芦苇硫酸盐浆残余木素特性的研究

从元素组成、功能基含量、结构单元三种基的比例和分子量及其分布等方面研究了苇浆残余木素的性质 ,并与芦苇木素进行了比较。研究发现 ,苇浆残余木素比起芦苇木素具有较高的氢含量和较低的氧含量 ;较低的甲氧基含量和较高的酚羟基和醇羟基含量 ;明显低的总醛含量、平均分子量及更高的多分散性。     

Chemical Structure of Residual Lignin from Kraft Pulp

Structural characteristics of wood lignin and residual lignin in conventional and modified kraft pulps were examined employing elemental and methoxyl analysis and ¹³C, ¹H, and ³¹P-NMR. The structural analysis revealed that kraft residual lignin differs significantly from wood lignin while differences between residual lignins in conventional and EMCC® pulps have similar structural characteristics at kappa numbers corresponding to the point where the selectivity of the cook becomes poor. NMR analysis suggested that residual lignin, compared to the wood lignin, is much less reactive towards pulping chemicals due to the low content of aryl ether linkages and the prevalence of condensed type structures.     

生物漂白过程木素结构的红外光谱分析

利用富里埃变换红外光谱技术分析了尾叶桉硫酸盐浆原浆的残余木素、经生物处理后浆的残余木素及生物处理后纸浆经氢氧化钠抽出的木素。结果证实 ,在漆酶 助剂生物处理纸浆的过程碳水化合物不发生氧化 ,而木素的Cα羟基发生氧化产生α -羰基 ;酶作用后纸浆进一步碱处理导致木素溶出。从溶出木素的结构分析 ,推断纸浆中具有紫丁香基结构的残余木素优先发生降解     

针叶木硫酸盐浆中残留木素的GIF体系仿酶降解机理的研究

由于针叶木硫酸盐浆中的残留木素含有大量难降解的LCC结构及其它缩合型木素结构,所以硫酸盐浆的分离木素可以用作难降解型木素大分子的一种结构模型。文章采用Cu2+/吡啶/过氧化氢组成的GIF仿酶体系对马尾松硫酸盐未漂浆的纤维素酶酶解木素(CEL)进行了仿酶降解,并对降解产物进行了分离和化学组成分析。通过FT-IR以及GC-MS测定,解析了CEL在降解过程中的结构变化,并对CEL的仿酶降解机理进行了探讨。研究结果表明:这种仿酶降解方法对浆中残留木素有较强的降解能力,一部分木素大分子被氧化降解为香草醛和香草酸等低分子化合物,使得降解后的产物中羰基和羟基增多。研究发现木素在仿酶体系中存在苯环及其侧链上C-H键的破坏、木素结构中Ca-Cb连接键的断裂、苯环的开环等反应。因此,该项研究可以为开发纸浆的仿酶漂白技术提供理论依据。     

Characterization of the Residual Kraft Pulp Lignin In Situ by Sulfite Treatments

Abstract

The O₂ delignification of kraft pulps from Norway spruce was shown having a significant impact on the reactivity of the residual pulp lignin as revealed from their responses to sulfite treatments at pH 7.5. A substantial higher ratio of lignin sulfonation to the phenolic hydroxyl group content of residual pulp lignin was observed for the O₂ -delignified kraft pulps (～ 0.8) as compared to a value of ～ 0.3 for the unbleached samples and ～ 1 for the spruce wood lignin. Under the prevailing sulfite treatment conditions, the sulfonation would be largely attributed to the phenolic lignin component and the etherified structures containing an α -carbonyl or -unsaturated group. The contribution from the latter units, evaluated by a borohydride pretreatment of pulps prior to the sulfite treatment, can only account for approximately 15% of the sulfonation observed for the O₂ -delignified sample. Thus, the nature of phenolic structures in the O₂ -delignified pulps was more similar to that of the wood lignin than that of the kraft pulps.     

漆酶与助剂氧化体系降解苇浆残余木素的研究

用溶剂抽提法制取了苇浆残余木素 ,用漆酶 /助剂和氧气与其反应 ,通过甲氧基的测定、元素分析、1 3C -NMR、1 H -NMR和IR分析研究苇浆残余木素与漆酶 /助剂反应前后结构的变化。研究发现苇浆残余木素在反应后其甲氧基、酚羟基减少 ,醇羟基增多 ,木素结构中羰基增多 ,木素的苯环结构发生了开环反应     

硫酸盐苇浆残余木素生物降解前后结构特征的对比研究

从元素组成 ,功能基含量 ,结构单元三种基团的比例和分子量及其分布等方面研究了生物降解纤维素酶苇浆残余木素的性质。发现生物降解后的苇浆残余木素具有较高的氧含量 ,较低的甲氧基含量、酚羟基含量和较高的醇羟基含量 ,略低的经碱性硝基苯氧化后得到的总醛含量及对羟苯基单元含量 ;另外 ,生物降解以后硫酸盐苇浆残余木素平均分子量有显著降低。     

