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。     

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。     

Structural Changes in Lignin During Kraft Cooking Part 3. On the Structure of Dissolved Lignins

Two series of pine kraft lignins were prepared by a) normal kraft cooks to different pulp yield levels and precipitation of the lignins from the black liquors by acidification and b) by successive acidification of the black liquor obtained from a flow-through cook. All the lignins were extensively purified, subjected to elemental and methoxyl analysis and subsequently acetylated.

Quantitative ¹³C-NMR analysis was carried out on acetylated samples and the results were combined with the results of phenolic group determination by means of aminolysis and with elemental analysis data. The various acetylated lignins were also subjected to analysis by size exclusion chromatography.

All results are discussed with reference to known features of kraft cooking and of kraft lignins.     

Molar mass-dependent profiles of functional groups and carbohydrates in kraft lignin

Technical lignins are complex, irregular, polyphenolic compounds obtained in large quantities as by-products of the pulp and paper industries or according to current biorefinery setups. The availability of kraft lignin is increasing due to larger scale retrieval from process liquors, which opens new possibilities for further refining or new applications of such lignins. In the present study, sequential ultrafiltration of kraft lignin was performed to fractionate the lignin and to elucidate molar mass-dependent changes in lignin structure. Two industrial black liquors and three precipitated lignins were fractionated, and their functional groups were determined, providing molar mass-dependent profiles. Interrelations between structural parameters and functional groups, the molecular weight ranges, and the different lignin sources are discussed. This will help to establish structure-property-application relationships (SPARs) for technical lignins which are required for any future large-scale application.     

Structural Characterization of Pine Kraft Lignin: BioChoice Lignin vs Indulin AT

BioChoice lignin (BCL) is a newly commercialized pine kraft lignin from Plymouth Mill of Domtar, which is precipitated from black liquor of bleachable-grade pulp. Indulin AT is a pine kraft lignin commercialized by Meadwestvaco for the past 60 years, which is precipitated from black liquor of linerboard-grade pulp. Thus, the two technical lignins are produced under quite different conditions in terms of alkali charge and pulping time/temperature. While the chemical structure of Indulin AT is well documented, that of BCL is totally unknown. In this study, chemical structures of BCL and Indulin AT are characterized using modern analytical techniques and compared with those of pine milled wood lignin (MWL) in order to elucidate the structural changes that occur during kraft pulping and the structural differences, if any, between BCL and Indulin AT. Both BCL and Indulin AT are structurally very different from the native lignin (MWL) in wood, indicating drastic structural modification during the kraft pulping process. Surprisingly, BCL and Indulin AT are structurally very similar, in spite of the fact that they are produced under different process conditions. However, there are subtle structural differences between BCL and Indulin AT. BCL has higher phenolic hydroxyl, catechol, enol ether, and stilbene contents, but lower methoxyl and β-O-4 contents. These differences are explained by the different pulping conditions under which the two technical lignins are produced.     

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     

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.     

麦草碱木质素的过氧化氢氧化氨解 Ⅱ.氧化氨解对木质素主要官能团的影响

研究了麦草碱木质素的过氧化氢氧化氨解对主要官能团的影响。结果表明过氧化氢用量、反应温度和时间对氧化氨解木质素的甲氧基、酚羟基和羧基含量均有明显的影响 ,在反应中甲氧基和酚羟基含量下降 ,而羧基含量呈上升趋势。木质素的甲氧基、羧基含量与总氮、有效氮含量均呈较好的线性关系。     

木质素分级对其应用性能的影响

木质素是一种结构复杂的天然芳香类聚合物,功能基团丰富,具有良好的开发应用前景。工业碱木质素是当前木质素转化利用的主体,主要源于制浆黑液。由于原料来源、制浆工艺的影响,木质素多分散性高、结构与性能不一,致使相应的木质素基产品的均一性与稳定性较差。通过木质素分级可以获得具有不同分子量或特定化学结构特征的木质素级分,促使各级分的多分散性降低、均一性提高,进而针对特定性能的级分进行改性或者直接利用可进一步提高产品的稳定性。对现行木质素的主要分级方式进行了总结,重点探讨了工业碱木质素的分级方式对其后续利用的影响及存在问题。最后,针对木质素不同级分的特点对木质素未来分级的方向及应用前景提出了展望。     

