Infrared spectroscopic study of alkaline oxygen treatment of lignin with ATR technique in aqueous state 1: method for determining quantitative spectra of oxygen-degraded lignin

For the fundamental study of oxygen delignification of kraft pulp, structural changes of kraft lignin during alkaline oxygen treatment were investigated with the use of infrared measurement with attenuated total reflectance (ATR) technique. In the neutralized reaction mixture of alkaline oxygen-treated kraft lignin, there is a significant amount of NaCl, so that the spectral changes of water due to the coexistence of NaCl was investigated, and how to remove the huge absorption of NaCl solution is discussed. Sodium vanillate–NaCl solutions were employed as model solutions for the reaction mixture. Partial least square (PLS) regression was applied for the prediction of NaCl concentration, and the spectrum of NaCl solution was subtracted from the spectrum of sodium vanillate–NaCl solution as background measurement. This allowed us to obtain the vanillate spectra free from the absorption of NaCl solution. In addition, the mathematical method for reconstructing the spectrum of NaCl solution is discussed. The spectrum of NaCl solution is reconstructed as the linear combination of basic spectra calculated by singular value decomposition (SVD), and it was subtracted from that of the sodium vanillate–NaCl solution. By this procedure, the vanillate spectra were also obtained quantitatively, as has been demonstrated in PLS regression study. It was also confirmed that the quantitative spectra of high molecular weight fraction of alkaline oxygen-treated kraft lignin were obtained by the use of this reconstruction technique.Parts of this report were presented at the 52nd Annual Meeting of the Japan Wood Research Society, Gifu, Japan, April 2002 and the 12th International Symposium on Wood and Pulping Chemistry, Madison, USA, June 2003     

Semi-quantitative method to evaluate the α-carbonyl content in lignin

A method to estimate the content of -carbonyl structures in lignin was developed. This method consists of two successive treatments: NaBD₄ treatment of pulp to reduce an -carbonyl structure in lignin, and nitrobenzene oxidation. NaBD₄ was used to convert an -carbonyl structure to a deuterium-labeled hydroxymethine structure. The ratio of D-vanillin [(HO)(H₃CO)C₆H₃CDO] to H-vanillin [(HO)(H₃CO)C₆H₃CHO] or that of their syringyl analogues obtained by nitrobenzene oxidation was used as the measure of the content of -carbonyl structure. Model experiments demonstrated that when sodium hydroxide was used as alkali for the nitrobenzene oxidation, the retention of deuterium at the side chain -position was very low due to the displacement of deuterium with hydrogen by an unknown reaction mechanism. In order to depress this unexpected displacement, the reaction conditions of the nitrobenzene oxidation were modified. The modified nitrobenzene oxidation employs 0.5mol/l of lithium hydroxide as a reaction medium instead of 2.0mol/l sodium hydroxide. By this modification, this method could successfully trace the formation and the degradation of the -carbonyl structure in milled wood lignins.This paper was presented in part at the 11th International Symposium on Wood and Pulping Chemistry, Nice, France, June 2001 and at the 46th Lignin Symposium, Kyoto, Japan, November 2001     

Lignin fragments rich in detached side-chain structures found in water-soluble LCC

The content of the glyceraldehyde-2-aryl ether-type structure in water-soluble lignin–carbohydrate complex (LCC) fractions, which were obtained from Japanese cedar and birch residual wood meal after milled wood lignin isolation, was determined by ozonation. Quite high amounts of the glyceraldehyde-2-aryl ether-type structure were found in water-soluble LCC fractions of both species; about 3–5 times higher than those of other fractions. This result, as well as the high content of the β-1 structure in these fractions shown in our previous reports, suggest that lignin in these fractions has the characteristics of endwise-type lignin, because the glyceraldehyde-2-aryl ether-type structure and β-1 structure are typical characteristics of this type of lignin fraction. These results are in good agreement with the generally accepted hypothesis that the glyceraldehyde-2-aryl ether-type structure and β-1 structure are generated at the same time by a radical coupling reaction. The results also indicated that these two structures are present in close proximity in the lignin.     

Detailed examination of the degradation of phenol derivatives under oxygen delignification conditions

Several phenolic compounds were subjected to oxygen-alkali oxidations under oxygen delignification conditions, and their degradations were examined in detail by applying a novel formula. The formula was established on the basis of the two following considerations. The degradation of the phenolic compounds should be expressed by the sum of two types, each of which is caused by molecular oxygen and by highly reactive active oxygen species (HAOS). The degradation should be described by a mathematical equation to which a rate function, k(t), dependent on reaction time t, is applied instead of a rate constant. By rearrangements, the following formula was obtained: k(t) = A/(t + B) (A, B are constants). This is hyperbola, and the illustration of k(t) visualized the contribution of HAOS to the degradation of the phenolic compounds. HAOS did not contribute so much to the degradation, especially at 70 degrees C, which suggests the low energy supply for the HAOS generation at 70 degrees C. The extrapolation of k(t) to the beginning of the reaction gives its initial value, k(initial), which is the rate constant of the reaction between the phenolic compounds and molecular oxygen. As expected, k(initial) was dependent on the electronic property of their substituents. Quantification of the phenolic compounds degraded by HAOS showed that the contribution of HAOS to the degradation is not great. The maximum contribution was observed in the oxidation of 2,6-dimethylphenol at 85 degrees C. In this case, 5 and 95% of the compound were degraded by HAOS and molecular oxygen, respectively.     

Application of the amount of oxygen consumption to the investigation of the oxidation mechanism of lignin during oxygen-alkali treatment

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. Part of this article was presented at the 13th International Symposium on Wood, Fiber, and Pulping Chemistry (13th ISWFPC), Auckland, New Zealand, May 2005     

Evaluation of the extent of the oxidation reaction during chlorine bleaching of pulp

A modified method was developed to evaluate how much chlorine is consumed by the oxidation reaction during the chlorine bleaching process. This evaluation is, in principle, based on the sum of chloride produced during the chlorination stage (C-stage) and produced during alkali treatment of both the C-stage effluent and the chlorinated pulp. Results obtained by this method proved that about 50%–75% of chlorine was consumed by the oxidation reaction during chlorine bleaching, depending on the reaction condition of chlorination. Even under a reaction condition that is not favorable to an oxidation reaction (low pH), approximately three electrons were abstracted from one lignin structural unit by chlorine bleaching. This result provides additional evidence for our recent observation that lignin is extensively oxidized during chlorine bleaching even when pure chlorine without any chlorine dioxide substitution was used.Part of this paper was presented at the 40th Lignin Symposium. Tsukuba, Japan, October 12, 1995     

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

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.Part of this paper was presented at the 9th ISWPC, Montreal, June 1997; and at the 42nd Lignin Symposium, Sapporo, October 1997