Abstract
The dioxygen consumption by kraft lignin and several lignin model compounds during oxygen-alkali treatments were directly analyzed using a dioxygen fl owmeter. The average dioxygen consumption by 200 g of kraft lignin was about 3 moles. Because this value was as much as those obtained for monomeric phenolic lignin model compounds, guaiacol and vanillyl alcohol, it was postulated that not only phenolic but also nonphenolic moieties in kraft lignin are extensively oxidized. The dioxygen consumption by 0.5 moles (one equivalent of aromatic units) of a dimeric lignin model compound, guaiacylglycerol-β-guaiacyl ether (GG), was also similar to that for 1 mole of guaiacol and vanillyl alcohol, regardless of the type of the aromatic moiety, which supports the above postulation. The most plausible mechanism for the oxidation of nonphenolic moieties is the oxidation of side chains of residual β-O-4 substructures by active oxygen species. By this mechanism, nonphenolic moieties in kraft lignin and GG are converted into corresponding phenolic moieties, and the oxidation by dioxygen progresses.
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Chen C-L (1991) Lignin — occurrence in woody tissues, isolation, reactions, and structure. In: Levin M, Goldstein IS (eds) Wood structure and composition. Marcel Dekker, New York, pp 183–261
Tong G, Yokoyama T, Matsumoto Y, Meshitsuka G (2000) Analysis of progress of oxidation reaction during oxygen-alkali treatment of lignin 1: method and its application to lignin oxidation. J Wood Sci 46:32–39
Tong G, Matsumoto Y, Meshitsuka G (2000) Analysis of progress of oxidation reaction during oxygen-alkali treatment of lignin 2: significance of oxidation reaction of lignin during oxygen delignification. J Wood Sci 46:371–375
Eckert RC, Chang H-M, Tucker WP (1973) Oxidative degradation of phenolic lignin model compounds with oxygen and alkali. TAPPI 56:134–138
Gierer J, Imsgard F (1977) Studies on the autoxidation of t-butylsubstituted phenols in alkaline media 1: reaction of 4-t-butylguaiacol. Acta Chem Scand B31:537–545
Johansson E, Ljunggren S (1994) The kinetics of lignin reactions during oxygen bleaching part 4: the reactivities of different lignin model compounds and the infl uence of metal ions on the rate of degradation. J Wood Chem Technol 14:507–525
Li S, Lundquist K, Paulsson M (1995) Synthesis of guaiacylglycerol-β-guaiacyl ether. Acta Chem Scand 49:623–624
Yokoyama T, Matsumoto Y, Meshitsuka G (1999) The role of peroxide species in carbohydrate degradation during oxygen bleaching III: effect of metal ions on the reaction selectivity between lignin and carbohydrate model compounds. J Pulp Pap Sci 22:J151–J154
Yokoyama T, Matsumoto Y, Yasumoto M, Meshitsuka G (1996) The role of peroxide species in carbohydrate degradation during oxygen bleaching II: effect of oxygen pressure on the degradation of lignin and carbohydrate model compounds and on the reaction selectivity. J Pulp Pap Sci 22:J151–J154
Yokoyama T, Matsumoto Y, Meshitsuka G (1999) Reaction selectivity of active oxygen species in oxygen-alkali bleaching. J Wood Chem Technol 19:187–202
Yokoyama T, Matsumoto Y, Meshitsuka G (2005) Characterization of active oxygen species under oxygen-alkali bleaching conditions. Holzforschung 59:269–275
Lautsch W, Plankenhorn E, Klink F (1940) Über die bildung des vanillins aus dem holz, dem lignin und der sulfitcelluloseablauge der fichte. Angew Chem 53:450–452
Deineko IP, Nikol’skii SN, Zarubin MY (1983) Quantitative determination of oxygen consumption in oxygen pulping. Khimiya Drevesiny 1983:54–57
Capanema EA, Balakshin MY, Chen C-L, Gratzl JS, Kirkman AG (2001) Oxidative ammonolysis of technical lignins part 1: kinetics of the reaction under isothermal conditions at 130°C. Holzforschung 55:397–404
Capanema EA, Balakshin MY, Chen C-L, Gratzl JS, Kirkman AG (2001) Oxidative ammonolysis of technical lignins part 2: effect of oxygen pressure. Holzforschung 55:405–412
Capanema EA, Balakshin MY, Chen C-L, Gratzl JS, Kirkman AG (2002) Oxidative ammonolysis of technical lignins part 3: effect of temperature on the reaction rate. J Wood Chem Technol 26:5–20
Capanema EA, Balakshin MY, Chen C-L, Gratzl JS (2006) Oxidative ammonolysis of technical lignins part 4: effects of the ammonium hydroxide concentration and pH. Holzforschung 56:402–415
Miksche GE (1980) Lignin reactions in alkaline pulping processes. In: Gratzl JS, Nakano J, Singh RP (eds) Chemistry of delignification with oxygen, ozone, and peroxides. Uni, Tokyo, p 108
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Part of this article was presented at the 13th International Symposium on Wood, Fiber, and Pulping Chemistry (13th ISWFPC), Auckland, New Zealand, May 2005
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Imai, A., Tomoda, I., Yokoyama, T. et al. Application of the amount of oxygen consumption to the investigation of the oxidation mechanism of lignin during oxygen-alkali treatment. J Wood Sci 54, 62–67 (2008). https://doi.org/10.1007/s10086-007-0906-8
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DOI: https://doi.org/10.1007/s10086-007-0906-8