Behavior Of Calcium,Magnesium and Manganese Compounds During Oxygen Bleaching of Kraft Pulps

During oxygen bleaching of kraft pulps manganese compounds can, depending on their amounts, the charges of sodium hydroxide and of magnesium protector, and on the presence of trace amounts of catalytically active transition metals retard or promote the depolymerization of the cellulose. The present report deals with pulps pretreated with 2 % nitrogen dioxide. As shown in forthcoming papers similar results were obtained with pulps without pretreatment with nitrogen compounds.

Pretreatment with nitrogen dioxide at 80°C followed by washing with water removed about 95 % of the magnesium and manganese from kraft pulps. Subsequent oxygen bleaching for 180 min removed 40–90 % of the calcium remaining in the pretreated pulps. Produced hydroxycarboxylate ions gave rise to low molecular complexes of calcium and of magnesium, added as protector. Competition for complexing ligands contributed to a decreased dissolution of calcium with increasing addition of magnesium. When magnesium was applied large amounts of colloids of polynuclear magnesium species were produced. These contained lignin fragments and less abundant metal compounds such as manganese and calcium.

Wet oxidation of both low molecular complexing agents and of organic fragments of larger size contributed to a decreased or unchanged concentration of low molecular metal complexes and metal compounds linked to the colloids with hydrated magnesium oxide as the main constituent. The conditions which favored the wet oxidation were similar to those which led to an increased attack on the lignin and carbohydrates in the fibers and thus promoted the dissolution of low molecular metal complexes and the formation of metal ions containing colloids. Under certain conditions precipitation of sparingly soluble manganese compounds of oxidation states higher than +2 had a predominant influence on the concentration of manganese in the liquor.     

Characterization of Residual Lignins Isolated from Unbleached and Semibleached Softwood Kraft Pulps

Abstract

Residual lignins in an unbleached and a semibleached softwood (Pinus taeda L.) kraft pulp were isolated by enzymatic hydrolysis of polysaccharides in the pulps. After purification, the residual lignins were characterized. A dissolved lignin was also isolated from the alkaline extraction spent liquor by acidification and characterized.

Results of the characterization indicate that extensive degradation of residual lignin in kraft pulp occurred during the first two stages of bleaching. The results also strongly support the previous finding that stable covalent linkages between residual lignins and carbohydrates in pulp any be the most probable cause for the residual lignins to resist delignification during kraft pulping and prebleaching.     

乙酰溴法对小兴安岭碱法杨木黑液提取物成分的研究

衍生化后的还原裂解(DFRC)法作为木质素结构解析的新方法,可以对碱法杨木黑液提取物中大分子结构的β-O-4醚键和α芳基醚键实施选择性的高效断裂.实验采用DFRC法对碱法萃取的杨木木质素进行降解,通过GC及GC-MS,分析研究了小兴安岭碱法杨木黑液提取物的成分和结构.结果表明:碱法杨木黑液提取物中主要包括4类化合物:B...     

CONTRIBUTION OF CARBOHYDRATE-DERIVED CHROMOPHORES TO KRAFT PULPING LIQUOR COLOUR

Pine wood, holocellulose, glucose and milled wood lignin were kraft cooked and the acid-insoluble materials isolated. Based on the amounts of precipitates isolated and their absorbances, most, or all, of the absorbance of the acid-insoluble material in kraft spent liquor (kraft lignin, KL) could be ascribed to lignin-derived chromophores. The absorption spectrum of kraft-cooked glucose (KG) differed significantly from that of KL and kraft-cooked milled wood lignin (KMWL), with a higher absorbance in the visible region of the spectrum. It also responded differently on treatment with a number of chemicals, strongly suggesting that carbohydrate-derived chromophores could only contribute slightly to the absorbance of KL. The effect of sequential treatment with oxygen, chlorine dioxide and alkali on the absorption spectra of KL, KG and KMWL was also determined. This produced no evidence to suggest that carbohydrate-derived chromophores contribute significantly to chromophore changes during these bleaching stages.     

Influence of Supercritical CO2 Pretreatment of Corn Stover with Ethanol‐Water as Co‐Solvent on Lignin Degradation

The process of delignification during the pretreatment of corn stover in supercritical CO₂ with ethanol‐water as co‐solvent was investigated. After pretreatment, many lignin droplets were found deposited on the fiber surface which hinder cellulose digestibility. These lignin droplets were removed by ethanol‐water and after washing the optimal glucose yield increased significantly. Lignin degradation reactions competed with condensation reactions during pretreatment. The cleavage of ether bonds and the high solubility of lignin fragments in ethanol‐water co‐solvent were the key factors for lignin removal and degradation behavior during pretreatment.     