硫化钠预处理制浆残余木质素的化学结构特性

用化学和波谱分析研究了硫化钠预处理硫酸盐制浆中残余木质素的化学结构特性。结果表明 ,硫化钠处理能促进硫与木片中木质素的结合 ,而甲氧基的含量有所下降。与对照硫酸盐制浆相比 ,预处理条件下木质素的缩合程度较低 ,经过蒸煮后残余木质素的缩合程度有较大的提高。     

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.     

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。     

Lignin and Other Aromatic Substances Released from Spruce Wood During Pressurized Hot-Water Extraction,Part 2: Structural Characterization

Extraction of ground spruce sapwood with pressurized hot water in an accelerated solvent extractor (ASE) at 170°C during 20, 60, and 100 min resulted in isolation of galactoglucomannans and aromatic substances, including lignin. The isolated lignin preparations were characterized by spectrometric (UV, FT-IR, ¹H NMR, liquid and solid-state ¹³C NMR), chromatographic (RP-HPLC, HP-SEC, GC-FID, and GC-MS), conventional pyrolysis, thermally assisted hydrolysis, and methylation techniques in tandem with GC-MS, and classical wet chemistry (methoxyl groups, total and phenolic hydroxyl groups, derivatization followed by reductive cleavage—DFRC). The content of β-O-4 bonds in isolated lignins was similar to that in MWL and their proportion decreased with extraction time. The oxidation of isolated lignins and content of total hydroxyl groups were significantly increased with extraction time. The lignin structure underwent condensation and demethylation reactions during hot-water extraction. The induction of new phenylcoumaran substructures was proposed in isolated lignins.     

裂解-气质联用分析氧漂过程中木素结构的变化

从针叶木硫酸盐原浆、氧漂浆以及氧漂后的废液中分离出残余木素,在四甲基氢氧化铵（TMAH）存在下,采用裂解气相色谱-质谱联用(Py-GC-MS)的方法研究了氧漂过程中木素分子结构的变化.对裂解产物的分析表明,木素裂解时产生多种甲基化的芳香化合物,以愈创木基型化合物为主;氧漂能够氧化和降解木素分子,产生更多的羧基化合物,氧化程度高的木素分子容易从纸浆中溶出,氧漂优先脱除沉积在纤维表面上的短侧链木素.     

BEHAVIOR OF EUCALYPTUS GLOBULUS LIGNIN DURING KRAFT PULPING. I. ANALYSIS BY CHEMICAL DEGRADATION METHODS

ABSTRACT

Eucalyptus globulus wood was subjected to kraft pulping, reaching different extents of delignification. The residual and dissolved lignins were isolated by soft acidolysis and acidic precipitation, respectively, and submitted to analysis of residual sugars and methoxyl groups, as well as to analysis by nitrobenzene and permanganate oxidation and thioacidolysis. Results from both residual and dissolved lignins analyses indicated that in the initial phase of pulping there is a preferential removal of lignin enriched in guaiacylpropane (G) and p-hydroxyphenylpropane (H) units, which is highly condensed and bonded with polysaccharides, predominantly with xylan. During the bulk and residual phases of pulping, lignin enriched in syringylpropane (S) units is progressively removed, leading to the increase of S/G ratio of black liquor lignin. After a purification step of dissolved lignins, two fractions with distinct levels of carbohydrates and with different structural features were obtained. The overall results were interpreted in terms of the topochemistry of the kraft pulping process.     

