Antibody-based assay for galacturonan deesterification on wood pulp fibers during bleaching

Antibodies recognizing galacturonan were used in immunoassays for industrial unbleached and hydrogen peroxide-bleached chemithermomechanical pulp (CTMP). The assays were based on a colorimetric method using specific monoclonal antibody recognition of acidic and methylated homogalacturonan, respectively, on the pulp fiber surfaces. Alkaline phosphatase-conjugated antibodies were linked to the galacturonan specific antibodies, and an alkaline phosphatase substrate (p-nitrophenylphosphate) was used to develop a yellow reaction product that can be followed spectrophotometrically. Together the newly developed immunoassays were able to describe the deesterification, specifically, of surface-localized galacturonan on CTMP, induced by alkaline hydrogen peroxide bleaching. Unbleached CTMP showed relatively more labeling by methylated galacturonan recognizing antibodies, whereas bleached CTMP was relatively more labeled for acidic galacturonan. The increase in negative charge of the bleached pulp was also shown by polyelectrolyte titration; the negative surface charge was 9.3 μeq g⁻¹ in unbleached CTMP and 21.7 μeq g⁻¹ in bleached pulp.     

Characteristic fragment ions from lignin and polysaccharides in ToF–SIMS

Different model compounds for lignin, hemicelluloses and pectins were studied by time-of-flight secondary-ion mass spectrometry (ToF–SIMS). Mass spectra of Klason lignin from normal and compression spruce wood, aspen wood and wheat straw were compared. Spectra of brominated spruce and aspen wood sections showed fragment ions attributed to brominated guaiacyl and syringyl units in lignin at m/z 215, 217, 229 and 231, and m/z 245, 247, 249 and 261, respectively. Spectra of mono-, oligo- and polysaccharides showed fragment ions at m/z 127 and 145 characteristic for hexose units, and ions at m/z 115 and 133 characteristic for pentose units. The same ions were detected in spectra of delignified spruce and aspen wood sections. Labelling of anionic groups by Sr²⁺ ions followed by ToF–SIMS analysis showed that pectins were present at specific locations on the surfaces of spruce and aspen wood sections still after delignification with hydrogen peroxide in acetic acid.     

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     

毛竹水解渣木质素氢解制备芳香化学品

以毛竹水解渣为原料,分别采用过氧化氢法和甲醇法提取木质素,在相同的反应条件下对比了两种木质素转化及产物分布的结果,并进一步优化了过氧化氢法提取的木质素的氢解转化最优条件.研究结果表明:温度为220℃,反应时间60 min时,过氧化氢木质素可以全部转化为可溶物,单体收率为14.85％;甲醇法提取的甲醇木质素,转化产物中可...     

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。     

The reactions of alkaline hydrogen peroxide with lignin model dimers

Summary Three lignin model dimers of the phenacyl -aryl ether type were treated with alkaline hydrogen peroxide under simulated technical bleaching conditions in the presence and absence of peroxide stabilization agents. The reaction products were characterized and their yields determined using a combination of gas chromatography and gas chromatography-mass spectrometry. The principal reaction in each case consisted in the displacement of the side chain via the Dakin reaction. In the case of one of the dimers, -guaiacoxy--hydroxypropioguaiacone, a competing dehydration reaction occurred, resulting in the formation of guaiacyl -guaiacoxyvinyl ketone, which subsequently was degraded to guaiacol and glycolic acid. Stabilization of the peroxide with Na₅DTPA enhanced the yield of acyclic Dakin products (-guaiacoxy carboxylic acids). Product analysis supported the conclusion that oxygen, formed from the decomposition of peroxide, was itself relatively unreactive in the initial phase of the reaction under peroxide bleaching conditions.Contribution No. 139 from the Empire State Paper Research Institute, State University of New York College of Environmental Science and Forestry, Syracuse, New York. The authors gratefully acknowledge financial support received from the Empire State Paper Research Associates, Inc.     

