at low concentration (2 % w/v). This work has not only provided the new evidence of cellulose dissolution which facilitated the development of cellulose solvent, but also suggested a convenient way to directly transfer cellulose with high molecular weight into materials without structure modifications.

Keywords

Spruce cellulose Sulfuric acid Low-temperature Rapid dissolution Regenerated cellulose film 
This is a preview of subscription content, log in to check access.

Notes

Acknowledgments

The authors are grateful to the Natural Sciences and Engineering Research Council of Canada (NSERC), Alberta Crop Industry Development Fund Ltd. (ACIDF), Alberta Innovates Bio Solutions (AI Bio) and Alberta Barley Commission for financial support as well as Canada Foundation for Innovation (CFI) for equipment support. Lingyun Chen would like to thank the Natural Sciences and Engineering Research Council of Canada (NSERC)-Canada Research Chairs Program for its financial support. Weijuan Huang thanks the support from China Scholarship Council (CSC).

References

  1. Aaserud O, Hommeren OJ, Tvedt B, Nakstad P, Mowé G, Efskind J, Russell D, Jörgensen EB, Nyberg-Hansen R, Rootwelt K (1990) Carbon disulfide exposure and neurotoxic sequelae among viscose rayon workers. Am J Ind Med 18:25–37CrossRefGoogle Scholar
  2. 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 Physicochem Eng Asp 142:75–82CrossRefGoogle Scholar
  3. Beck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromolecules 6:1048–1054CrossRefGoogle Scholar
  4. Bondeson D, Mathew A, Oksman K (2006) Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose 13:171–180CrossRefGoogle Scholar
  5. Cai J, Zhang L (2005) Rapid dissolution of cellulose in LiOH/urea and NaOH/urea aqueous solutions. Macromol Biosci 5:539–548CrossRefGoogle Scholar
  6. Cai J, Liu Y, Zhang L (2006) Dilute solution properties of cellulose in LiOH/urea aqueous system. J Polym Sci Part B Polym Phys 44:3093–3101CrossRefGoogle Scholar
  7. Cai J, Zhang L, Liu S, Liu Y, Xu X, Chen X, Chu B, Guo X, Xu J, Cheng H (2008) Dynamic self-assembly induced rapid dissolution of cellulose at low temperatures. Macromolecules 41:9345–9351CrossRefGoogle Scholar
  8. Camacho F, Gonzalez-Tello P, Jurado E, Robles A (1996) Microcrystalline-cellulose hydrolysis with concentrated sulphuric acid. J Chem Technol Biotechnol 67:350–356CrossRefGoogle Scholar
  9. Dawsey T, McCormick CL (1990) The lithium chloride/dimethylacetamide solvent for cellulose: a literature review. J Macromol Sci Rev Macromol Chem Phys 30:405–440CrossRefGoogle Scholar
  10. Dogan H, Hilmioglu ND (2009) Dissolution of cellulose with NMMO by microwave heating. Carbohydr Polym 75:90–94CrossRefGoogle Scholar
  11. Fink H-P, Weigel P, Purz H, Ganster J (2001) Structure formation of regenerated cellulose materials from NMMO-solutions. Prog Polym Sci 26:1473–1524CrossRefGoogle Scholar
  12. Fink H-P, Ganster J, Lehmann A (2014) Progress in cellulose shaping: 20 years industrial case studies at Fraunhofer IAP. Cellulose 21:31–51CrossRefGoogle Scholar
  13. Fort DA, Remsing RC, Swatloski RP, Moyna P, Moyna G, Rogers RD (2007) Can ionic liquids dissolve wood? Processing and analysis of lignocellulosic materials with 1-n-butyl-3-methylimidazolium chloride. Green Chem 9:63–69CrossRefGoogle Scholar
  14. Freudenberg K (1936) The kinetics of long chain disintegration applied to cellulose and starch. Trans Faraday Soc 32:74–75CrossRefGoogle Scholar
  15. Gong X, Wang Y, Tian Z, Zheng X, Chen L (2014) Controlled production of spruce cellulose gels using an environmentally “green” system. Cellulose 21:1667–1678CrossRefGoogle Scholar
  16. Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110:3479–3500CrossRefGoogle Scholar
  17. Hernberg S, Tolonen M, Nurminen M (1976) Eight-year follow-up of viscose rayon workers exposed to carbon disulfide. Scand J Work Environ Health 2:27–30CrossRefGoogle Scholar
