蔗渣硫酸盐浆次氯酸盐漂白中有害物质的研究

本文对蔗渣硫酸盐浆次氨酸盐漂白中有机氯及三氯甲烷的形成情况进行了研究，结果表明：这些有害物质的生成量与漂白用氟量、漂白浓度、温度和时间等条件有关；在次氨酸盐漂白时加入少量H2O2,可以有效地减少三氯甲烷的生成量，通过GC及ESR分析阐明H2O2能减少废液中三氯甲烷含量的机理。     

Effect of xylanase on ozone bleaching kinetics and properties of Eucalyptus kraft pulp

Environmental pressure has led the pulp and paper industry to develop new technologies in order to reduce or suppress the presence of various pollutants in effluents from bleaching plants. One of the choices for this purpose is enzyme‐based biotechnology. This study deals with the effect of using a xylanase‐based enzymatic pretreatment, in a TCF (Totally Chlorine Free) sequence, on the properties of the resulting paper pulps. The hexenuronic acid content in the pulp and the physical properties of the paper were also studied. The performance of the xylanase was analysed through kinetic studies on ozone bleaching. The enzymatic pretreatment results in easier bleaching and delignification of the pulp, causing a bleach‐boosting effect. The decreased consumption of reagent is related to a decreased content of hexenuronic groups. The physical properties of the treated pulp are similar to those of untreated pulps. Cellulose degradation, delignification and chromophores' removal show first‐order kinetics. Enzyme pretreatment leads to differences between the kinetic constants of cellulose degradation and chromophores' removal, due to an increased accessibility to bleaching agents. The xylanase treatment leads to a lower floor kappa number (IK_∞) during the ozone stage. Copyright © 2003 Society of Chemical Industry     

Characterization of kraft pulp delignification using sodium dithionite as bleaching agent

Abstract

The delignification of kraft pulp with sodium dithionite was studied to remove lignin content in the pulp. The sodium dithionite dissolves the chromophoric groups and residual lignin present in the pulp. The increase in dosage of sodium dithionite and reaction temperature of delignification has positive effect on kappa reduction of pulp. X ray diffraction was used to determine the crystallinity index of bleached pulp. The crystallinity increased from 83.3% for unbleached pulp to 86.7% after delignification. Fourier transform infrared spectroscopy shows the reduction in hydrogen bonding in bleached pulp and also the conversion of cellulose I to cellulose II. FT-Raman spectra shows that the fluorescence observed in the spectra of unbleached pulp reduced significantly in comparison to the spectra of bleached pulp resulting in removal of residual lignin and chromophoric groups present in the pulp. Scanning electron imaging shows the smoothening of fiber surface after bleaching. The delignification reaction followed first-order kinetics and activation energy is 33.57kJ/mol.     

Simulating the impact of kraft pulping and bleaching parameters on Eucalyptus camaldulensis pulp properties using MATLAB

In this work, Eucalyptus camaldulensis was evaluated as the raw material for chemical pulp under different pulping and bleaching conditions. The pulping was carried out at different H‐factors, and at different effective alkalis. The resulting pulps were then oxygen delignified and bleached using various dosages of bleaching chemicals in a D₀EpD₁ sequence. The effect of independent variables (pulping or bleaching variables) on dependent variables (pulp properties) was analysed based on the multivariable least square method via MATLAB software. An agreement was found between the results predicted from the models and the experimental data. To obtain a kappa number of 15, the optimum pulping conditions were a temperature of 155°C, a time of 225 min, and an EA of 23%. Also, the hexenuronic acid (HexA) content of cooked pulp was significantly decreased in the chlorine dioxide bleaching stages, and was only marginally related to the final HexA content of bleached pulps.     