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     

喷雾法提高中纤板表面白度的试验研究

为了使中纤板板面具有更好的色泽,增加销量,文章就如何提高中纤板表面白度进行了试验性研究。采用以草酸、漂白粉、VBL型荧光增白剂、双氧水为主剂的处理配方分别用涂刷的方法对小样中纤板表面进行增白试验,通过测定和分析处理效果发现,草酸、双氧水是适合中纤板板面增白的处理剂,综合考虑处理结果,以及成本和环保要求等因素,最后确定H2O2（27．5％）、NaOH（5％）、Na2SiO3（5％）以适当比例混合和浓度为5％的草酸为最佳中纤板板面增白配方。最后采用喷雾法用最佳处理配方对大样中纤板进行增白试验。结果表明,采用这两个配方对中纤板表面进行喷雾增白处理,白度分别可提高42．6％和17．5％,处理成本分别为127．11元／m^3和38．35元／m^3。     

漆酶在生物造纸中的应用

利用生物酶（如漆酶）预处理可以降低化学浆的残余木素量,减少制浆中的能源消耗,提高纸浆强度特性和光泽度等。在介体参与下,漆酶能够降解木素,使残余木素的摩尔质量减少、木素中的酚羟基减少、羰基和羧基增加,对后续的漂白过程起到活化木素的作用。漆酶等酶活系统能将漂白废水中的有机氯化物转变成无机氯和CO2,破坏发色基团组织和结构,降低漂白废水中的TOCl、BOD、COD和色度。漆酶在氧气和介体存在下能使木素产生自由基的缩合,提高纤维间的粘合性,改善高木素含量和纸浆的性能。漆酶作为一种非专一型聚酚酶,在一定程度上可与树脂反应,可以催化好氧污染物的酚羟基基固,生成苯氧自由基和水。     

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     

TCF Bleaching of Populus tomentosa Kraft Pulps with H2O2 Pretreatment under Acid Condition

The process of peroxide bleaching of Populus tomentosa kraft pulp with H2O2 pretreatment under acid condition was studied. The variations of pulp characteristics such as brightness, Kappa number and viscosity during the peroxide bleaching process were discussed and the concept of the A/B value was presented for the first time. The results show that acid pretreatment with H2O2 is essential to improve pulp brightness and avoid viscosity loss. The conclusion is reached that the A/B value has great influence on pulp properties when the total amount of peroxide used in the bleaching process is 2%–5%. Pulp with a high viscosity and brightness can be obtained when A/B is about 0.15.     

Surface analysis of explosion pulps by ESCA Part 1. Carbon (1s) spectra and oxygen-to-carbon ratios

Summary The surface composition of explosion pulp and conventional CMP and CTMP underwent ESCA spectroscopy. Explosion pulps exhibited a higher oxygen-to-carbon ratio and less C1 peak areas compared to conventional CMP/CTMP. Based on the theoretical O/C ratios and C1 contents for the main components of wood fibers (i.e., carbohydrates, lignin and extractives), a triangular graph was used to illustrate the relative amounts of the three components on the surface. This analysis indicated that explosion pulps had more carbohydrates exposed on their fiber surface, which may explain their high physical strength. A bulk analysis indicated that these differences could not depend on their bulk compositions, since the latter were similar.     

Determination of the cellulose and lignin content on wood fibre surfaces of eucalypts as a function of genotype and site

We compared the chemical composition of wood fibres and fibre surfaces of several eucalypt species and hybrids originating from various growth sites in South Africa. The objective was to test for differences in chemical surface composition due to genetics or site with the ultimate aim to facilitate a tailor-made supply of wood for pulping that results in an optimal blend of fibres that can be pulped together with similar yields. This, however, requires a sound knowledge of the fibre properties. The surface functionality on the single fibre level is a key property, because it determines how good inter-fibre bonding will be when paper is formed, which depends amongst other fibre properties on the amount of free hydroxyl groups that are available and therefore on the cellulose content on the fibre surface. The cellulose and lignin content on the fibre surface were determined with chemical force microscopy, a variation of atomic force microscopy. Since the general bulk composition of the fibre and the surface composition might differ, both parameters were determined. We found significant differences in the cellulose and lignin content on fibre surfaces, with regard to genotype and site, respectively. In some, but not all, cases, the surface composition of wood fibres followed the bulk composition, and differences were generally more pronounced. Differences due to genotype were significant, especially with regard to the surface lignin content—but variation due to site was also distinctly recognisable. This variation in surface functionality could be the reason why some pulpwood blends result in a lower pulp yield and different quality.     

Lignin Characterization of Triploid Clones of Populus tomentosa Carr.

