Oxidative cleavage of lignin aromatics during chlorine bleaching of kraft pulp

Methanol liberation and methoxyl loss during chlorine bleaching of softwood kraft pulp were quantitatively investigated to estimate the degree of structural modification of lignin aromatics. An increase in the chlorine multiple led to enhanced methoxyl loss from lignin. Our result, using pH-adjusted chlorine water (pH 5.7), by which chlorination under oxidation-favorable conditions was achieved, strongly supported the importance of the oxidation reaction by chlorine during delignification and lignin degradation. It was also suggested that methanol can be produced not only via catalytic hydrolysis by chlorine but via oxidative cleavage of the ether bond as well. The infrared spectrum of chlorolignins suggested that chlorine oxidation can open aromatic rings to muconic acid derivatives without cleaving ether bonding of the methoxyl group. No straight relation between the methoxyl content and the kappa number of chlorinated pulps was shown. The methoxyl content of bleached kraft pulps subjected to successive chlorination and alkali extraction showed a good relation with the kappa number. This means that almost all the portions of the oxidatively modified lignin structure were successfully removed during these treatments, and the aromatic structures of residual lignin in chlorinated and alkali-extracted pulps were thought to remain intact.Part of this paper was presented at the 46th Annual Meeting of the Japan Wood Research Society, Kumamoto, April 1996; the 10th International Symposium on Wood and Pulping Chemistry, Yokohama, June 1999; and the 67th Pulp and Paper Research Conference, Tokyo, June 2000     

氧漂过程中脱木质素与木质素氧化之间定量关系的研究

对氧碱漂白过程中木质素氧化进行定量分析,分析方法是基于氧化前后高锰酸钾消耗量的变化。该方法对溶出残余木质素的氧化结果分析发现其呈明显3个阶段：第一段木质素氧化的当量电荷数约4～5／木质素单元;木质素总氧化电荷数大约为9／木质素单元。这些数据以及甲氧基的脱除（75％）均表明：木质素的氧化不仅发生在酚型木质素单元,同时也发生在非酚型结构单元上。只有第一阶段氧化反应是木质素与氧气直接反应,而在第二、三阶段主要是协同氧化作用,氧化反应过程中产生的活性氧基团扮演了一定角色。通过对低浓度针叶材硫酸盐浆的氧漂研究发现：当卡伯值下降一半（25．4至13．4）时平均每个木质素单元氧化3当量电子,氧漂后的纸浆中仍然有大量未被氧化的残余木质素。定量地证明了在氧漂过程中木质素氧化是脱木质素反应的实质。     

Analysis of progress of oxidation reaction during oxygen-alkali treatment of lignin 2: significance of oxidation reaction of lignin during oxygen delignification

The progress of lignin oxidation during oxygenalkali bleaching of pulp was evaluated by the method based on the difference between permanganate consumption of original pulp and that of the mixture of pulp and effluent after oxygen-alkali bleaching. By low-consistency oxygen bleaching of softwood kraft pulp, the permanganate consumption decreased very little. When the kappa number of the pulp was halved (from 25.4 to 13.4), the decrease in permanganate consumption of 1 g pulp was only 1.22ml of 0.02mol/l potassium permanganate. This value was smaller than that obtained for the oxygen-alkali treatment of a corresponding amount of isolated residual lignin, 6.40ml. This was not due to the slow oxidation of lignin in pulp but to the formation of permanganate-consuming substances from carbohydrates. Those newly formed substances cannot be oxidized by oxygen-alkali treatment. Taking these facts into account, lignin originally present in pulp was found to be oxidized well. Reduction of carbonyl groups in carbohydrates prevented the formation of such substances.Part of this paper was presented at the 10th ISWPC, Yokohama, June 1999; and at the 43rd Lignin Symposium, Fuchu, October 1998     