Strategies to reduce the brightness reversion of industrial ECF bleached Eucalyptus globulus kraft pulp

BACKGROUND: Brightness stability is a key property of bleached chemical pulps and is primarily determined by wood species and bleaching process conditions. Eucalyptus globulus is becoming a very important raw material for hardwood pulp production. In spite of this importance, there is a relative lack of systematic studies in the literature dealing with the subject. This research aims to study the effect of some of the foremost bleaching parameters of a DEDD bleaching sequence as well as the effect of a final P stage (DEDP instead of DEDD) in the brightness stability of bleached E. globulus kraft pulps. RESULTS: The increase of the D₀ stage temperature from 55 °C to 90 °C caused an increase in brightness stability. Increasing the ClO₂ charges from 2.8% to 3.2% also improved significantly the brightness stability. A high H₂SO₄ charge in the D₀ stage (10 kg tonne^?1 pulp) diminished the brightness stability. The combination of H₂O₂ addition to the E stage and ClO₂ reduction in the two final D stages does not affect brightness reversion. Raising the D₂ stage temperature from 65 °C to 82 °C decreased the brightness reversion, while an increase was obtained when the temperature rose above 82 °C. Substitution of the last ClO₂ stage in the DEDD sequence by a H₂O₂ stage (DEDP) significantly reduced the brightness reversion. CONCLUSION: For an existing pulp mill in which the implementation of new technologies to improve brightness reversion is considered, the results obtained showed that brightness stability can be improved without any significant capital investment. Copyright © 2007 Society of Chemical Industry     

Chlorine dioxide delignification kinetics and eop extraction of softwood kraft pulp

A kinetic model for 100% chlorine dioxide delignification based on experimental data is presented. From the unbleached kappa number, chlorine dioxide charge and reaction time, the model predicts kappa, brightness and residuals after the first bleaching stage. The model consists of two ordinary differential equations representing the slow and fast reactions of lignin with chlorine dioxide. In addition we found that the relationship between the chlorine dioxide consumption and the kappa number decrease was linear in the range studied and independent of the unbleached pulp kappa number.     

Electrochemical treatment of pentachlorophenol in water and pulp bleaching effluent

Adsorbable organic halides (AOX) compounds produced during bleaching of pulp are recalcitrant and known to have eco-toxic effect. We have studied the removal of pentachlorophenol (PCP) as a model AOX compound in water as well as in pulp bleaching effluent of a bamboo based mill by electrochemical treatment in batch mode. It was found that 10 mg L⁻¹ of PCP in water was removed almost completely in <10 min at a current density of 6 mA cm⁻² in the presence of 1000 mg L⁻¹ NaCl serving as an electrolyte and source of chloride ions. The initial rate of PCP removal was found to decrease at alkaline pH (9.3) as compared to that at acidic pH (5.5). PCP removal in neutralized raw pulp bleach effluent (containing 1830 mg L⁻¹ of chloride) was very slow and incomplete even after 2 h of electrochemical treatment at a current density of 15 mA cm⁻². Various pretreatments of raw bleach effluent such as, alkaline sulfide using sodium sulfide, alkaline reduction using ferrous sulfate and coagulation using potash alum were evaluated. Electrochemical treatment of potash alum pretreated effluent (spiked with PCP) could achieve >90% removal of initial colour, COD and PCP in <1 h. The treatment scheme presented here may be a promising technology for removal of AOX, COD and colour from pulp bleaching effluent. The estimated cost of combined treatment (potash alum coagulation + electrochemical) is US$ 0.7–0.9 per cubic meter of the raw pulp bleach effluent.     

黏胶纤维用落叶松溶解浆的清洁漂白

引言近年来,随着棉花价格的总体上涨和消费者对纺织材料舒适度的要求,给黏胶纤维带来了需求增长空间。作为黏胶纤维的原材料,国内目前的溶解浆产能难以满足客户需求。据统计,国内溶解浆存     

纸浆漂白废水中可吸附有机氯化物的特性研究进展

纸浆漂白废水中含有的可吸附有机氯化物是国内外造纸工业严控的废物,是造纸环保界关注的重点。在查阅资料基础上,对目前关于纸浆漂白废水中可吸附有机氯化物的成分、分布、生成以及降解特性等方面的研究进行了述评,重点介绍了纸浆漂白废水中可吸附有机氯化物的生成及降解性能方面的研究成果,并在此基础上对今后的研究趋势进行了展望。     

