Thermal and Physiochemical Characterization of Lignin Extracted from Wheat Straw by Organosolv Process

Original Paper
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Abstract

The purified lignin extracted from wheat straw by organosolv process was characterized for the existence of lignin subunits, functional groups and physical and thermal behaviours. Presence of carboxyl, hydroxyl, methoxyl groups and C–C, C–O, C=O linkages were conducted by Fourier Transform Infrared (FT-IR). By 1H-NMR (Nuclear Magnetic Resonance Spectroscopy) presence of aromatic protons, phenolic hydroxyls, carboxylic acids, and aldehydes were established. Moreover, 13C-NMR spectra have disclosed the presence of condensed and uncondensed aliphatic and aromatic aryls and ethers. The existence of syringyl and guaiacyl units also were confirmed with both FTIR and NMR spectroscopies. Furthermore, the results from Thermal Gravimetric Analysis (TGA) showed the weight of extracted lignin is changed in temperatures between 180 and 670 °C by devolatization, formation and condensation of different chemicals. Also, the Differential Scanning Calorimetry (DSC) graph displayed a glass transition temperature of 105 °C for extracted lignin. As a result, the extracted lignin with high purity can be a suitable candidate for carrying out value-added products.

Keywords

Wheat straw Organosolv lignin FT-IR NMR DSC TGA 

Notes

Acknowledgements

The authors would like to acknowledge the financial support from the Natural Science and Engineering Research Council of Canada (NSERC) and Ontario Research Fund (ORF). We also thank Dr. Krishan Goel, who helped us a lot in this project.