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     

漂白胶贮存性质的研究(二报)——紫胶树脂在漂白过程中性质变化的研究

本文研究了紫胶树脂在漂白和脱氯过程中分子量、热寿命、酸价、碘价、羟基值和氯含量的变化情况。结果证明:漂白过程中,氯主要以自由基加成的方式进入紫胶树脂,同时还有氯的自由基取代和树脂上醛基、伯羟基的氧化反应。在脱氯过程中,漂白胶树脂上大部分危害其贮存性的结合氯被除去,这些氯通过消去和取代反应脱离树脂,同时产生双键和羟基。脱氯后仍残留在紫胶树脂上的氯相当稳定,难以自行脱落,经过脱氯处理,漂白胶具备了片胶所具备的优良性质。     

Location and fate of carboxyl groups in aspen alkaline peroxide-impregnated chemithermomechanical pulp fibres during alkaline peroxide bleaching

The origin and kinetic changes of carboxyl groups in aspen chemithermomechanical pulp (CTMP) fibres during alkaline peroxide bleaching were evaluated. The results showed that the major contributors of carboxyl groups in aspen CTMP fibres were the 4-O-methylglucuronic acid, galacturonic acid and the carboxyl groups in oxidized lignin. Alkaline peroxide bleaching could increase the total carboxyl groups, surface charge and dissolved anionic substances. However, the excess degradation by superfluous hydroxide and peroxide could result in the reduction of carboxyl groups in fibres because of the production and dissolution of low-molar-mass substances. The total carboxyl groups from polysaccharides in fibres remained constant, and the increase of carboxyl groups in fibres should result from the carboxyl groups newly formed by the lignin oxidation during peroxide bleaching. Alkaline peroxide bleaching could also result in the removal of a large part of extractives and a small fraction of lignin on the fibre surface.     

DMD的活化预处理及其全无氯漂序的研究

研究了桉木硫酸盐浆对氧脱木质素段和过氧化氢漂段的活化作用以及ＤＭＤ用量对氧段和过氧化氢段浆性能的影响,使经ＭＯＱＭＰ多段漂白的纸浆最终白度达８０％以上,纸浆粘度满足要求,可以实现桉木硫酸盐浆的全无氯漂白。     

Industrial utilization of tobacco stalks II: preparation and characterization of tobacco pulp by steam explosion pulping

Our previous paper showed tobacco stalks to posses the characteristics of a raw material for pulp and paper application. It contains the major biomass constituents and cell components common to wood species. In this study, preparation and characterization of tobacco stalk pulp by steam explosion (SE) pulping at two chemical pretreatments were attempted. Chemical pretreatment prior to SE pulping improved the brightness, yield, and strength properties of the resulting tobacco SE pulps in the order: 6% Na₂SO₃ + 1% NaOH > 6% Na₂SO₃ > control (untreated). The 6% Na₂SO₃ + 1% NaOH-impregnated tobacco stalks produced SE pulps of good fiber length distribution and considerable properties that compare well with pulps from other raw materials obtained from previous studies, and the nonimpregnated ones showed strength properties superior to those of their poplar counterpart. Prior to bleaching, pretreating the tobacco stalk SE pulps with two stages, 2% NaOH at 90°C, improved the initial pulp brightness by about 5 points. Two-stage 6% H₂O₂ bleaching gave a comparable effect with hypochlorite bleaching for both tobacco and poplar, giving a 29–34 brightness point increase for tobacco SE pulp and 61 for the poplar samples. The differences in the bleaching responses for untreated tobacco and poplar SE pulps were attributed to the differences in their lignin structure, as shown in the total yield of their respective nitrobenzene oxidation products and FT-IR spectra. Tobacco SE pulps contain more of the guaiacyl-type lignin and poplar the syringyl-type lignin.This paper was presented in part during the 1998 CORESTA (Cooperation Centre for Scientific Research Relative to Tobacco) Congress, Brighton, UK, October 1998     

Sulfuric acid bleaching of kraft pulp II: Behavior of lignin and carbohydrate during sulfuric acid bleaching