The final bleaching of eucalypt kraft pulps with hydrogen peroxide: relationship with industrial ECF bleaching history and cellulose degradation

BACKGROUND: The process of chemical pulp bleaching is based for the most part in chlorine dioxide within elemental chlorine free (ECF) technologies. The use of greener alternatives such as bleaching with hydrogen peroxide (P stage) is not widely used owing to selectivity concerns related to transition metal‐catalyzed decomposition reactions. Even at the final stage where peroxide is recognized to boost brightness and improve the brightness stability of the bleached pulp, cellulose degradation often overcomes these advantages. This paper presents the results of studies intended to optimize final peroxide bleaching performance considering two standard ECF industrial bleaching sequences: the conventional DED and the ECF‐light OQ(PO)D (stages name: D—chlorine dioxide; E—alkaline extraction; O—oxygen; Q—chelation, (PO)—hydrogen peroxide pressurized with oxygen). RESULTS: The addition of sodium diethylenetriaminepentaacetate (DTPA) was the most effective option in terms of DED pulp bleachability and selectivity with hydrogen peroxide, as well as in terms of brightness reversion. As regards the OQ(PO)D pulp, a blend of DTPA and magnesium was the most beneficial in those properties. CONCLUSIONS: The choice of the best hydrogen peroxide stabilizer, among the different tested combinations of magnesium and chelants (EDTA and DTPA) studied, in terms of pulp bleachability, bleaching selectivity and brightness reversion is dependent on the impact of the previous bleaching stages on metallic nature and content. The pulp Mg/(Fe + Cu) ratio was highlighted as a process parameter controlling cellulose degradation in peroxide bleaching. Copyright © 2010 Society of Chemical Industry     

Integrating laccase–mediator treatment into an industrial‐type sequence for totally chlorine‐free bleaching of eucalypt kraft pulp

Enzymatic delignification using the high‐redox potential thermostable laccase from the fungus Pycnoporus cinnabarinus and a chemical mediator (1‐hydroxybenzotriazole) was investigated to improve totally chlorine‐free (TCF) bleaching of Eucalyptus globulus kraft pulps. Different points of incorporation of the enzyme treatment into an industrial‐type bleaching sequence (consisting of double oxygen, chelation and peroxide stages) were investigated in pressurized laboratory reactors. The best final pulp properties were obtained using an O? O? L? Q? PoP sequence, where a laccase–mediator stage (L) was incorporated between double oxygen and chelation. The worse results, when the enzymatic and chelation treatments were combined in a unique stage, seemed related to partial inhibition of laccase‐mediator activity by the chelator. The new TCF sequence including the laccase stage permitted to improve eucalypt pulp delignification to values around kappa 5 (hexenuronic acid contribution over 50%) compared to kappa 7 using only TCF chemical reagents. In a similar way, the final brightness obtained, over 91% ISO, was 3–4 points higher than that obtained in the chemical sequences. Although technical and economic issues are to be solved, the results obtained show the feasibility of integrating a laccase–mediator treatment into a TCF sequence for bleaching eucalypt kraft pulp. Copyright © 2006 Society of Chemical Industry     

Electrodialysis for bleach effluent recycling in kraft pulp production: Simultaneous control of chloride and other non-process elements

In the United States, more than 50 million tons of kraft pulp are produced per year. A strong effort by kraft pulp producers has been under way for several years to reduce water use. The in-process recycling of the acidic bleach effluent carrying metals, transition metals, calcium, and often large amounts of chloride is still a significant challenge. The simultaneous selective removal of chloride, and detrimental cations from the acidic bleach effluent of bleached kraft pulp mills by electrodialysis was investigated. The laboratory results with actual effluents show that very good removal levels can be achieved in an economical process. The chloride removal from acidic bleach effluent will aid significantly in keeping chloride levels acceptable in the recovery cycle.     