Hydroxymethylation of technical lignins from South American sources with potential use in phenolic resins

This work investigates the valorization of sodium lignosulfonate, kraft, and organosolv lignins from South America. A detailed characterization of the lignins and their chemical modification by hydroxymethylation through its reaction with formaldehyde were performed. The characterization included measurements of moisture, ash, carbohydrate contents, elemental and thermogravimetric analysis, and functional groups, molar mass distributions by Fourier transform infrared spectroscopy, and size exclusion chromatography, respectively. Also, reactive aromatic hydrogens ( H_Ar) were quantified by the measurement of phenolic hydroxyl groups (P-OH) content by UV–Vis spectroscopy. The different initial formaldehyde/lignin weight ratios (0.07, 1.47), temperatures (40, 50, and 70 °C), and pHs (9, 11); and the following of hydroxymethylation reactions by UV–Vis spectroscopy were investigated. All lignins resulted attractive for the use as replacement of phenol in phenolic resins, but sodium lignosulfonate was the most appropriate due to its water solubility. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47712.     

Investigation of the Chemistry of Oxygen Delignification of Low Kappa Softwood Kraft Pulp using an Organic/Inorganic Chemical Selectivity System

Abstract

Oxygen delignification (OD) of low kappa softwood kraft pulp was examined in two steps without inter‐stage washing as part of an overall program to evaluate the efficiency of a selectivity enhancement system consisting of phenol and magnesium sulfate. Black liquor carryover in the reaction system did not substantially affect delignification and the selectivity of these OD reactions. The residual lignins from both the original pulp and oxygen‐delignified pulp with and without the phenol/MgSO₄ selectivity enhancement system were prepared and characterized using NMR spectroscopy. The effluent lignins after oxygen delignification were also prepared and characterized. The lignin characterizations provided the basis for the rationalization of the selectivity observed. A significant finding of this study was that the phenol/MgSO₄ system in the oxygen delignification reaction appeared to hinder phenolic guaiacyl unit condensation. It also appeared to enrich the levels of p‐hydroxyphenyls in the residual lignin.     

Quantitative Phosphorus-31 NMR Analysis of Six Soluble Lignins

By using a set of lignin samples, which have been subjected to thorough analyses by the international wood chemistry community, the recently developed quantitative method of ³¹P NMR spectroscopy was comprehensively examined. The values of total phenolic hydroxyl groups and those of total hydroxyl groups were found to favourably compare with those obtained by other laboratories, applying independent methods of analysis. Furthermore, the application of quantitative ³¹P NMR spectroscopy offered additional detailed structural information for the examined lignins which was in accord with literature accounts for similar wood species and lignin preparations. More specifically, the steam explosion lignins from aspen and yellow poplar woods and that produced by ball milling/enzyme hydrolysis of cottonwood were found to contain relatively high amounts of β-O-4 structures. In contrast, the kraft, organosolv, and the acid hydrolysis processes were found to induce significant chain scission on the resulting lignins. Ball milled cottonwood lignin contained the highest frequency of β-O-4 bonds and the lowest amount of free phenolic hydroxyls. The erythro form of β-O-4 structures were invariably predominant in the lignins from aspen, yellow poplar and cottonwood, in accord with the conclusions of previous reports on hardwood lignins. Thus, the application of quantitative ³¹P NMR spectroscopy offered the detailed chemical composition of the examined lignins.     

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.     

Chemical Groups and Structural Characterization of Lignin via Thiol-Mediated Demethylation

A new approach to increase the reactivity of lignin by thiol-mediated demethylation was investigated in this study. Demethylated lignin was characterized by the changes in its hydroxyl and methoxyl groups, molecular weight, and other properties using titration and spectroscopy methods including FT-IR, ¹H NMR, UV, and GPC. The total, phenolic, and aliphatic hydroxyl contents in lignin increased while the methoxyl content decreased after demethylation reaction, which indicated the occurrence of demethylation reaction. The results from FT-IR and UV analysis also indicated that the kraft lignin in this study contains mainly guaiacyl moiety and demethylated lignin has a higher guaiacyl content than original lignin. The average molecular weight of lignin decreased after demethylation reaction due to the cleavage of ether linkages in lignin macromolecules. No severe degradation of lignin was observed during the demethylation reaction.