The purpose of this study was to investigate the behavior of lignin and carbohydrates in kraft pulps during sulfuric acid bleaching. Beech kraft pulp and red pine kraft pulp were bleached with dilute sulfuric acid at pH 1.3 with addition of sodium nitrate and sodium nitrite at 100°C for 1 h. The pulps were then extracted with aqueous sodium hydroxide solution at 70°C for 1 h. Lignin and carbohydrates in the acid effluents and the alkali effluents were analyzed. The carbohydrate compositions of unbleached and bleached kraft pulps were also determined. The residual lignin in kraft pulp was degraded to a molecular size similar to that of milled wood lignin during sulfuric acid bleaching without additives, and it was further degraded to a much smaller molecular size during sulfuric acid bleaching with additives. It was found that the amount of carbohydrate dissolved in the bleach effluents were only about 1 of the dry weight of the kraft pulp under these bleaching conditions. The carbohydrates dissolved during bleaching were mostly of hemicellulose origin.Part of this report was presented at the 8th International Symposium on Wood and Pulping Chemistry, Helsinki, July 1995     

生物技术在制浆造纸工业中的应用前景

在制浆造纸工业中应用生物技术，在提高纸浆得率、降低纤维原料消耗量、消除污染、节约能源等方面具有较大潜力。作者从几个方面论述了生物技术的应用前景：生物改良树种、原木肃皮和木片贮存、生物制浆和漂白、高质量溶解浆的生产、废纸脱墨、利用造纸废液和废料制取副产品、废水处理。     

竹浆GIF仿酶漂白木质素降解产物气相色谱-质谱解析

利用气相色谱-质谱联用(GC-MS)方法对GIF仿酶漂白中的木质素降解产物进行了分析,进一步探讨这种仿酶系统对木质素的降解机制.结果显示GIF仿酶处理使竹浆残余木质素进一步氧化降解,降解的主要方式有脱甲基作用、醌型结构的产生和开环、烷基-芳基醚键的开裂、侧链碳-碳连接的氧化断裂等.GC-MS检测所得的降解产物中,含羰基的化合物较多,这是GIF仿酶系统催化氧化的结果.一些醌式结构、共轭羰基和酚类的脱除,也使纸浆因发色基团减少而白度提高.此外,检测出一些糖类降解产物,说明GIF仿酶系统对纸浆碳水化合物有一定的降解作用.     

Sulfuric acid bleaching of kraft pulp III: reactivity of kraft pulping-resistant structures under acidic conditions

To investigate the bleaching mechanism, a lignincarbohydrate complex (LCC) model compound, a vinyl ether-type lignin model dimer, and a hexeneuronic acid model compound were treated with dilute sulfuric acid of different pHs. Beech kraft pulp and red pine kraft pulp were also treated with dilute sulfuric acid and then extracted with aqueous alkali. The amount of hexeneuronic acid degradation products in acid effluents and lignin dissolved in alkali effluents were determined. It was found that the benzyl ether-type LCC bond and the vinyl ether bond in lignin were effectively cleaved under the pH where sulfuric acid bleaching of kraft pulp was effective. Hexeneuronic acid group was also effectively degraded during sulfuric acid bleaching. In beech kraft pulp bleaching, both lignin removal and hexeneuronic acid removal contributed to the kappa number reduction. In red pine bleaching, the contribution of hexeneuronic acid removal was negligible, and most of the kappa number reduction was achieved by the lignin removal.Part of this report was presented at the 9th International Symposium on Wood and Pulping Chemistry, Montreal, July 1997     

Evaluation of chloroform formed in process of kraft pulp bleaching mill using chlorine dioxide

Chloroform formation, balance, and discharge were estimated in a kraft pulp mill that used an elemental chlorine-free (ECF) bleaching line with chlorine dioxide as well as an effluent treatment process. This was achieved by collecting and analyzing discharge water and air samples that contained measurable levels of chloroform. Chloroform formation in ECF bleaching of hardwood oxygen-delignified kraft pulp (LOKP) was estimated to be 2.07–5.34g/pulp air-dried ton (adt), and approximately 30% of the chloroform produced was discharged to bleaching effluents. Chloroform in the effluents was not decomposed by activated sludge, and more than 97% was emitted to the air by volatilization. It is suggested that chloroform formation in Japanese LOKP bleaching mills can be decreased to 16–42t/year with a production of 8 million adt pulp by introducing ECF bleaching into all mills. This is a considerable fall from the chloroform discharge from ECF and chlorine bleaching mills in Japan that was estimated to be approximately 1000t for the 1999 fiscal year.     