Eucalyptus globulus kraft process modifications: Effect on pulping and bleaching performance and papermaking properties of bleached pulps

BACKGROUND: Increasing the yield of the wood pulping process allows the reduction of specific wood costs. Process modifications with a great impact on pulp yield are the profiling of chemical charges and addition of anthraquinone (AQ). The aim of the present work is to investigate the influence of effective alkali (EA) profiling and addition of anthraquinone on E. globulus kraft pulping performance. The impact of such process modifications on the ECF bleaching process and on the papermaking properties of the resulting bleached pulps is also evaluated. RESULTS: An EA profiling cook may lead to a pulp yield gain, which is more significant as the total EA charge used in the kraft cook increases. AQ addition to kraft pulping leads to a significant yield increase. The ClO₂ charge required to fully bleach the pulps is lower for EA profiling and higher for kraft + AQ unbleached pulps. Bleached AQ pulp presents a high beatability due to high pulp xylan retention. CONCLUSION: A low total EA charge is the key parameter for high polysaccharide retention on pulp. AQ addition constitutes a feasible strategy to increase pulp yield. Bleaching performance and papermaking properties of pulps produced with the three different methods may be affected by the kraft pulping modifications. Copyright © 2008 Society of Chemical Industry     

Diffusion of lignin macromolecules within the fibre walls of kraft pulp. Part I: Determination of the diffusion coefficient under alkaline conditions

The intrinsic rate of diffusion of soluble lignin from fibre walls to bulk liquor has never been determined previously because of experimental difficulties; for example, the diffusion rate determined in a stirred cell is affected by the mechanical action of stirring. In our work, the intrinsic rate of diffusion of lignin macromolecules from the fibre walls of a softwood kraft pulp was determined under alkaline conditions using a displacement cell which eliminated external heat and mass transfer resistances and pulp fibre disturbances. The effects of such experimental conditions as pulp bed height and liquid flow rate were studied. The diffusion rate can be described by a diffusion model for a hollow cylinder with a very wide range of diffusion coefficients. The diffusion rate increased with increasing pH. Our results provide a new understanding of the lignin diffusion process in fibre walls, which is affected by the size of lignin molecules and the pores, and by the electrostatic interactions between intrafibre pore walls and lignin.     

Kinetics of peracetic acid decomposition: Part I: Spontaneous decomposition at typical pulp bleaching conditions

Peracetic acid may become one of alternative non-chlorine bleaching chemicals in the production of fully bleached chemical pulps. In this paper, the stability of peracetic acid was studied in an aqueous solution under conditions most likely encountered in the industrial processes. It was found that three potential reactions, namely i) the spontaneous decomposition, ii) the hydrolysis and iii) the transition metal catalyzed decomposition, are responsible for the consumption of peracetic acid. Furthermore, the kinetics of the spontaneous decomposition was developed. It was found that the reaction follows a second-order kinetics with the maximum rate at pH 8.2, which is the pK_a of peracetic acid. Finally, the developed kinetic equation can describe very well the experimental results obtained in this study as well as the earlier data from Koubek (1964).     

麦草浆二氧化氯与氧气脱木素效率及相应漂白流程的对比

对麦草浆二氧化氯与氧气脱木素效率及相应的漂白流程进行了对比研究。结果表明,ClO2脱木素(D0)对木素的修饰和改性效果好于氧脱木素(O),在脱木素率低于及接近氧脱木素率的条件下,D0浆的可漂性均大于O浆。在D0段和O段脱木素率相同的条件下,采用D0A/QP、D0EP漂白流程漂后纸浆白度分别比OA/QP漂白流程高11.2和10.3个百分点。D0段废液和相应D0A/QP漂白流程三段混合废水的CODCr负荷均比O段和OA/QP漂白流程混合废水的CODCr负荷轻。D0段和O段废液的紫外光谱都呈现出木素苯环的特征吸收。纸浆的FT-IR谱图分析表明,D0浆和O浆中的羟基和羰基数量增多,随着漂白的进行,羰基等主要发色基团逐渐消除,纸浆白度得到提高。纸浆纤维形态的SEM分析显示,D0段和相应的D0A/QP漂白流程对纤维表面的破坏和损伤较O段和相应的OA/QP漂白流程轻。     

Synergism of enzymes in chemical pulp bleaching from an industrial point of view: A critical review