References

  1. 1.
    Nadel S (2016) Pathway to cutting energy use and carbon emissions in half. American Council for an Energy-Efficient Economy, Washington, DCGoogle Scholar
  2. 2.
    Jefferson M (2016) A global energy assessment. Wiley Interdiscip Rev 5(1):7–15Google Scholar
  3. 3.
    Balakshin M, Capanema E, Berlin A (2014) Isolation and analysis of lignin–carbohydrate complexes preparations with traditional and advanced methods-Chapter 4, A ReviewGoogle Scholar
  4. 4.
    Zhao X, Cheng K, Liu D (2009) Organosolv pretreatment of lignocellulosic biomass for enzymatic hydrolysis. Appl Microbiol Biotechnol 82(5):815–827CrossRefGoogle Scholar
  5. 5.
    Holladay J, Bozell J, White J, Johnson D (2007) Top value-added chemicals from biomass. DOE Report PNNL 2007; 16983.Google Scholar
  6. 6.
    Perlack RD, Wright LL, Turhollow AF, Graham RL, Stokes BJ, Erbach DC Biomass as feedstock for a bioenergy and bioproducts industry: the technical feasibility of a billion-ton annual supply 2005Google Scholar
  7. 7.
    Hambardzumyan A (2014) Preparation of cellulose whiskers monolayers on water silicon surface by Langmuir-Blodgett technique. Chem Biol 3:13–18Google Scholar
  8. 8.
    Smook GA (1992) Handbook for pulp and paper technologists. Tappi, Peachtree CornersGoogle Scholar
  9. 9.
    Saad R, Hawari J (2013) Grafting of lignin onto nanostructured silica SBA-15: preparation and characterization. J Porous Mater 20(1):227–233CrossRefGoogle Scholar
  10. 10.
    Lora JH, Glasser WG (2002) Recent industrial applications of lignin: a sustainable alternative to nonrenewable materials. J Polym Environ 10(1–2):39–48CrossRefGoogle Scholar
  11. 11.
    Sieminski A (2014) International energy outlook. Energy Information Administration (EIA), Washington, DCGoogle Scholar
  12. 12.
    Balat M, Balat H (2009) Recent trends in global production and utilization of bio-ethanol fuel. Appl Energy 86(11):2273–2282CrossRefGoogle Scholar
  13. 13.
    Sarkar N, Ghosh SK, Bannerjee S, Aikat K (2012) Bioethanol production from agricultural wastes: an overview. Renew Energy 37(1):19–27CrossRefGoogle Scholar
  14. 14.
    Argyropoulos DS (2016) High value lignin derivatives, polymers, and copolymers and use thereof in thermoplastic, thermoset, composite, and carbon fiber applications. US Patent 9,340,426Google Scholar
  15. 15.
    Buranov AU, Mazza G (2009) Extraction and purification of ferulic acid from flax shives, wheat and corn bran by alkaline hydrolysis and pressurised solvents. Food Chem 115(4):1542–1548CrossRefGoogle Scholar
  16. 16.
    Yuan T, Xu F, Sun R (2013) Role of lignin in a biorefinery: separation characterization and valorization. J Chem Technol Biotechnol 88(3):346–352CrossRefGoogle Scholar
  17. 17.
    Delmas G, Benjelloun-Mlayah B, Bigot YL, Delmas M (2011) Functionality of wheat straw lignin extracted in organic acid media. J Appl Polym Sci 121(1):491–501CrossRefGoogle Scholar
  18. 18.
    Xu F, Sun J, Sun R, Fowler P, Baird MS (2006) Comparative study of organosolv lignins from wheat straw. Ind Crops Prod 23(2):180–193CrossRefGoogle Scholar
  19. 19.
    Xiao L, Shi Z, Xu F, Sun R (2012) Characterization of MWLs from Tamarix ramosissima isolated before and after hydrothermal treatment by spectroscopical and wet chemical methods. Holzforschung 66(3):295–302CrossRefGoogle Scholar
  20. 20.
    Derkacheva D, Sukhov D (2008) Investigation of lignins by FTIR spectroscopy. Wiley Online Library, Macromolecular SymposiaGoogle Scholar
  21. 21.
    McDonough TJ (1992) The chemistry of organosolv delignification. Tappi, Peachtree CornersGoogle Scholar
  22. 22.
    Sundquist J (1999) Organosolv pulping. Chemical pulping Helsink: Fapet Oy 404:405Google Scholar
  23. 23.
    Sakakibara A (1980) A structural model of softwood lignin. Wood Sci Technol 14(2):89–100CrossRefGoogle Scholar
  24. 24.
    Ramezani N, Sain M (2017) Optimizing conditions for organosolv lignin extraction from wheat straw using data analysis approach (submitted)Google Scholar
  25. 25.
    Huijgen W, Telysheva G, Arshanitsa A, Gosselink R, De Wild P (2014) Characteristics of wheat straw lignins from ethanol-based organosolv treatment. Ind Crops Prod 59:85–95CrossRefGoogle Scholar
  26. 26.
    Faix O (1991) Classification of lignins from different botanical origins by FT-IR spectroscopy. Holzforschung 45(s1):21–28CrossRefGoogle Scholar
  27. 27.
    Negrão DR, Sain M, Leão AL, Sameni J, Jeng R, de Jesus JP, Monteiro RT et al (2015) Fragmentation of lignin from organosolv black liquor by white rot fungi. BioResources 10(1):1553–1573CrossRefGoogle Scholar
  28. 28.
    Kline LM, Hayes DG, Womac AR, Labbe N (2010) Simplified determination of lignin content in hard and soft woods via UV-spectrophotometric analysis of biomass dissolved in ionic liquids. BioResources 5(3):1366–1383Google Scholar
  29. 29.
    Nimz H (1974) Beech lignin—proposal of a constitutional scheme. Angewandte Chemie International Edition in English 13(5):313–321CrossRefGoogle Scholar
  30. 30.