Development of Phenolic Lignin During ClO2 Bleaching of Kraft Pulp

The development of the phenolic lignin content in kraft pulp during ClO₂ bleaching was quantitatively determined by the periodate oxidation method. The effect of hypochlorous acid, an intermediate formed during chlorine dioxide bleaching, was eliminated by addition of sulfamic acid, a scavenger of hypochlorous acid. It was found that the number of free phenolic lignin groups per 100 lignin monomer units decreased from about 29 for unbleached kraft lignin to about 6.5 after 1 minute of ClO₂ bleaching. It was also shown that the in-situ generated hypochlorous acid created phenolic hydroxyl groups during chlorine dioxide bleaching. Since it was found that delignification by chlorine dioxide itself was mostly restricted to free phenolic lignin, these findings were used to explain the effect on delignification of addition order of chlorine and chlorine dioxide during bleaching of kraft pulp.     

Dissolution of Lignin in Kraft Pulp by Oxygen Bleaching

Gel permeation chromatography of spent liquors from oxygen bleaching showed that cleavage of covalent linkages in the fiber was a prerequisite for the dissolution of the lignin. The reactions continued in the liquor phase. The cleavage was related to the oxidation of the lignin. With pulps pretreated with nitrogen dioxide an appreciable number of lignin linkages were cleaved also by the direct influence of the hydroxide ions on the nitrated lignin. In the alkaline medium the acidic sites in the fiber and in dissolved lignin fragments are ionized. Donnan-exclusion and an increased fiber swelling promote the transfer of the fragments into the liquor. Hydrophilic groups introduced into the lignin during oxygen bleaching promote the delignification.     

Dissolution of Lignin from Kraft Pulp after Treatment with Nitrogen Oxides

Laboratory experiments show that pretreatment with NO₂ including heating and ripening at 5% consistency and 90°C for 3 hours in the presence of NO₃- and H⁺ led to a dissolution of approximately 50–60% of the lignin in unbleached kraft pulp. Only 5–15% were dissolved when the treatment was terminated after heating to 90°C. An extensive fragmentation of the lignin during the ripening explains the extensive delignification in acid medium.

Fractionated dissolution of the remaining lignin by alkaline extraction gave fractions with small variation in N-contents (2.9–3.4%) and hydrophilicity. The last fraction exhibited the highest sorption of water vapor. The delignification was related to the decrease in molecular size during the pretreatment and during the subsequent alkaline treatments.     

酶解―弱酸解法提取麦草浆残余木素的研究

对非木材浆中残余木素的分离和提纯方法进行了研究。利用酶解―弱酸解两段法提取麦草浆残余木素,研究了酶用量对纤维长度、细小纤维含量、纤维形态、酶解率及木素提取率的影响。研究证明这种方法适用于麦草浆,并得出了最佳酶用量为3mL/g。对提取出的木素经衍生化后,通过磷谱核磁共振(31P-NMR)技术得出木素结构谱图,对木素结构中脂肪羟基、总酚羟基和羧基以及总酚羟基中各酚羟基等功能基团进行定量分析对比,对麦草浆残余木素结构有了更全面的了解。     

Reactions of Conventional Kraft and Superbatch Pulp Residual Lignins with Peroxyformic Acid

Abstract

The residual lignins KRL and SRL, isolated from a conventional kraft pulp and a SuperBatch pulp respectively, were reacted with peroxyformic acid (PFA). The reagent consumptions were determined and the products fractionated according to their solubility. Both lignins consumed a roughly equal amount of PFA, which was nearly 50% higher than that consumed by kraft lignin. The undissolved fractions of PFA-treated residual lignins (yield >80%) contained less aromatic units, phenolic hydroxyl and methoxyl groups, and considerably more carboxyl groups (including those of formate esters) than the untreated lignins. The extent of these modifications was approximately equal for KRL and SRL, which together with the similar PFA consumptions and product yields of KRL and SRL indicates that the two residual lignins showed no essential difference in reactivity toward PFA. The effect of fiber wall morphology on delignification efficiency during PFA delignification is suggested to be small because of the cleavage of lignin-carbohydrate linkages occurring under acid conditions. The part of KRL remaining insoluble after PFA-treatment had a 40% higher molar mass than KRL while in the case of SRL there was hardly any such difference in molar mass. The lignins solubilized during the PFA treatments represented the most highly degraded part of the lignins, having very low molar masses and being richer in carboxyl groups and lower in aromatic units, phenolic hydroxyl, and methoxyl groups than the undissolved lignins.     

