Characterisation of pulp demethylation during chlorine dioxide bleaching

Summary The methoxyl loss from softwood kraft pulp during chlorine dioxide treatment can be accounted for by methanol and the methoxyl content of dissolved organic material in the bleach filtrate. This was established by a methoxyl group mass balance made at different bleaching times. It was found that ClO₂ rather than the in-situ generated hypochlorous acid is mainly responsible for the methanol formation. It was shown that fully methylated pulp is hardly demethylated by ClO₂ under industrial ClO₂ bleaching conditions when hypochlorous acid is effectively captured. Furthermore, the rates of formation of methanol and methoxyl group containing dissolved organic material are proportional to each other. The experimental evidence suggest that demethylation and delignification are closely related during ClO₂ treatment of softwood kraft pulp.     

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。     

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     

Performance of new and commercial xylanases for ECF and TCF bleaching of eucalyptus kraft pulp

Since xylanases can differ widely in their bleaching efficiency, the performance of one new and two commercial xylanases was evaluated in an eucalyptus kraft pulp following XD (X: xylanase; D: chlorine dioxide) and XP (P: hydrogen peroxide) sequences. The new xylanase did not show a significant bleach boosting effect but increased the hexenuronic acid (HexA) removal by 10% after the D stage. The two commercial xylanases behaved in a different way, being one of them (X_C) the most effective in increasing delignification (9%) and brightness (3%ISO). Its effectiveness was related to its greater action on releasing the xylan polymer, thus producing also a strong decrease in the HexA contents during the enzymatic stage (15%). All xylanases produced morphological changes in the fibre surfaces, but only with X_C cracks and holes that improved the diffusion of reactives were observed. Finally, the best bleaching results were obtained with the XD sequence and therefore, a complete bleaching sequence XDEopD₁ (Eop: alkaline extraction with oxygen and peroxide) was carried out with the best enzyme.     

Examination of polychlorinated dibenzo-<Emphasis Type="Italic">p</Emphasis>-dioxins and polychlorinated dibenzofurans in process water of kraft pulp bleaching mill using chlorine dioxide from the aspect of environmental water quality

Process water of a pulp mill with extended kraft cooking, two-stage oxygen delignification, and chlorine dioxide bleaching was examined from the aspect of a new standard for environmental water quality in Japan. According to the new standard, the concentration of dioxins – polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, coplanar polychlorinated biphenyls – in environmental water is restricted to less than 1pg TEQ/l. We clarified that the concentrations of the dioxins in sewers in the chlorine dioxide stage and the alkali stage were less than 1pg TEQ/l and that the 2,3,7,8-tetrachlorodibenzofuran concentrations were 0.5pg/l or less. In addition, a main source of 1,3,6,8- and 1,3,7,9-tetrachlorodibenzo-p-dioxins in the process water seemed to be an agrochemical in water supplied from a river.     

仿酶催化脱木质素研究进展

综述了目前金属配合物仿酶催化脱木质素的研究现状及发展趋势，着重评价了卟啉类和非卟啉类金属配合物作为木质素氧化降解的仿酶催化剂的效果，对金属配合物仿酶催化脱木质素技术的应用前景进行了展望。金属卟啉配合物由于在相对温和的条件下具有较高的催化活性而受到瞩目。氯代铁卟啉由于氯原子对卟啉骨架环的保护作用而十分稳定，表现出高活性及可循环性。卟啉中心金属离子的种类也对脱木质素的催化活性产生影响。由于金属卟啉配合物的成本较高，因而给实际应用带来一定困难。非卟啉金属配合物如金属酞菁、Gif体系、希夫碱等，由于具有较高的催化活性和选择性以及易于合成等特点正倍受关注。     

Sulfuric acid bleaching of kraft pulp 1: Bleaching of hardwood and softwood kraft pulps

To develop a new nonchlorine bleaching technology, hardwood and softwood kraft pulps, before and after oxygen-alkali predelignification, were treated with dilute sulfuric acid solutions (pH 1.0-1.8) at 100°C for 1 h and then extracted with aqueous sodium hydroxide at 70°C for l h. Hardwood kraft pulp was successfully bleached. The delignification selectivity was similar to that seen with oxygen-alkali bleaching; and it was greatly enhanced by the addition of sodium nitrate and sodium nitrite. The sulfuric acid bleaching can replace the presently adopted oxygen and chlorine stages if the additives are allowed. This bleaching process was also effective for oxygen-bleached hardwood kraft pulp, but it was less effective for softwood kraft pulp and oxygen-bleached softwood kraft pulp. The effectiveness of the addition of sodium nitrate and sodium nitrite was more apparent for softwood kraft pulp than for hardwood kraft pulp.Part of this report was presented at the 7th International Symposium on Wood and Pulping Chemistry, Beijing, July 1993     

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。     

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.     