  18. Ioelovich M (2012) Study of cellulose interaction with concentrated solutions of sulfuric acid. ISRN Chem Eng. doi: 10.5402/2012/428974 Google Scholar
  19. Kargarzadeh H, Ahmad I, Abdullah I, Dufresne A, Zainudin SY, Sheltami RM (2012) Effects of hydrolysis conditions on the morphology, crystallinity, and thermal stability of cellulose nanocrystals extracted from kenaf bast fibers. Cellulose 19:855–866CrossRefGoogle Scholar
  20. Kataoka Y, Kondo T (1998) FT-IR microscopic analysis of changing cellulose crystalline structure during wood cell wall formation. Macromolecules 31:760–764CrossRefGoogle Scholar
  21. Kim JS, Lee Y, Torget RW (2001) Cellulose hydrolysis under extremely low sulfuric acid and high-temperature conditions. Appl Biochem Biotechnol 91:331–340CrossRefGoogle Scholar
  22. Kolpak F, Blackwell J (1975) The structure of regenerated cellulose. Macromolecules 8:563–564CrossRefGoogle Scholar
  23. Kondo T, Sawatari C (1996) A Fourier transform infra-red spectroscopic analysis of the character of hydrogen bonds in amorphous cellulose. Polymer 37:393–399CrossRefGoogle Scholar
  24. Kupiainen L, Ahola J, Tanskanen J (2012) Distinct effect of formic and sulfuric acids on cellulose hydrolysis at high temperature. Ind Eng Chem Res 51:3295–3300CrossRefGoogle Scholar
  25. Li R, Wang S, Lu A, Zhang L (2015) Dissolution of cellulose from different sources in an NaOH/urea aqueous system at low temperature. Cellulose 22:339–349CrossRefGoogle Scholar
  26. Marrinan H, Mann J (1954) A study by infra-red spectroscopy of hydrogen bonding in cellulose. J Appl Chem 4:204–211CrossRefGoogle Scholar
  27. McCormick CL (1981) Novel cellulose solutions. US Patent 4, 278, 790Google Scholar
  28. McCormick C, Lichatowich D (1979) Homogeneous solution reactions of cellulose, chitin, and other polysaccharides to produce controlled-activity pesticide systems. J Polym Sci Polym Lett Ed 17:479–484CrossRefGoogle Scholar
  29. McCormick CL, Callais PA, Hutchinson BH Jr (1985) Solution studies of cellulose in lithium chloride and N, N-dimethylacetamide. Macromolecules 18:2394–2401CrossRefGoogle Scholar
  30. McCorsley III CC (1979) Process for making amine oxide solution of cellulose. US Patent 4,144,080Google Scholar
  31. McCorsley III CC, Varga JK (1979) Process for making a precursor of a solution of cellulose. US Patent 4,142,913Google Scholar
  32. McCorsley III CC, Varga JK (1980) Process for making a solid impregnated precursor of a solution of cellulose. US Patent 4,211,574Google Scholar
  33. Mülhaupt R (2013) Green polymer chemistry and bio-based plastics: dreams and reality. Macromol Chem Phys 214:159–174CrossRefGoogle Scholar
  34. Nayak JN, Chen Y, Kim J (2008) Removal of impurities from cellulose films after their regeneration from cellulose dissolved in DMAc/LiCl solvent system. Ind Eng Chem Res 47:1702–1706CrossRefGoogle Scholar
  35. Nishiyama K, Takanosu S (1992) Cellulose dope (in Japanese) Google Scholar
  36. Nishiyama Y, Langan P, Chanzy H (2002) Crystal structure and hydrogen-bonding system in cellulose Iβ from synchrotron X-ray and neutron fiber diffraction. J Am Chem Soc 124:9074–9082CrossRefGoogle Scholar
  37. Ono H (1999) New cellulose materials: structure and properties of transparent cellulose gel. Cellul Commun 6:101–105 (In Japanese) Google Scholar
  38. Ono H, Matsui T, Miyamoto I (1998) Cellulose dispersion. US 6,541,627 B1Google Scholar
  39. Qi H, Chang C, Zhang L (2008) Effects of temperature and molecular weight on dissolution of cellulose in NaOH/urea aqueous solution. Cellulose 15:779–787CrossRefGoogle Scholar
  40. Qi H, Chang C, Zhang L (2009) Properties and applications of biodegradable transparent and photoluminescent cellulose films prepared via a green process. Green Chem 11:177–184CrossRefGoogle Scholar
  41. Rabek J (1980) Experimental methods in polymer chemistry: applications of wide-angle X-ray diffraction (WAXD) to the study of the structure of polymers. Wiley, London, p 505Google Scholar