Significance of benzylic hydroxymethylene group in the reaction of lignin side-chain with active oxygen species under oxygen bleaching conditions

To examine the effect of the presence of benzylic hydroxyl group on the reaction of β-O-4 type lignin moiety with active oxygen species (AOS) under oxygen bleaching conditions, a specially designed β-O-4 type model compound carrying the benzylic methoxyl group, 2-(3,5-difluorophenoxy)-3-methoxy-3-(3,4-dimethoxyphenyl)propan-1-ol (IV), was treated together with a phenolic compound, 4-hydroxy-3-methoxybenzyl alcohol (II), under oxygen bleaching conditions. In this reaction system, AOS were generated by reactions of compound II with dioxygen and attacked compound IV. Compound IV was rather stable, while an analogous model compound carrying the benzylic hydroxyl group, 2-(3,5-difluorophenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (I), was rather degraded. This result and the previous knowledge on the relatively high stability of 3,4-dimethoxybenzyl alcohol carrying only the hydroxymethyl group as side-chain under the identical reaction conditions suggested that the existence of benzylic hydroxymethylene group is essential in the extensive reaction of side-chain of β-O-4 type lignin moiety with AOS. To compare the reactivity of AOS toward different types of hydroxyl and aryloxyl carbons, 2-(3,5-difluorophenoxy)propane-1,3-diol (VI) or 3-(3,5-difluorophenoxy)propane-1,2-diol (VII) was also subjected to this reaction system. Compound VII was degraded by AOS more extensively than compound VI.     

Progress of oxidation of non-phenolic lignin moiety in an oxygen bleaching process via the conversion of non-phenolic into phenolic lignin moiety

To examine whether non-phenolic lignin moiety is converted into the new phenolic counterpart by the participation of active oxygen species (AOS) under oxygen bleaching conditions, a β-O-4 type dimeric lignin model compound, 2-(2-methoxyphenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (I), 2-(3,5-difluorophenoxy)-1-(4-hydroxy-3-methoxyphenyl)propane-1,3-diol (III), or 2-(3,5-difluorophenoxy)-1-(3,4-dimethoxyphenyl)propane-1,3-diol (IV), was treated under conditions similar to those for oxygen bleaching. A phenolic compound, 4-hydroxy-3-methoxybenzyl alcohol, was added together to generate AOS in the reaction of compound I or IV. The results obtained suggested that AOS attack the side chains of compounds I, III, and IV accompanied by the β-O-4 bond cleavages and the liberations of the corresponding phenolic compounds, 2-methoxyphenol (II), 3,5-difluorophenol (V), and compound V, respectively. However, the rapid liberation of compound V in the oxygen-alkali treatment of compound III may mainly be caused by alkaline-induced reactions and/or some oxidation reactions of the primary degradation product of compound III, a muconic acid derivative.     

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     

Delignification of cell walls of <Emphasis Type="Italic">Chamaecyparis obtusa</Emphasis> during alkaline nitrobenzene oxidation