世界木材制浆技术新进展

文章论述了木材制浆技术的新进展，在硫酸盐法制浆技术的革新方面，推荐了间歇蒸煮的快速置换加热（ＲＤＨ）技术与连续蒸煮的改良连续蒸煮（ＭＣＣ）和深度脱木素改良连续蒸煮（ＥＭＣＣ）技术。还介绍了超高得率制浆方法，特别是碱性过氧化氢机械制浆（ＡＰＭＰ）法和爆破制浆（ＥＰ）法，用这两种方法生产的纸浆得率高、白度高、强度高、能耗较低。     

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     

硫酸盐竹浆氧脱木质素和全无氯漂白的研究

通过比较不同条件下氧脱木质素后浆料的卡伯值、黏度、得率、白度和脱木质素选择性等指标,研究了硫酸盐竹浆卡伯值25.6氧脱木质素工艺参数,发现用碱量和温度是决定氧脱木质素效果的主要因素.最佳工艺条件为:用碱量3.5%,温度85℃,氧气压力0.6MPa,保温时间80min.两段氧脱木质素(中间不洗涤)可以提高木质素脱除率和选择性.研究还发现,在氧碱脱木质素过程中加入醌类混合物助剂(表示为Oq),可使浆料的黏度和氧脱木质素的选择性大大提高.采用OQ(PO)、(O1O2)Q(PO)、OQ(PO)1(PO)2和OqQ(PO) 4种短漂序都可使竹浆白度达到80%(ISO) 以上,且具有很好的白度稳定性.OQ(PO)、(O1O2)Q(PO)和OQ(PO)1(PO)2 3种漂序漂后浆纸页强度性能相近,OqQ(PO)漂后浆的抗张指数、撕裂指数和耐破指数明显高于其它3种漂序.     

Modeling hydrogen peroxide bleaching to predict optical properties of bleached hardwood CMP

Due to the variations in opacity and brightness of peroxide bleached pulp at Mazandaran Wood and Paper Industries Company (MWPI), empirical models were developed to predict chemimechanical pulp (CMP) brightness and opacity from peroxide bleaching conditions and to drive the optimum operating conditions. To overcome the inconsistency problem, a multi-variate regression analysis method was used for model building. The models were then validated using a new data set from the bleach plant at MWPI, assessing the models’ predictive ability and performance. The results show that there is a relationship between bleaching variables and such dependent variables as pulp brightness and opacity. In addition to the hydrogen peroxide charge and pulp initial brightness, the initial opacity had a significant reverse effect on the final CMP brightness. It was also found that the concentration of total Na⁺ in the CMP tower was the most important variable affecting the final pulp opacity. The validation results demonstrated that these models can be employed as useful tools for process optimization purposes.     

Chemistry of delignification

Summary Delignification processes comprising various pulping and bleaching reactions are reviewed in the light of a general concept dividing these reactions into nucleophilic and electrophilic categories. It is shown by numerous examples that pulping is due to the action of external nucleophilic species attacking electron-deficient centres in carbonyl and conjugated carbonyl (=enone) structures and to the presence of neighbouring nucleophilic groups attacking the -carbon atom of side chains. On the other hand, bleaching is initiated by electrophilic species attacking electron-rich centres in aromatic nuclei and unsaturated, ring-conjugated side chains. These initial bleaching reactions are followed by nucleophilic reactions taking place during the same or during subsequent bleaching steps.The efficiency of a particular delignification procedure is determined by the extent of cooperation between nucleophilic and electrophilic reactions.During delignification processes carbohydrate constituents of wood are subject to reactions which follow mechanisms analogous to those of lignins. This provides an explanation for the fact that the selectivity of pulping and bleaching processes is limited.Academy Lecture presented at the Ninth Cellulose Conference, Syracuse, USA, May 24–27, 1982. Extended Version of a survey article published in Holzforschung 36 (1982): 43–51 and 55–64 Part 2: Reactions of lignins during bleaching, will be published in No. 1/86 and contains all literature references     

Modeling carbon allocation in trees: a search for principles

We review approaches to predicting carbon and nitrogen allocation in forest models in terms of their underlying assumptions and their resulting strengths and limitations. Empirical and allometric methods are easily developed and computationally efficient, but lack the power of evolution-based approaches to explain and predict multifaceted effects of environmental variability and climate change. In evolution-based methods, allocation is usually determined by maximization of a fitness proxy, either in a fixed environment, which we call optimal response (OR) models, or including the feedback of an individual's strategy on its environment (game-theoretical optimization, GTO). Optimal response models can predict allocation in single trees and stands when there is significant competition only for one resource. Game-theoretical optimization can be used to account for additional dimensions of competition, e.g., when strong root competition boosts root allocation at the expense of wood production. However, we demonstrate that an OR model predicts similar allocation to a GTO model under the root-competitive conditions reported in free-air carbon dioxide enrichment (FACE) experiments. The most evolutionarily realistic approach is adaptive dynamics (AD) where the allocation strategy arises from eco-evolutionary dynamics of populations instead of a fitness proxy. We also discuss emerging entropy-based approaches that offer an alternative thermodynamic perspective on allocation, in which fitness proxies are replaced by entropy or entropy production. To help develop allocation models further, the value of wide-ranging datasets, such as FLUXNET, could be greatly enhanced by ancillary measurements of driving variables, such as water and soil nitrogen availability.     

