Oxidation of Lignins and Mechanistic Considerations

  • Adilson R. Gonçalves
  • Priscila Benar
  • Ulf Schuchardt
Chapter
Part of the Green Chemistry and Sustainable Technology book series (GCST)

Abstract

Oxidation of Acetosolv and Organosolv lignins and model dimers was performed with O2 and Co/Mn/Br catalyst. Evidence for the mechanisms was obtained by analyzing the monomeric and macromolecular products. The oxidation yielded 30–40 % of oxidized lignin containing 7–41 % more oxygenated groups than the original lignin, as evaluated by analytical pyrolysis. Kinetic data showed that oxidation of lignin is a pseudo-first-order reaction with the following rate constants for the formation of the oxidation products: 3.2 × 10−2 min−1 (Organosolv), 1.0 × 10−3–9.5 × 10−3 min−1 (Acetosolv), and 4.3 × 10−3–1.6 × 10−1 min−1 (model dimers). Oxidized lignins have chelating capacity for removing heavy metals from industrial effluents.

Keywords

Oxidation of Organosolv lignins Lignin dimers Oxidation mechanism Acetosolv lignin 
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Notes

Acknowledgments

This work was supported by the Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP – grants 95/7490-3, 95/9872-0, 96/12306-0, 00/00637-9), Deutscher Akademischer Austauschdienst (DAAD), National Brazilian Research Council (CNPq), and Fundação Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES).

