【作者】 崔红艳；

【导师】 杨桂花； 刘玉；

【作者基本信息】 山东轻工业学院 ， 制浆造纸工程， 2011， 硕士

【摘要】 目前随着能源短缺和环境污染等问题日益严重,生物技术应用到制浆造纸中的研究成为一大热点。本论文研究的主要内容是利用漆酶和过氧化氢对纸浆进行处理,从而达到减轻环境污染、节约自然资源、改善纸浆性能和扩大纸浆应用范围的目的。论文采用纤维质量分析仪（FQA）、环境扫描电镜（ESEM）等测试方法对漆酶改性处理后及漂白后的纸浆纤维表面性能进行分析。分析结果表明,纤维的卷曲指数、扭结指数均有增加,说明漆酶改性处理和漂白对纸浆纤维有较大的作用。分析研究了打浆、磨浆等操作对木素含量的影响。与对照纸浆相比,漂白后纸浆和磨浆、打浆后纸浆经过漆酶或漆酶介体体系改性处理后,酸不溶木素的含量均有下降,说明漆酶或漆酶介体体系对纸浆中的酸不溶木素含量的变化有一定影响。以速生杨APMP浆为研究对象,研究探讨了漆酶介体体系改性处理和过氧化氢漂白的主要影响因素,并对漆酶介体体系处理条件和漂白工艺条件进行了优化。漆酶介体体系最佳处理条件为:在通氧条件下,漆酶用量2u/g,介体用量（HBT） 0.5%,pH值5.0,浆浓4.0%,温度50℃,反应时间60min。漆酶介体体系处理以后H₂O₂漂白最优工艺条件为:NaOH 4%（质量分数,下同）,H₂O₂ 5%,Na₂SiO₃ 5%,MgSO4 0.1%,EDTA（乙二胺四乙酸）0.5%,浆浓10%,温度70℃,时间1.5h。此条件下,APMP浆白度可达到72.2% ISO,抗张指数由对照浆的8.30 N·m·g^-1增加到了32.80 N·m·g^-1,提高了2.95倍;撕裂指数由对照浆的1.48 mN·m²·g^-1增加到了3.61 mN·m²·g^-1,提高了1.44倍。与对照浆相比,经过漆酶介体处理和漂白APMP浆的物理强度性能有了明显改善。采用酶解-弱酸解两段法分离出漆酶改性未漂和漂白纸浆中的木素以后,采用FTIR、¹³C-NMR、³¹P-NMR测试技术,对木素结构中脂肪族羟基、总酚羟基、羧基和总酚羟基中各酚羟基等功能基团进行定性、定量分析比较。分析结果显示,与未经过酶处理APMP纸浆相比,经过漆酶处理的纸浆的木素结构基团中脂肪族羟基的含量稍微有所增加,而羧基、总酚羟基二者的含量有所减少,缩合型酚羟基、紫丁香基型酚羟基、愈创木基和脱甲基酚羟基和对酚羟基的含量均有所减少。在经过漆酶-介体体系处理以后,木素中脂肪羟基含量有所减少,羧基含量也有一定程度的减少,而总酚羟基含量有非常显著的下降幅度;总酚羟基中缩合酚羟基、紫丁香基酚羟基、愈创木基和脱甲基酚羟基、对酚羟基的含量均有所下降。经过漆酶处理以后,APMP漂白纸浆中木素的脂肪羟基含量明显减少,总酚羟基含量减少,羧基含量有所增加,缩合酚羟基含量有所降低,紫丁香基酚羟基含量略有降低,愈创木基和脱甲基酚羟基的含量明显降低,而对酚羟基的含量有所增加。在经过漆酶-介体体系处理以后,木素中脂肪族羟基的含量明显降低,总酚羟基和羧基的含量有所降低,缩合酚羟基的含量明显降低,紫丁香基酚羟基、愈创木基和脱甲基酚羟基含量均有降低,而只有对酚羟基含量明显增加。更多还原