  42. Saeman JF (1945) Kinetics of wood saccharification-hydrolysis of cellulose and decomposition of sugars in dilute acid at high temperature. Ind Eng Chem Res 37:43–52CrossRefGoogle Scholar
  43. Sèbe G, Ham-Pichavant FDR, Ibarboure E, Koffi ALC, Tingaut P (2012) Supramolecular structure characterization of cellulose II nanowhiskers produced by acid hydrolysis of cellulose I substrates. Biomacromolecules 13:570–578CrossRefGoogle Scholar
  44. Shen L, Haufe J, Patel MK (2009) Product overview and market projection of emerging bio-based plastics PRO-BIP 2009. Report for European polysaccharide network of excellence (EPNOE) and European bioplastics, p 243Google Scholar
  45. Shi Z, Yang Q, Kuga S, Matsumoto Y (2015) Dissolution of wood pulp in aqueous NaOH/Urea solution via dilute acid pretreatment. J Agric Food Chem 63:6113–6119CrossRefGoogle Scholar
  46. Swatloski RP, Spear SK, Holbrey JD, Rogers RD (2002) Dissolution of cellose with ionic liquids. J Am Chem Soc 124:4974–4975CrossRefGoogle Scholar
  47. Tang Y, Yang S, Zhang N, Zhang J (2014) Preparation and characterization of nanocrystalline cellulose via low-intensity ultrasonic-assisted sulfuric acid hydrolysis. Cellulose 21:335–346CrossRefGoogle Scholar
  48. Tolonen M, Hernberg S, Nurminen M, Tiitola K (1975) A follow-up study of coronary heart disease in viscose rayon workers exposed to carbon disulphide. Br J Ind Med 32:1–10Google Scholar
  49. Turner MB, Spear SK, Holbrey JD, Rogers RD (2004) Production of bioactive cellulose films reconstituted from ionic liquids. Biomacromolecules 5:1379–1384CrossRefGoogle Scholar
  50. Vanhoorne M, De Rouck A, De Bacquer D (1995) Epidemiological study of eye irritation by hydrogen sulphide and/or carbon disulphide exposure in viscose rayon workers. Ann Occup Hyg 39:307–315CrossRefGoogle Scholar
  51. Varshney V, Naithani S (2011) Chemical functionalization of cellulose derived from nonconventional sources. In: Kalia S, Kaith BS, Kaur I (eds) Cellulose fibers: bio-and nano-polymer composites. Springer, Berlin, Heidelberg, pp 43–60CrossRefGoogle Scholar
  52. Vedernikov NA, Kal’nina VK (1972) Wood cell wall and its changes at chemical treatments. Chemistry, RigaGoogle Scholar
  53. Wang Y, Chen L (2011) Impacts of nanowhisker on formation kinetics and properties of all-cellulose composite gels. Carbohydr Polym 83:1937–1946CrossRefGoogle Scholar
  54. Wang S, Lu A, Zhang L (2015) Recent advances in regenerated cellulose materials. Prog Polym Sci. doi: 10.1016/j.progpolymsci.2015.07.003 Google Scholar
  55. Zhang H, Wu J, Zhang J, He J (2005) 1-Allyl-3-methylimidazolium chloride room temperature ionic liquid: a new and powerful nonderivatizing solvent for cellulose. Macromolecules 38:8272–8277CrossRefGoogle Scholar
  56. Zhang Y-HP, Cui J, Lynd LR, Kuang LR (2006) A transition from cellulose swelling to cellulose dissolution by o-phosphoric acid: evidence from enzymatic hydrolysis and supramolecular structure. Biomacromolecules 7:644–648CrossRefGoogle Scholar
  57. Zhang X, Liu X, Zheng W, Zhu J (2012) Regenerated cellulose/graphene nanocomposite films prepared in DMAC/LiCl solution. Carbohydr Polym 88:26–30CrossRefGoogle Scholar
  58. Zhou S, Tashiro K, Hongo T, Shirataki H, Yamane C, Ii T (2001) Influence of water on structure and mechanical properties of regenerated cellulose studied by an organized combination of infrared spectra, X-ray diffraction, and dynamic viscoelastic data measured as functions of temperature and humidity. Macromolecules 34:1274–1280CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2016

Authors and Affiliations

  • Weijuan Huang
    • 1
  • Yixiang Wang
    • 1
  • Lina Zhang
    • 2
  • Lingyun Chen
    • 1
  1. 1.Department of Agricultural, Food and Nutritional ScienceUniversity of AlbertaEdmontonCanada
  2. 2.College of Chemistry and Molecule SciencesWuhan UniversityWuhanChina

Personalised recommendations