To clarify the behavior of whole lignins in wood cell walls during alkaline nitrobenzene oxidation, the delignification process from cell walls in normal and compression woods of Chamaecyparis obtusa Endl. (Cupressaceae) was observed using ultraviolet and transmission electron microscopies. The lignin content conspicuously decreased to around 10% after 35min in normal wood. The lignin content in compression wood finally leveled off at aroumd 10% after 50min. In gel filtration of oxidation products in ethyl acetate, a high molecular weight fraction was prominent in extracts from the early stage of the reaction. As the oxidation progressed, the high molecular weight fraction became less prominent in both normal and compression wood. Changes in the weights of cell wall residues during reaction indicated that approximately half of the components other than lignin were also removed from the cell walls. This shows that the majority of lignin with relatively high molecular weight is removed from the cell walls together with polysaccharides in the early stage of the reaction and that further oxidative degradation occurs in solution in later stages. Only a small amount of the lignin with low molecular weight could be analyzed by gas chromatography.Parts of this report were presented at the 47th (Kochi, April 1997) and 48th (Shizuoka, April 1998) Annual Meetings of the Japan Wood Research Society, and at the Lignin Symposium, Sapporo, October 1997     

提高杨木线性振动摩擦焊接胶合性能的研究

研究了杨木线性振动摩擦焊接的干剪切强度、湿剪切强度和木破率。为提高杨木摩擦焊接的湿剪切强度与木破率,采用表面氧化、表面磺化以及表面涂覆的方式处理杨木板材,再经线性振动摩擦焊接进行黏合,使用万能力学试验机测得其剪切强度,对比表面处理前后剪切强度的变化,并利用傅里叶红外光谱分析了其表面处理前后基材和摩擦焊接层的化学基团变化情况,对胶合性能的变化做出解释。研究结果表明:杨木经过表面氧化磺化涂覆醋酸锌处理后,摩擦焊接层的干剪切强度为5.41 MPa,木破率为63%,与未处理的杨木相比,分别提高了48.22%和96.88%;湿剪切强度从0提高到1.34 MPa;摩擦焊接时厚度损失减少了46.4%。杨木分别经过表面氧化和表面磺化处理后,摩擦焊接层的干剪切强度仅为3.45和4.10 MPa,木破率为28%和42%,湿剪切强度为0.76和0.96 MPa。摩擦焊接层的红外光谱分析表明,经表面氧化磺化涂覆醋酸锌处理后,杨木中的纤维素和半纤维素分解,使木质素的相对含量有所增加,且活化了杨木中的—OH,与醋酸锌生成多醚,消耗了亲水性的—OH。     

木质素电氧化的影响因素研究

木质素是天然高分子聚合物，具有一定的化学反应惰性。本文率先研究草类木质素在膜助电解时的电化学氧化作用。其结果表明：膜助电解对黑液中的有机物具有一定的氧化作用，能使木质素中的芳环被氧化而打开；同时木质素的氧化作用与施加的电压、阳极的电极材料等因素有关。通过对木质素氧化产物结构的进一步研究，可为木质素的电化学改性提供了新的方法。     

Characterization of the lignin-derived products from wood as treated in supercritical water

Sugi (Cryptomeria japonica D. Don) and buna (Fugus crenata Blume) woods were treated with supercritical water (>374°C, >22.1 MPa) and fractionated into a water-soluble portion and a water-insoluble residue. The latter was washed with methanol to be fractionated further into a methanol-soluble portion and a methanol-insoluble residue. Whereas the carbohydrate-derived products were in the water-soluble portion, most of the lignin-derived products were found in the methanol-soluble portion and methanol-insoluble residue. The lignin-derived products in the methanol-soluble portion were shown to have more phenolic hydroxyl groups than lignin in original wood. The alkaline nitrobenzene oxidation analyses, however, exhibited much less oxidation product in the methanol-soluble portion and methanol-insoluble residue. These lines of evidence suggest that the ether linkages of lignin are preferentially cleaved during supercritical water treatment. To simulate the reaction of lignin, a study with lignin model compounds was performed;-O-4-type lignin model compounds were found to be cleaved, whereas biphenyl-type compounds were highly stable during supercritical water treatment. These results clearly indicated that the lignin-derived products, mainly consisting of condensed-type linkages of lignin due to the preferential degradation of the ether linkages of lignin, occurred during supercritical water treatment.This study was presented in part at the 45th lignin symposium, Ehime, Japan, October, 2000; and the 49th Annual Meeting of the Japan Wood Research Society, Tokyo, April 1988