The Influence of Sulfidity in Kraft Pulping on the Nature of Residual Lignin

The influence of sulfidity in kraft pulping of Norway spruce chips on the characteristics of residual lignin has been examined at two levels 25 and 40%. Comparing with the reference kraft cook at similar kappa number, the high sulfidity pulp lignin displayed a significantly lower phenolic hydroxyl group content, and a lower response to O₂ delignification, but it gave a slightly higher yield of nitrobenzene oxidation products, and was more responsive to a neutral sulfite treatment.     

Compatibility of Kraft Lignin,Organosolv Lignin and Lignosulfonate With PLA in 3D Printing

The compatibility of three different types of lignin, such as Kraft lignin, Organosolv lignin, and lignosulfonate, with PLA, in particular without the addition of any further reagents or compatibilizers, is investigated. The unmodified lignins were thoroughly characterized to establish their interaction potential in lignin-PLA composite formation. The obtained double-extruded binary systems containing 5, 10, and 15?wt % lignin in PLA were characterized in terms of chemical conversion (^31?P NMR), thermal behavior (TGA, DSC), and cellular morphology (SEM). Additionally, the flexural and impact properties as well as the melt volume rate (MVR) of the extruded materials, in the form of 3D-printed bars, were analyzed, and the effect of lignin addition to PLA studied. The results revealed poor mechanical properties for the Kraft lignin-PLA blends, but higher compatibility of Organosolv lignin-PLA blends. Lignosulfonate-PLA blends showed a promising behavior for 3D-printing. A special nucleation effect, potentially useful in foaming applications, was observed in this study.     

Changes of Molecular Characteristics of Residual Pulp Lignin in Two-Step Soda-Oxygen Pulping

In order to explain the behavior of soda pulp in the following next oxygen stage, the molecular characteristics of the residual lignins isolated from spruce and pine wood pulps cooked to yieldB between 71.8 and 49.8% in the soda pretreatment step were examined. The revealed differences in the cross-linking density and degree of condensation correlated with the effectiveness of lignin removal from soda pulps in the oxygen stage.     

Influence of Oxygen During Pretreatment of Kraft Pulp with NO2

Abstract

Large additions of O₂ during the pretreatment of modified or industrial kraft pulp with NO₂ under conditions which favored an autocatalytic generation of NO₂ from produced and added HNO₃ led to a decreased viscosity after a subsequent oxygen bleaching, If the comparison was made at high kappa numbers. The difference was less apparent when the oxygen bleaching was extended. The yield of pulp at a given kappa number was reduced by large O₂ additions. An Increased yield of nitric acid contributed to these effects.

Hydrogen cyanide and ammonia were produced during the pretreatment in reactions between lignin and generated nitrogen oxides. Addition of O₂ led to decreased yields of these products.     

The Potential of 13C Cp/Mas Nmr in the Study of Kraft Pulping Kinetics

Abstract

Solid state ¹³C CP/MAS nuclear magnetic resonance spectra were obtained for unbleached kraft pulps prepared from white spruce with yields ranging from 47.6 to 96.1%. The observed trends of the relative peak intensities were found to correspond to established facts on kraft kinetics. These results suggest that ¹³C CP/MAS NMR of wood and pulp could be used to study kinetics in situ.     

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.     

Dissolution of Ethylenediamine Pretreated Pulp with High Lignin Content in LiCl/DMSO without Milling

Abstract

Various hardwood and softwood chemical pulps, including those with relatively high lignin content (up to ca. 10.5%), were completely dissolved without milling in lithium chloride/dimethyl sulfoxide (LiCl/DMSO) after a pretreatment with ethylenediamine (EDA). Because milling of the sample is not required, degradation of the cell wall components caused by milling does not take place. After the EDA pretreatment, the crystallinity of the pulps remained as high as the original pulps, although the crystal structure changed. This is the first time that transparent solutions of underivatized pulps with high lignin content were obtained in a simple organic solvent system. Interestingly, even in the case of coarse wood meal (40–80 mesh) about 70% could be dissolved after repeating the dissolving procedure two times. The formation of a pulp–EDA or wood–EDA complex seems to be critical for the dissolution in LiCl/DMSO. The nuclear magnetic resonance (NMR) spectrum of the EDA treated pulp solution had good resolution even though the degree of polymerization (DP) of the cellulose in the pulp is very high.     

气相色谱法测定维生素D2中残留有机溶剂

建立了维生素D2中残留有机溶剂的气相色谱测定方法。使用DB-wax毛细管柱,FID检测器,能快速测定(20min)甲醇、乙醇、乙酸乙酯等有机溶剂残留量。乙醇检测限为0．3μg／mL(信噪比为2),精密度试验的RSD均小于3％(n=6),重现性试验的RSD均小于2％(n=5),回收率为99．86％100．6％。该方法可以作为维生素D2产品中有机溶剂残留量的限度检测方法。