Charge Density of Lignin Samples from Kraft Cooking of Birch Wood

Abstract

Black liquor, isolated dissolved lignin and residual lignin samples corresponding to different cooking times were obtained from flow-through kraft cooking of birch wood. Dissolved lignin was isolated from black liquor by acid precipitation and residual lignin was isolated from pulp by acid-dioxane extraction. The average mobility (μav) of the lignin-containing samples was determined by capillary zone electrophoresis. The lignin samples have a broad mobility distribution that reflects the charge-to-size ratio of the molecules. At pH 12, i.e. when lignin is completely dissociated, the μav of each type of sample increases during the cook, reflecting an increase in charge density of the lignin. For samples corresponding to the initial and beginning of the bulk delignification phases, the μav decreases in the order dissolved lignin>black liquor>residual lignin. The lower charge density of black liquor compared to dissolved lignin is proposed to be caused by associations between lignin and carbohydrate fragments dissolved in the black liquor. As from the middle of the bulk delignification phase, the μav of the three series of samples is quite similar. The decrease in mobility on lowering the pH is an indication of the degree of dissociation of the lignin phenol groups. At pH 10, i.e. about the pK_a of lignin, the μav of black liquor is highest throughout the cook. The relative order of μ_av is then black liquor>dissolved lignin≈residual lignin.     

黑液和碱木素在石油工业中的应用

本文综述了碱法制浆黑液以及碱木素在石油工业中的应用。黑液可以直接作为低粘度稠油的驱油剂,也可作为高粘度稠油的降粘剂。与蒸汽驱或蒸汽吞吐配合使用,可显著地提高稠油的采收率。从黑液中分离出的碱木素,可用作钻井泥浆添加剂、注水或注蒸汽采油的堵水剂和调剖剂、表面活性剂驱油的牺牲剂、污水处理的絮凝剂等。在石油工业中充分利用碱法制浆黑液和碱木素,对解决黑液污染问题,降低油田化学剂成本,具有重要意义。     

Recovery and characterization of lignin from alkaline straw pulping black liquor: As feedstock for bio‐oil research

Conversion of lignin derived from lignocellulosic biomass to bio‐oil has the promising potential to significantly reduce petroleum dependence. For that purpose, it is necessary to search for a low‐cost lignin source. In this study, lignin sample was separated from straw pulping black liquor by HCl‐precipitation, followed by extraction with a mixture of dioxane and water. The content of lignin in the total black liquor solid reached up to 34.8%, determined by UV spectroscopy, and the yield could account for 74.4% of the total lignin composition. The structure of lignin was investigated by various spectroscopic techniques such as FTIR, ¹H‐NMR, XRD, and XPS. The structural analysis revealed that recovered lignin preserved basic lignin structure, but had relatively lower amount of β‐O‐4 linkages. The molecular weights were studied through THF‐eluted GPC showing that separated lignin had the low M_n, which was favorable for the full degradation process during conversion of lignin to bio‐oil. Therefore, a feasible solution for effective utilization of lignin in straw pulping black liquor as feedstock for bio‐oil was proposed in the study. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42057.     

竹子木素在GIF仿酶漂白中的降解机理

研究了竹子木素在GIF仿酶漂白中的降解机理,结果表明,GIF仿酶处理后,竹子木素酚羟基、醇羟基和对羟苯基增加,甲氧基、羰基、愈创木基和紫丁香基减少,β-O-4、β-1、β-5联接发生断裂,芳环开裂。此外,GIF仿酶处理后,竹子木素分子量下降,多分散性提高。     

Selective Degradation of Lignin Polymer by Chlorine Dioxide During Chemical Pulp Delignification in Flow Through Reactor

The delignification of pulp in a conventional batch reactor provides convenient conditions for inutile secondary reactions in which ClO₂ reacts with oxidized aromatic units of lignin. In this study the flow-through reactor was applied to minimize secondary reactions. The obtained results showed that the removal of oxidized lignin from the reaction zone significantly enhanced the ClO₂ reaction toward non-oxidized units of lignin. Application of an organic solvent-water solution, bleaching liquor, significantly increased the removal of oxidized lignin and decreased considerably the secondary reactions. Although this technique considerably improved ClO₂ effective efficiency, large amounts of chlorate formation decreased the overall effect of improved ClO₂ global efficiency.     

