Skip to main content

Official Journal of the Japan Wood Research Society

Journal of Wood Science Cover Image

Analysis of progress of oxidation reaction during oxygen-alkali treatment of lignin I: method and its application to lignin oxidation

Abstract

A new method is applied to evaluate the progress of the oxidation reaction of lignin during oxygen-alkali treatment. This method employs the difference in permanganate consumption of the sample before and after the oxygen-alkali treatment as an indication for the lignin oxidation. When kraft lignin and residual lignin isolated from unbleached softwood kraft pulp were subjected to oxygen-alkali treatment up to 6000min, the progress of the oxidation expressed by this method was separated into clearly distinguished three phases. During the first and second phases, the progress of oxidation was well correlated to the loss of methoxyl group and to the decrease in the yield of nitrobenzene oxidation products. The addition of Mn+ to the oxygen-alkali treatment depressed oxidation during the second phase partly and that during the third phase almost completely. Calculations based on the change in the permanganate consumption revealed that the oxidation during the first phase corresponded to 4.2 electrons abstracted from one lignin structural unit on average. The oxidation process by oxygen-alkali treatment was hypothetically attributed to the direct reaction between molecular oxygen and the phenolic unit of lignin, which mainly took place during the first phase, and to the autooxidation-type oxidation during the second and third phases.

References

  1. 1.

    Olm L, Teder A (1979) The kinetics of oxygen bleaching. TAPPI J 62(12):43–46

    CAS  Google Scholar 

  2. 2.

    Hsu CL, Hsieh JS (1988) Reaction kinetics in oxygen bleaching: AIChE J 34(1):116–122

    CAS  Article  Google Scholar 

  3. 3.

    Iribarne J, Schroeder LR (1997) High-pressure oxygen delignification of kraft pulps. Part 1. Kinetics. TAPPI J 80(10):241–250

    CAS  Google Scholar 

  4. 4.

    Ljunggren S (1990) The kinetics of lignin reactions during oxygen bleaching. Part 1. The reactivity of p,p′-dihydroxystilbene. Nord Pulp Pap Res J 5(1):38–43

    CAS  Article  Google Scholar 

  5. 5.

    Ljunggren S, Johansson E (1990) The kinetics of lignin reactions during oxygen bleaching. Part 2. The reactivity of 4,4′-dihydroxy-3,3′-dimethoxy-stilbene andβ-aryl ether structures. Nord Pulp Pap Res J 5(3):148–154

    CAS  Article  Google Scholar 

  6. 6.

    Ljunggren S, Johansson E (1990) The kinetics of lignin reactions during oxygen bleaching. Part 3. The reactivity of 4-n-propylguaiacol and 4,4′-di-n-propyl-6,6′-biguaiacol. Holzforchung 44:291–296

    CAS  Article  Google Scholar 

  7. 7.

    Johansson E, Ljunggren S (1994) The kinetics of lignin reactions during oxygen bleaching. Part 4. The reactivities of different lignin model compounds and the influence of metal ions on the rate of degradation: J Wood Chem Technol 14:507–525

    CAS  Article  Google Scholar 

  8. 8.

    Ljunggren S (1986) Kinetic aspects of some lignin reactions in oxygen bleaching: J Pulp Pap Sci 12(2):J54-J57

    Google Scholar 

  9. 9.

    Ericsson B, Lindgren BO, Theander O (1971) Factors influencing the carbohydrate degradation under oxygen-alkali bleaching: Svensk Papperstidn 74:757–765

    CAS  Google Scholar 

  10. 10.

    Yasumoto M, Matsumoto Y, Ishizu A (1996) The role of peroxide species in carbohydrate degradation during oxygen bleaching. Part 1. Factors influencing the reaction selectivity between carbohydrate and lignin model compounds. J Wood Chem Technol 16:95–107

    CAS  Article  Google Scholar 

  11. 11.

    Yokoyama T, Matsumoto Y, Yasumoto M, Meshitsuka G (1996) The role of peroxide species in carbohydrate degradation during oxygen bleaching. Part 2. Effect of oxygen pressure on the degradation of lignin and carbohydrate model compounds and on the reaction selectivity. J Pulp Pap Sci 22(5):J151-J154

    Google Scholar 

  12. 12.

    Froass P, Ragauskas A, Mcdonough T, Jiang J (1996) Chemical structure of residual lignin from kraft pulp. J Wood Chem Technol 16:347–365

    CAS  Article  Google Scholar 

  13. 13.

    Thring RW, Chornet E, Bouchard J, Vidal PF, Overend RP (1990) Characterization of lignin residues deived from the alkali hydrolysis of glycol lignin. Can J Chem 68:82–89

    CAS  Article  Google Scholar 

  14. 14.

    Chen C-L (1992) Nitrobenzene and cupric oxide oxidations. In: Lin SY, Dence CW (eds) methods in lignin chemistry. Springer, Berlin, pp 301–321

    Google Scholar 

  15. 15.

    Matsumoto Y, Minami K, Ishizu A (1993) Studies on chemical structure of lignin by oxidation: erythro and threo ratio of arylglycerol-β-aryl ether structure correlates to low lignin polymerizes. In: Proceedings of the 7th International. Symposium on Wood Pulping Chemistry, Book 1, pp 98–101

  16. 16.

    Yokoyama T, Matsumoto Y, Meshitsuka G (1999) The role of peroxide species in carbohydrate degradation during oxygen bleaching. Part III. Effect of metal ions on the reaction selectivity between lignin and carbohydrate model compounds. J Pulp Pap Sci 25(2):42–46

    CAS  Google Scholar 

Download references

Author information

Affiliations

Authors

Corresponding author

Correspondence to Gyosuke Meshitsuka.

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Tong, G., Yokoyama, T., Matsumoto, Y. et al. Analysis of progress of oxidation reaction during oxygen-alkali treatment of lignin I: method and its application to lignin oxidation. J Wood Sci 46, 32–39 (2000). https://doi.org/10.1007/BF00779550

Download citation

Key words

  • Lignin
  • Oxygen-alkali treatment
  • Permanganate consumption
  • Oxidation
  • Electron