References

  1. 1.
    Zakzeski J, Bruijnincx PCA, Jongerius AL, Weckhuysen BM (2010) The catalytic valorization of lignin for the production of renewable chemicals. Chem Rev 110:3552–3599CrossRefGoogle Scholar
  2. 2.
    Laurichesse S, Avérous L (2014) Chemical modification of lignins: towards biobased polymers. Prog Polym Sci 39:1266–1290CrossRefGoogle Scholar
  3. 3.
    Tomani P (2010) The Lignoboost process. Cellul Chem Technol 44:53–58Google Scholar
  4. 4.
    Rocha GJM, Nascimento VM, Silva VFN, Corso DLS, Gonçalves AR (2014) Contributing to the environmental sustainability of the second generation ethanol production: delignification of sugarcane bagasse with sodium hydroxide recycling. Ind Crop Prod 59:63–68CrossRefGoogle Scholar
  5. 5.
    Oliveira LRM, Nascimento VM, Gonçalves AR, Rocha GJM (2014) Combined process system for the production of bioethanol from sugarcane straw. Ind Crop Prod 58:1–7CrossRefGoogle Scholar
  6. 6.
    Gambarato BC (2014) Ph. D. thesis, Universidade de São Paulo, LorenaGoogle Scholar
  7. 7.
    Miléo PC (2015) Ph. D. thesis, Universidade de São Paulo, LorenaGoogle Scholar
  8. 8.
    Chang H-M, Allan GG (1971) In: Sarkanen KV, Ludwig CH (eds) Lignins – occurrence, formation, structure and reactions. Wiley, New York, pp 433–485Google Scholar
  9. 9.
    Goheen DW (1981) In: Goldstein IS (ed) Organic chemicals from biomass. CRC, Boca Raton, pp 143–161Google Scholar
  10. 10.
    Hocking MB (1997) Vanillin: synthetic flavoring from spent sulfite liquor. J Chem Educ 74:1055–1059CrossRefGoogle Scholar
  11. 11.
    Kenny J (1997) The Brazilian expansion seems to just grow on and on. Pulp Pap Int 3:23–27Google Scholar
  12. 12.
    Raymond AY, Akhtar M (eds) (1998) Environmentally friendly technologies for the pulp and paper industry. Wiley, New YorkGoogle Scholar
  13. 13.
    Lundquist K, Li S (1998) In: Proc. 5th Eur. workshop lignocell. Pulp, Aveiro-Portugal, pp 491–494Google Scholar
  14. 14.
    Benar P (1992) M.Sc. thesis, Universidade Estadual de Campinas, Campinas, BrazilGoogle Scholar
  15. 15.
    Kaszonyi A, Hronec M, Lauko L, Ilavsky J (1989) Study of the activity of Co-Br-Py catalysts during oxidation of p-xylene in acetic acid. J Mol Catal 57:105–112CrossRefGoogle Scholar
  16. 16.
    Gonçalves AR, Schuchardt U, Meier D, Faix O (1995) In: Proc. 8th int. symp. Wood Pulp. Chem., Helsinki-Finland, vol II, pp 331–336Google Scholar
  17. 17.
    Gonçalves AR, Schuchardt U (1991) In: Proc. Braz. symp. chem. lignins other wood compon., 2nd, Campinas-Brazil, pp 91–96Google Scholar
  18. 18.
    Gonçalves AR, Schuchardt U (1992) In: Proc. 2nd Eur. workshop lignocell. Pulp, Grenoble-France, pp 147–148Google Scholar
  19. 19.
    Orlandi M, Bolzacchini E, Rindone B, Morazzoni F, Canevali C, Scotti R, Sipila J, Brunow G (1998) In: Proc. 5th Eur. workshop lignocell. Pulp, Aveiro-Portugal, pp 305–308Google Scholar
  20. 20.
    Bassoli A, Brambilla A, Bolzacchini E, Chioccara F, Morazzoni F, Orlandi M, Rindone B (1996) In: Anastas PT, Williamson TC (eds) Green chemistry: designing chemistry of the environment, Symp. ser. 626. ACS, New York, pp 92–104CrossRefGoogle Scholar
  21. 21.
    Perng Y-S, Oloman CW, Watson PA, James BR (1994) Catalytic oxygen bleaching of wood pulp with metal porphyrin and phthalocyanine complexes. Tappi J 77:119–125Google Scholar
  22. 22.
    Erickson M, Larsson S, Miksche GE (1973) Gaschromatografische Analyse von Ligninoxydationsprodukten VIII Zur Struktur des Lignins der Fichte. Acta Chem Scand 27:903–914CrossRefGoogle Scholar
  23. 23.
    Gonçalves AR, Schuchardt U, Meier D, Faix O (1994) Proc. Braz. symp. chem. lignins other wood compon, 3rd., Belo Horizonte-Brazil, pp 253–256Google Scholar
  24. 24.
    Partenheimer W (1991) Characterization of the reaction of cobalt(III) Acetate, dioxygen and acetic acid, and its significance in autoxidation reactions. J Mol Catal 67:35–46CrossRefGoogle Scholar
  25. 25.
    Yoshikuni T (1994) Catalytic activity and kinetic study of cerium-catalyzed syntheses of hydroxybenzaldehydes by oxygen oxidation. II. J Chem Technol Biotechnol 59(353):357Google Scholar
  26. 26.
    Gonçalves AR (1999) In: Proc. 10th int. symp. wood pulp. chem., vol. II. Yokohama-Japan, pp 88–91Google Scholar
  27. 27.
    Gonçalves AR (1995) Ph.D. thesis, Universidade Estadual de Campinas, Campinas, BrazilGoogle Scholar
  28. 28.
    Gonçalves AR (1999) In: Proc. Proc. 10th int. symp. wood pulp. chem., vol II, Yokohama-Japan, pp 98–101Google Scholar
  29. 29.
    Gonçalves AR, Schuchardt U, Meier D, Faix O (1997) Pyrolysis-gas chromatography of the macromolecular fractions of oxidized Organocell lignins. J Anal Appl Pyrolysis 40–41:543–551CrossRefGoogle Scholar
  30. 30.
    Gonçalves AR, Soto-Oviedo MA, Cotrim AR, Silva FT (1998) In: Proc. 7th int. conf. Biotech. Pulp Paper Ind., vol B, Vancouver-Canada, pp 171–173Google Scholar
  31. 31.
    Gonçalves AR, Soto-Oviedo MA, Cotrim AR, Silva FT, Ferraz A (1998) In: Proc. 10th Biom. Energy Ind., Würzburg-Germany, pp 519–521Google Scholar
  32. 32.
    Gonçalves AR, Urbano MP, Cotrim AR, Silva FT (1997) In: Proc. 9th int. symp. wood Pulp. Chem., Quebec-Canadá, pp I4-1–I4-3Google Scholar
  33. 33.
    DiCosimo R, Szabo H-C (1988) Oxidation of lignin model compounds using single-electron-transfer catalysts. J Org Chem 53:1673–1679CrossRefGoogle Scholar
  34. 34.
    Gonçalves AR, Schuchardt U (1999) In: Proc. 10th int. symp. wood pulp. Chem., vol I. Yokohama-Japan, pp 228–231Google Scholar

Copyright information

© Springer Science+Business Media Singapore 2016

Authors and Affiliations

  • Adilson R. Gonçalves
    • 1
  • Priscila Benar
    • 2
  • Ulf Schuchardt
    • 3
  1. 1.Pontifícia Universidade Católica de Campinas, PUCCAMPCampinasBrazil
  2. 2.Instituto Agronômico de CampinasCampinasBrazil
  3. 3.Instituto de Química – UNICAMPCampinasBrazil

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