Treatment of wood pulp with nitrogen dioxide before oxygen bleaching

Summary Pretreatment of kraft pulp with nitrogen dioxide and oxygen before conventional oxygen bleaching with magnesium sulfate as protector leads to markedly decreased lignin contents after a given duration of the oxygen bleaching. An increased temperature during the pretreatment favours the delignification. The most striking effect of the pretreatment is that it leads to a suppressed rate of depolymerization of the cellulose during the oxygen bleaching.     

Lyocell纤维的漂白工艺

建立了一种应用于Lyocell纤维的新型漂白工艺 分析了漂白液中的过氧化氢质量分数、漂白时间、pH值、漂白温度、稳定剂质量分数对Lyocell纤维的白度和干断裂强度的影响.在确定的漂白工艺四步骤中第一步为预漂白,加入了稳定剂DELINOL9258,增加了漂白效果.漂白步骤最佳优化条件是：过氧化氢质量分数0.8％,漂白时间50 min,漂白液pH值11,漂白温度80℃,稳定剂LAVATEX9188质量分数0.3％     

Formation of Hydroxyl Radicals from Hydrogen Peroxide and their Effect on Bleaching of Mechanical Pulps

The formation of hydroxyl radicals from hydrogen peroxide in alkaline solutions and under the conditions of hydrogen peroxide bleaching of pulps was investigated. The results lend support to the generally accepted view that the decomposition of alkaline hydrogen peroxide is catalyzed by redox processes involving transition metal ion species. The formation of hydroxyl radicals by one-electron reduction of hydrogen peroxide in this process is believed to be catalyzed primarily by mononuclear transition metal ion complexes, polynuclear species being far less efficient in this respect. It was found that a certain formation of hydroxyl radicals during alkaline hydrogen peroxide bleaching of pulp may have a beneficial effect on the final brightness. This finding is ascribed to the cleavage of crosslinks in the rigid lignin matrix which facilitates penetration of the bleaching reagent(s). Silicate does not appreciably suppress the formation of hydroxyl radicals in alkaline hydrogen peroxide solution. The stabilizing effect of this additive is probably due to deactivation of finely dispersed colloidal particles of metal hydroxides and hydrated oxides which decompose hydrogen peroxide to give mainly molecular oxygen and water.     

Bis(o-phenanthroline)copper-catalysed oxidation of lignin model compounds for oxygen bleaching of pulp

The selectivity of the water-soluble and highly active catalyst bis(o-phenanthroline)Cu in the oxygen bleaching of pulp was explored in model compound studies. The experiments were carried out under reaction conditions typical for industrial oxygen bleaching (90 °C, pH 12, p(O₂) 8 bar). The generation of hydrogen peroxide was an essential step in the oxidation of the lignin model compounds, veratryl alcohol and 2,2′-biphenol. Unfortunately, bis(o-phenanthroline)Cu also catalysed the depolymerisation of the carbohydrate model compound, dextran, both with oxygen and with hydrogen peroxide. The results explain well the inadequate selectivity of bis(o-phenanthroline)Cu in the oxygen bleaching of pulp.     

聚木糖酶对纸浆中LCC的辅助去除作用

在造纸用植物原料中,木素与半纤维素之间存在着化学连接,形成木素与碳水化合物复合体（LCC）。在制浆过程中,当蒸煮进行到一定时间后,尤其是在蒸煮的后期,蒸煮液中药液的浓度下降,而聚木糖浓度较高,溶出的聚木糖有一部分又重新回吸到纤维上,而另一部分半纤维素与残余木素形成新的化学结合,形成LCC。聚木糖的回吸对纸浆中残余本素的进一步去除起到了屏蔽作用。聚木糖酶处理纸浆主要是当用内切聚木糖酶降解、溶出回吸到纸浆纤维上的聚木糖,提高了纤维表面的通透性,使漂白处理时漂白剂容易与残余木素作用,有利于残余木素的溶出。同时,由于聚木糖酶分解LCC中的部分聚木糖,使LCC的分子量降低,易于溶出,进而也促进了残余木素的去除,改善了纸浆的可漂性,降低了漂白剂用量和漂白废水中的AOX含量以及有害物质的排放量。但是,聚木糖酶处理需要与纸浆洗涤和化学漂白处理相结合,还不能完全替代纸浆的化学漂白处理。     

玉米秸秆木质素的超临界提取及结构表征

采用超临界CO2/乙醇-水三元体系反应提取玉米秸秆中的木质素,并采用沉淀法对提取液中的木质素进行回收,得到木质素产品.利用气相色谱-质谱联用、红外光谱、紫外光谱分析了提取液成分及提取木质素产品的结构特性.采用热重分析方法对提取木质素的热稳定性进行了研究.结果表明:本试验方法提取的玉米秸秆木质素具有木质素的典型结构.提取木质素主要在180 ～500℃温度范围内分解失重.原木质素在超临界提取反应过程中发生了相当程度的降解,醚键发生了较大程度的断裂,木质素-水化合物复合体发生了不完全降解,提取木质素中含有一定量的碳水化合物.     