Enzymes are biological catalysts and are very specific, catalyzing either a single chemical reaction or a limited number of closely related reactions. For example, xylanases are enzymes that catalyze the cleavage of polymeric xylan and thereby break down this hemicellulose. The first xylanase enzyme preparations used in the bleaching process of chemical pulp also contained cellulase, which catalyzes the hydrolysis of cellulose. This obviously had an adverse effect on pulp yield and quality. Unfortunately, this setback gave enzyme-assisted pulp bleaching a negative reputation. At a later stage, enzyme producers managed to engineer enzyme production strains that generated cellulase-free xylanase preparations. However, due to the initial negative experiences with the earlier enzyme mixtures, only a limited number of companies in the pulp industry have seriously considered using these so-called second-generation enzymes in their bleach plants. It is apparent that these improved enzyme preparations would bring about significant benefits in terms of chemical cost savings and effluent quality. In addition to xylanase-aided bleaching, it is possible to improve the effectivity further by adding other enzymes, such as lipase and esterase, to create an enzyme cocktail. This may be particularly beneficial in the bleaching of hardwood pulp, such as white birch, which often encounters complex and troublesome problems with wood extractives. By adding different types of enzymes at more than one position in the fiberline, even further improvements are possible. The main objective of this review is to discuss the advantages of incorporating modern enzyme preparations in the bleaching of chemical pulp.     

Use of a Novel Extremophilic Xylanase for an Environmentally Friendly Industrial Bleaching of Kraft Pulps

Xylanases can boost pulp bleachability in Elemental Chlorine Free (ECF) processes, but their industrial implementation for producing bleached kraft pulps is not straightforward. It requires enzymes to be active and stable at the extreme conditions of alkalinity and high temperature typical of this industrial process; most commercial enzymes are unable to withstand these conditions. In this work, a novel highly thermo and alkaline-tolerant xylanase from Pseudothermotoga thermarum was overproduced in E. coli and tested as a bleaching booster of hardwood kraft pulps to save chlorine dioxide (ClO₂) during ECF bleaching. The extremozyme-stage (EXZ) was carried out at 90 °C and pH 10.5 and optimised at lab scale on an industrial oxygen-delignified eucalyptus pulp, enabling us to save 15% ClO₂ to reach the mill brightness, and with no detrimental effect on paper properties. Then, the EXZ-assisted bleaching sequence was validated at pilot scale under industrial conditions, achieving 25% ClO₂ savings and reducing the generation of organochlorinated compounds (AOX) by 18%, while maintaining pulp quality and papermaking properties. Technology reproducibility was confirmed with another industrial kraft pulp from a mix of hardwoods. The new enzymatic technology constitutes a realistic step towards environmentally friendly production of kraft pulps through industrial integration of biotechnology.     

Peracetic acid pretreatment of sugarcane bagasse for enzymatic hydrolysis: a continued work

Previous work has shown that the enzymatic hydrolysis of sugarcane bagasse could be greatly enhanced by peracetic acid (PAA) pretreatment. There are several factors affecting the enzymatic digestibility of the biomass, including lignin and hemicelluloses content, cellulose crystallinity, acetyl group content, accessible surface area and so on. The objective of this work is to analyze the mechanism of the enhancement of enzymatic digestibility caused by PAA pretreatment. Delignification resulted in an increase of the surface area and reduction of the irreversible absorption of cellulase, which helped to increase the enzymatic digestibility. The Fourier transform infrared (FTIR) spectrum showed that the absorption peaks of aromatic skeletal vibrations were weakened or disappeared after PAA pretreatment. However, the infrared crystallization index (N.O'KI) was increased. X‐ray diffraction (XRD) analysis indicated that the crystallinity of PAA‐treated samples was increased owing to the partial removal of amorphous lignin and hemicelluloses and probable physical change of cellulose. The effect of acetyl group content on enzymatic digestibility is negligible compared with the degree of delignification and crystallinity. The results indicate that enhancement of enzymatic digestibility of sugarcane bagasse by PAA pretreatment is achieved mainly by delignification and an increase in the surface area and exposure of cellulose fibers. Copyright © 2008 Society of Chemical Industry