    Xiong Z, Zhang X, Wang H, Ma F, Li L, Li W (2007) Application of brown-rot basidiomycete Fomitopsis sp. IMER2 for biological treatment of black liquor. J Biosci Bioeng 104(6):446–450CrossRefGoogle Scholar
  31. 31.
    Lundquist K (1992) Proton (1H) NMR spectroscopy. Methods in lignin chemistry. Springer, Berlin, pp 242–249Google Scholar
  32. 32.
    Lundquist K (1980) NMR studies of lignins. 4. Investigation of spruce lignin by 1H NMR spectroscopy. Acta Chem Scand B 34:21–26CrossRefGoogle Scholar
  33. 33.
    Gellerstedt G, Robert D (1987) Quantitative 13C NMR analysis of kraft lignins. Acta Chem Scand B 41(7):541–546CrossRefGoogle Scholar
  34. 34.
    Hawkes GE, Smith CZ, Utley JH, Vargas RR, Viertler H (1993) A comparison of solution and solid state 13C NMR spectra of lignins and lignin model compounds. Holzforschung 47(4):302–312CrossRefGoogle Scholar
  35. 35.
    Wen J, Sun S, Xue B, Sun R (2013) Recent advances in characterization of lignin polymer by solution-state nuclear magnetic resonance (NMR) methodology. Materials 6(1):359–391CrossRefGoogle Scholar
  36. 36.
    She D, Xu F, Geng Z, Sun R, Jones GL, Baird MS (2010) Physicochemical characterization of extracted lignin from sweet sorghum stem. Ind Crops Prod 32(1):21–28CrossRefGoogle Scholar
  37. 37.
    Saliba ED, Rodriguez NM, de Morais SA, Piló-Veloso D (2001) Ligninas: métodos de obtenção e caracterização química. Ciência Rural 31(5):917–928CrossRefGoogle Scholar
  38. 38.
    Wang S, Wang K, Liu Q, Gu Y, Luo Z, Cen K et al (2009) Comparison of the pyrolysis behavior of lignins from different tree species. Biotechnol Adv 27(5):562–567CrossRefGoogle Scholar
  39. 39.
    Pan X, Kadla JF, Ehara K, Gilkes N, Saddler JN (2006) Organosolv ethanol lignin from hybrid poplar as a radical scavenger: relationship between lignin structure, extraction conditions, and antioxidant activity. J Agric Food Chem 54(16):5806–5813CrossRefGoogle Scholar
  40. 40.
    Sun R, Tomkinson J, Jones GL (2000) Fractional characterization of ash-AQ lignin by successive extraction with organic solvents from oil palm EFB fibre. Polym Degrad Stab 68(1):111–119CrossRefGoogle Scholar
  41. 41.
    El Hage R, Brosse N, Sannigrahi P, Ragauskas A (2010) Effects of process severity on the chemical structure of Miscanthus ethanol organosolv lignin. Polym Degrad Stab 95(6):997–1003CrossRefGoogle Scholar
  42. 42.
    Leschinsky M, Zuckerstätter G, Weber HK, Patt R, Sixta H (2008) Effect of autohydrolysis of Eucalyptus globulus wood on lignin structure. Part 1: comparison of different lignin fractions formed during water prehydrolysis. Holzforschung 62(6):645–652Google Scholar
  43. 43.
    El Hage R, Brosse N, Chrusciel L, Sanchez C, Sannigrahi P, Ragauskas A (2009) Characterization of milled wood lignin and ethanol organosolv lignin from miscanthus. Polym Degrad Stab 94(10):1632–1638CrossRefGoogle Scholar
  44. 44.
    Hansen B, Kusch P, Schulze M, Kamm B (2016) Qualitative and quantitative analysis of lignin produced from beech wood by different conditions of the Organosolv process. J Polym Environ 24(2):85–97CrossRefGoogle Scholar
  45. 45.
    Sun F, Chen H (2008) Enhanced enzymatic hydrolysis of wheat straw by aqueous glycerol pretreatment. Bioresour Technol 99(14):6156–6161CrossRefGoogle Scholar
  46. 46.
    Romaní A, Ruiz HA, Teixeira JA, Domingues L (2016) Valorization of Eucalyptus wood by glycerol-organosolv pretreatment within the biorefinery concept: an integrated and intensified approach. Renew Energy 95:1–9CrossRefGoogle Scholar
  47. 47.
    Domínguez J, Oliet M, Alonso M, Gilarranz M, Rodríguez F (2008) Thermal stability and pyrolysis kinetics of organosolv lignins obtained from Eucalyptus globulus. Ind Crops Products 27(2):150–156CrossRefGoogle Scholar
  48. 48.
    Wittkowski R, Ruther J, Drinda H, Rafiei-Taghanaki F (1992) Formation of smoke flavor compounds by thermal lignin degradation. ACS Publications, Washington, DCCrossRefGoogle Scholar
  49. 49.
    Glasser WG (2000) Classification of lignin according to chemical and molecular structure. ACS Publications, Washington, DCGoogle Scholar
  50. 50.
    Irvine G (1985) The significance of the glass transition of lignin in thermomechanical pulping. Wood Sci Technol 19(2):139–149CrossRefGoogle Scholar
  51. 51.
    Kaelble DH (1971) Physical chemistry of adhesion. Wiley, HobokenGoogle Scholar
  52. 52.
    Aklonis JJ, Macknight WJ, Shen M (1972) Rubber elasticity. In: Introduction to polymer viscoelasticity, 2nd edn. Wiley, New York, pp 102–138Google Scholar
  53. 53.
    Hu TQ (2002) Chemical modification, properties, and usage of lignin. Springer, BerlinCrossRefGoogle Scholar
  54. 54.
    Vallejos ME, Felissia FE, Cruvelo AA, Zambon MD, Ramos L, Area MC (2011) Chemical and physico-chemical characterization of lignins obtained from ethanol-water fractionation of bagasse. BioResources 6(2):pp 1158–1171Google Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Center for Biocomposites and Biomaterials Processing, Faculty of ForestryUniversity of TorontoTorontoCanada

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