Hydroxy Propylated Lignin-Isocyanate Combinations as Bonding Agents for Wood and Cellulosic Fibers

Lignin and hydroxy propylated lignin derivatives were reacted with diisocyanates in the presence of cellulose fibers and wood particles. The attachment of lignin and lignin derivates to hydroxyl-rich surfaces of lignocellulosic materials proved to be a convenient way for increasing strength properties of reconstituted fiber and particle materials. Results indicate that hydroxypropylated lignin derivatives are capable of contributing equal or even greater strength increases to relignified fiber composites than do monomeric or polymeric diisocyanates alone. With reinforced fiber mats, it was found that strength properties were virtually unaffected up to a level of approximately 50% replacement of diisocyanates by lignin-based materials. This beneficial contribution by lignin to bonding properties could not be verified for reconstituted wood products, the strength and swelling properties of which suffered in relation to lignin content. Thftse differences are explained with differences in method of adhesive preparation and application. Lignins were obtained from the spent pulping liquor of the Kraft process, and by alkaline extraction of steam exploded Aspen wood chips. These lignins were, for the most part, reacted with propylene oxide.     

Delignification of Pinus taeda wood chips treated with Ceriporiopsis subvermispora for preparing high‐yield kraft pulps

Pinus taeda wood chips were treated with the white‐rot fungus Ceriporiopsis subvermispora in 20‐dm³ bioreactors for periods varying from 15 to 90 days. Decayed samples, non‐inoculated controls and extractive‐free wood samples were submitted to kraft pulping using 25% of sulfidity and different active alkali concentrations in the cooking liquor. Cooking reactions were carried out isothermally at 170 °C. Residual lignin contents of pulps prepared from biotreated wood chips were lower than those observed in pulps from the undecayed control. Delignification kinetic studies showed that the initial delignification phase was accelerated and shortened by the fungal pretreatment. At a cooking time fixed before the end of the bulk delignification phase, the fungal pretreatment provided pulps with significantly lower kappa numbers or pulps with a fixed kappa number were obtained by reducing the amount of active alkali added to the liquor. Pulps of kappa 80 were obtained both from the undecayed control cooked with 20.8% of active alkali and from the 15‐day‐biotreated sample cooked with only 15% of active alkali. The biopulping benefits were neither proportional to the extent of the biodelignification nor to the biological removal of some specific wood component. DFRC‐determination (derivatization followed by reductive cleavage) of the amount of aryl–ether linkages in residual lignins of biotreated samples indicated an extensive depolymerization during the initial stages of biodegradation, which suggested that bio‐depolymerized lignin was easily released during the first stages of cooking, resulting in a faster and shorter initial delignification phase. © 2002 Society of Chemical Industry     

Removal of residual lignin of ethanol‐based organosolv pulp by an alkali extraction process

Organosolv pulps usually have high kappa number. This research investigated an alkaline extraction method prior to bleaching for reducing the kappa number of organosolv pulp. Ethanol wheat straw pulp with a kappa number of 58.2 was extracted with 1% NaOH solution. The results show that the ethanol pulp has a large amount of lignin particles on the fiber surface. After 1 min alkali extraction, the kappa number of the ethanol pulp is reduced by 60%, to 22.2, and both the number and the size of the lignin particles on the fiber surface are significantly reduced. In comparison with a further ethanol washing/extraction, the alkali extraction is much more effective in terms of lignin removal. X‐ray photoelectron spectroscopy results show that a thin layer of lignin remained on the fiber surface after alkli extraction, but this did not reduce the internal bond strength. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

蒸煮液的物理化学特征及在制浆过程中的行为 Ⅱ.木素对蒸煮液的表面张力的影响

通过加入木素自制黑液及取自一个连续等温蒸煮过程的黑液的数据比较,研究了木素对蒸煮液的表面张力的影响。结果显示,木素起着表面活性剂的作用使蒸煮液的表面张力降低。但木素对实际取得的黑液的表面张力的影响要大于人工自制的,其主要原因是前者还含有木材的其它成分,如半纤维素及脂肪酸。黑液表面张力的主要成分是Lifshitz-van der Waals引力 γLLW,其次是Lewis酸碱反应力γLAB。