In order to understand the structural characteristics of lignin in triploid clones ofPopulus tomentosa and its changes in the processes of pulping and bleaching, milled wood lignin （MWL）, lignin carbohydrate complex （LCC） and the residual lignin from kraft pulp （KP） and sulfite pulp （SP） were isolated and analyzed by Fourier transform infrared （FTIR） spectrum and ^13C nuclear magnetic resonance （NMR）. The most diagnostic peaks were assigned and the differences were discussed. The spectral patterns reveal that triploid P tomentosa shows the specific features of hardwood from temperate areas, but in the spectrum of FTIR, the strength ratio orAl270 cm^-1 to A1226 cm^-1 is 0.88, higher than the average of hardwood from temperate areas, which will make the lignin delignification more difficult during pulping and bleaching. The LCC from triploid P tomentosa is mainly composed of xyloglucan and glucuronic acid, and other glucides have much lower ratio. In LCC FTIR, there are three peaks at 1 427, 1 329 and 1 046 cm^-1, indicating that both semi-cellulose and cellulose could exist in LCC, and that there might be relationships between cellulose and lignin. Compared with the residual lignin from KP and SP, the condensed structure in KP is more than that in SP.     

Surface analysis of explosion pulps by ESCA

Summary The oxygen (1s) ESCA peak for aspen explosion pulp consists of two components, O1 and O2. A tentative assignment was made for them. O1 with lower binding energy is assigned to oxygen in lignin; while O2 comes mainly from the oxygen elements in carbohydrates. Thus, an O1 area percentage might be viewed as a measure of lignin exposed on the fiber surface. Sulfur (2p) spectra show that the sulfur on the fiber surface of the pulps studied here is in the form of sulfonate groups. Compared to conventional pulps, the lower percentage of O1 and higher sulfur-to-carbon ratio for explosion pulps imply higher number of hydrophilic groups exposed on their fiber surface.     

麦草碱木质素的氧化降解及产物特性的研究(Ⅰ)

对不同氧化条件下 ,麦草氧化碱木质素的分子质量、酸溶木质素含量、酚羟基、羧基、甲氧基含量、表面活性的变化进行了研究。研究表明 ,当用碱量较高 (60 % ,30 % )时 ,其分子质量均一化程度较高 ,加入H2 O2 后分子质量 >10 0 0 0的高分子组分含量明显下降 ,但用碱量较低(10 % ,5 % )时则变化不大 ,说明在O2 /H2 O2 氧化时碱有着明显作用。对酸溶木质素含量来说 ,也呈现出这一规律。木质素经氧化后 ,酚羟基含量升高 ,而羧基、甲氧基含量下降。在高用碱量条件 (60 %、30 % )下 ,氧化木质素的表面张力下降较大 ,添加H2 O2 后下降更为明显。当用碱量为60 %、H2 O2 用量 10 %时 ,氧化木质素 4 %水溶液的表面张力可由原木质素的 4 6.8mN/m降至 38.8mN/m。     

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     

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     

Changes in chemical characteristics of bamboo (Phyllostachys pubescens) components during steam explosion

Chemical changes in cell wall components of bamboo internode during steam explosion process were analyzed to investigate self-binding mechanism of binderless board from steam-exploded pulp. More than 30% of xylose on initial mass, which is a major hydrolyzate of bamboo hemicelluloses, was lost after steam explosion treatment. Bamboo lignin is characterized by the presence of ester- and/or ether-linked p-coumaric acid to lignin. The content of phenolic hydroxyl groups of lignin isolated from steam-exploded pulp was characterized 2.3 times higher than those of the extract-free bamboo internode due to the cleavage of β-O-4 linkages. Alkaline nitrobenzene oxidation of the bamboo lignin gave vanillin, syringaldehyde and p-hydroxybenzaldehyde as major products. The content of p-hydroxybenzaldehyde decreased after steam explosion treatment, indicating the cleavage of ester- and/or ether-linked p-coumaric acid. The total yield of erythronic and threonic acids in ozonation products of the extract-free bamboo internode lignin was 268 mmol (200 g lignin)⁻¹, while those of lignins in the steam-exploded pulp and powdery fraction were 96 and 129 mmol (200 g lignin)⁻¹, respectively, suggesting the significant cleavage of β-O-4 linkages during steam explosion treatment. The cleavage of β-O-4 linkages was also confirmed by ¹H- and ¹³C-NMR spectroscopic observations.     

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。