【Abstract】 At present, the shortage of energy and the pollution of environmental problems have become increasingly serious, the research of biotechnology will to be a hot spot. The main content of this research is to use laccase and hydrogen peroxide process with pulp, so as to reduce environmental pollution, conserve natural resources, improve pulp properties and expand the application range of pulp, etc.The fiber surface properties of pulp which were modified and processed by enzyme and bleaching were analyzed by FQA, ESEM and other testing methods. The analysis results show that the curl index, kink index of fiber have increased, indicating that the laccase modification and bleaching had a great influence on the pulp fibers.The beating, refining and other operations on the impact of lignin content were analyzed. Compared with the control pulp, bleached pulp after refining, pulp after beating the Klason Lignin content decreased after laccase or laccase mediator system modification, suggesting that the laccase or laccase mediator system had a certain extent influence on the Klason Lignin content in the pulp.The Alkalin Peroxide Mechanical Pulps （APMP） of fast-growing poplar were modified by Laccase-Mediator-System （LMS）, and then were bleached with hydrogen peroxide. The main impacting factors were investigated, optimizing its bleaching processes. The optimum conditions of laccase/mediator system process were: pulp consistency 4%, pH 5, at temperature 50℃for 60min and the optimum charge of laccase was 2U·g^-1 with 0.5% mediator （HBT）. It was found that the optimum bleaching conditions were: 4% NaOH, 5% H₂O₂, 5% Na₂SiO₃, 0.1% MgSO₄, 0.5% EDTA, 10% pulp consistency at 70℃for 1.5 hours. The effects on pulp physical properties were analysed by testing the hand-made sheets. During the modification with laccase/ mediator system process under the optimum conditions, the brightness of APMP reached 72.2% ISO, with an increase of 18.7% compared to the control pulp.The tensile index increased from 8.30 N·m·g^-1 to 32.80 N·m·g^-1, which increased 2.95 times. The tear index increased from 1.48 mN·m²·g^-1 to 3.61 mN·m²·g^-1, an increased of 1.44 times. These results showed that the strength properties of APMP treated with laccase/mediator followed by hydrogen peroxide bleaching increased significantly compared to control pulp.Lignin samples were isolated from the unbleached and bleached pulp before or after the modified with laccase through a two-stage method: enzymatic and mild acidic hydrolysis. Then the contents of Aliphatic OH, total Phenolic OH, COOH and different phenolic function groups in the lignin structures were analyzed and compared qualitatively and quantitatively using infrared spectroscopy FTIR, 13C-NMR, 31P-NMR techniques.The analysis results show that: during the Unbleached pulp of the APMP modified process with the laccase, the content of aliphatic OH （A-OH） increased, but the contents of the total phenolic OH （T-OH）、the COOH decreased. In the lignin the contents of the syringyl phenolic （S-OH）、the p-hydroxyl-phenyl OH （p-OH）、the condensed phenolic OH （C-OH）、the guaiacyl and dementhylated OH （G-OH） decreased. During the Unbleached pulp of the APMP modified process with Laccase-Mediator-System, the contents of the aliphatic OH （A-OH）、the total phenolic OH （T-OH）、the COOH decreased. In the lignin the contents of the syringyl phenolic （S-OH）、the p-hydroxyl-phenyl OH （p-OH）、the guaiacyl and the dementhylated OH （G-OH）、the condensed phenolic OH （C-OH） decreased.After APMP bleached pulp modified with the laccase, the contents of aliphatic OH （A-OH） and total phenolic OH （T-OH） decreased, while the contents of the COOH increased. In the lignin the contents of the guaiacyl and dementhylated OH （G-OH）、the syringyl phenolic （S-OH）、the condensed phenolic OH （C-OH） decreased, but the contents of the p-hydroxyl-phenyl OH （p-OH） increased. After APMP bleached pulp modified with LMS, the content of aliphatic OH （A-OH）、the COOH、the total phenolic OH （T-OH） decreased. In the lignin the contents of the guaiacyl and dementhylated OH （G-OH）、the syringyl phenolic （S-OH）、the condensed phenolic OH （C-OH） decreased, but the contents of p-hydroxyl-phenyl OH （p-OH） increased in the lignin.更多还原