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。     

桉树制浆综述

本文介绍了(1)用桉木生产漂白化学浆,包括硫酸盐法和碱一蒽醌法制浆;(2)用按木生产漂白半化学浆,主要是中性亚硫酸盐半化学高得率浆;(3)用桉木生产漂白化学机械浆,包括冷碱法和亚硫酸盐法制浆;(4)用桉木生产漂白化学热磨机械浆。     

Comparison of cellulose extraction methods for analysis of stable-isotope ratios of carbon and oxygen in plant material

The Jayme-Wise and diglyme-HCl methods for extracting cellulose from plant material for stable-isotope analysis differ considerably in ease of use, with the latter requiring significantly less time and specialized equipment. However, the diglyme-HCl method leaves a small lignin residue in the crude cellulose that may affect stable-isotope values, whereas alpha-cellulose produced by the Jayme-Wise method is relatively pure. We examined whether adding a bleaching step to the diglyme-HCl method could produce cellulose of comparable purity to alpha-cellulose by comparing the yield, percent carbon, and carbon (delta13C) and oxygen (delta18O) stable isotope ratios of the two celluloses. We tested each method on the wood of five species that differ in ease of delignification, Eucalyptus maculata Hook., E. botryoides Sm., E. resinifera Sm., Pinus pinaster Ait. and Callitris glaucophylla J. Thompson & L.A.S. Johnson, as well as the foliage of C. glaucophylla. For hardwoods such as the eucalypts, the diglyme-HCl method without bleaching produced cellulose with delta13C and delta18O ratios similar to alpha-cellulose. For the softwood, C. glaucophylla, 3 h of bleaching with acidified chlorite following treatment with diglyme-HCl produced cellulose with delta13C and delta18O ratios similar to alpha-cellulose. Bleached and unbleached crude celluloses and alpha-cellulose of P. pinaster were similar in delta18O, but not delta13C. Both types of crude cellulose produced from the foliage of C. glaucophylla had significantly different isotope ratios from alpha-cellulose. Overall, the diglyme-HCl method, with or without bleaching, appears to be a simple, fast method for extracting alpha-cellulose from hardwoods for stable-isotope analyses, but its suitability for softwoods and foliage needs to be evaluated depending on the species.     

On the selectivity of ozone delignification of softwood kraft pulps

Summary Ozonation of kraft pulp and oxygen-delignified kraft pulp in acetic acid/water mixtures has been studied at different pulp consistencies with and without an inhibitor to obtain information about the limitations of the selectivity of the ozone treatment. The experiments have been performed according to a full factorial design and data have been analysed by stepwise regression analysis. The results show that a better delignification selectivity can be achieved when ozone is applied in acetic acid media instead of conventional aqueous media. By combining conventional oxygen delignification and ozonation in acetic acid, pulps with equal strength properties and better optical properties compared to those of conventional O(DC)E prebleached pulps can be obtained. This study has also revealed that the reagent is utilized far more efficiently in ozonation at high pulp consistency (35%) than in ozonation at low consistency (1%), and that a similar selectivity can be achieved in both types of ozonation by choosing appropriate conditions. The greater selectivity of ozonation in acetic acid than in water is interpreted in terms of different stabilities of the oxidant in these reaction media. The relation between the formation of hydroxyl radicals and the extent and selectivity of delignification during ozonation has been investigated. The final bleaching of pulps prebleached with ozone in acetic acid medium has been studied. Two final bleaching sequences are presented, by which pulps with ISO brightness levels of 79% and 90% can be produced.The authors are indebted to the Swedish National Board for Technical Development (Styrelsen för Teknisk Utveckling) for financial support for this work and to STORA Technology for pulp tests and analyses     

A review of stand basal area growth models

Growth and yield modeling has a long history in forestry. The methods of measuring the growth of stand basal area have evolved from those developed in the U.S.A. and Germany during the last century. Stand basal area modeling has progressed rapidly since the first widely used model was published by the U.S. Forest Service. Over the years, a variety of models have been developed for predicting the growth and yield of uneven/even-aged stands using stand-level approaches. The modeling methodology has not only moved from an empirical approach to a more ecological process-based approach but also accommodated a variety of techniques such as: 1) simultaneous equation methods, 2) difference models, 3) artificial neural network techniques, 4) linear/nonlinear regres-sion models, and 5) matrix models. Empirical models using statistical methods were developed to reproduce accurately and precisely field observations. In contrast, process models have a shorter history, developed originally as research and education tools with the aim of increasing the understanding of cause and effect relationships. Empirical and process models can be married into hybrid mod-els in which the shortcomings of both component approaches can, to some extent, be overcome. Algebraic difference forms of stand basal area models which consist of stand age, stand density and site quality can fully describe stand growth dynamics. This paper reviews the current literature regarding stand basal area models, discusses the basic types of models and their merits and outlines recent progress in modeling growth and dynamics of stand basal area. Future trends involving algebraic difference forms, good fitting variables and model types into stand basal area modeling strategies are discussed.