酶解木质素/植物纤维复合材料制备工艺研究
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摘要
本课题来源于国家自然科学基金“冷等离子体自由基引发与诱导接枝协同强化酶解木质素胶合力的机理”(编号：31070504)。
目前能源危机和环境污染已经成为影响人类可持续发展的重大障碍,随着纤维素燃料乙醇工业的发展,酶解木质素必将成为一类丰富的可再生资源。酶解木质素的增值利用可显著地降低纤维素燃料乙醇的生产成本,有效提升纤维素燃料乙醇工业的经济活力。
本文利用酶解木质素制备不添加合成树脂胶和任何化学助剂的植物纤维复合材料。研究了酶解木质素/植物纤维复合材料的制备工艺,并针对木质素分子大,芳环上的取代基较多,位阻大,反应活性不足的问题,提出采用氧冷等离子体处理活化酶解木质素,分析了氧冷等离子体处理对酶解木质素/植物纤维复合材料物理力学性能的影响。
研究结果表明：
1、酶解木质素的添加量、热压温度、纤维含水率、热压时间对酶解木质素/植物纤维复合材料的物理力学性能都有影响。在本文试验范围内,较优的工艺参数为：酶解木质素的添加量10%、热压温度210℃、纤维含水率20%、热压时间90s/mm。
2、利用响应面优化法研究了氧冷等离子体酶解木质素/植物纤维复合材料的制备工艺。在本文试验范围内,较优的工艺参数为：热压温度210℃、纤维含水率20%、热压时间90s/mm。
3、酶解木质素经氧冷等离子体改性后,能显著提高酶解木质素／植物纤维复合材料的物理力学性能,其中板材内结合强度提高21.8%,吸水厚度膨胀率减小了41.3%,静曲强度提高8.1%。
4、酶解木质素经氧冷等离子体改性后,表面含氧官能团显著增加,其中-OH增加20%、-C=O增加5%,-O-C=07%。同时,酶解木质素表面自由基浓度也有所增加。含氧官能团和自由基浓度的提高有利于植物纤维间结合强度的提高。
Nowadays, energy crisis and environmental pollution have become a significant barrier to human sustainable development. As cellulose ethanol industry is developing, enzymatic hydrolysis lignin (EHL) will become one of the renewable resources. Due to the molecular of the lignin is large and there are plenty of substituent groups of benzene ring, industrialized utilization of EHL has been limited. This paper discusses the properties of EHL that was obtained from the lignocellulosic ethanol production processes. It also describes the preparation technology and physical and mechanical properties of the bio-composite product.
This thesis used EHL to manufacture plant fiber composite material without any synthetic resin and chemical auxiliaries and researched the manufacture technology of EHL/plant fiber composite material. And aiming at the problem of large lignin molecule and large number of substituent group, great steric hindrance and lack of activity of aromatic ring, we proposed the using of oxygen cold plasma to treat the active EHL, analyzed the influence of oxygen cold plasma treatment on the physical and mechanical property of EHL/composite material.
The results of the research are showed as follows:
1.The additives of EHL, hot-pressing temperature, moisture content of fiber and hot-pressing time can influence the physical and mechanical property of EHL/composite material. In this experiment scale, the better technology parameters are:10% additive amount of EHL,210℃hot-pressing temperature,20% moisture content of fiber and 90s/mm hot-pressing time.
2.Response Surface Methodology(RSM)is used to research the manufacture technology of oxygen plasma EHL/composite material. In this experiment scale, the better technology parameters are:210℃hot-pressing temperature,20% moisture content of fiber and 90s/mm hot-pressing time.
3.The oxygen plasma modified EHL can obviously increase the physical and mechanical property of EHL/composite material,21.8% increase of IB,41.3% decrease of TS,8.1% increase of MOR.
4.The oxygen cold plasma modified EHL can obviously increase the oxygen containing functional groups on the surface, with 20%,5%,7% increase of -OH,-C=O,-O-C=O respectively. Meanwhile, the surface free radicals density of EHL was increased to a certain degree. The increase of oxygen containing functional groups and free radicals density can improve the bond strength of plant fiber.
目前能源危机和环境污染已经成为影响人类可持续发展的重大障碍,随着纤维素燃料乙醇工业的发展,酶解木质素必将成为一类丰富的可再生资源。酶解木质素的增值利用可显著地降低纤维素燃料乙醇的生产成本,有效提升纤维素燃料乙醇工业的经济活力。
本文利用酶解木质素制备不添加合成树脂胶和任何化学助剂的植物纤维复合材料。研究了酶解木质素/植物纤维复合材料的制备工艺,并针对木质素分子大,芳环上的取代基较多,位阻大,反应活性不足的问题,提出采用氧冷等离子体处理活化酶解木质素,分析了氧冷等离子体处理对酶解木质素/植物纤维复合材料物理力学性能的影响。
研究结果表明：
1、酶解木质素的添加量、热压温度、纤维含水率、热压时间对酶解木质素/植物纤维复合材料的物理力学性能都有影响。在本文试验范围内,较优的工艺参数为：酶解木质素的添加量10%、热压温度210℃、纤维含水率20%、热压时间90s/mm。
2、利用响应面优化法研究了氧冷等离子体酶解木质素/植物纤维复合材料的制备工艺。在本文试验范围内,较优的工艺参数为：热压温度210℃、纤维含水率20%、热压时间90s/mm。
3、酶解木质素经氧冷等离子体改性后,能显著提高酶解木质素／植物纤维复合材料的物理力学性能,其中板材内结合强度提高21.8%,吸水厚度膨胀率减小了41.3%,静曲强度提高8.1%。
4、酶解木质素经氧冷等离子体改性后,表面含氧官能团显著增加,其中-OH增加20%、-C=O增加5%,-O-C=07%。同时,酶解木质素表面自由基浓度也有所增加。含氧官能团和自由基浓度的提高有利于植物纤维间结合强度的提高。
Nowadays, energy crisis and environmental pollution have become a significant barrier to human sustainable development. As cellulose ethanol industry is developing, enzymatic hydrolysis lignin (EHL) will become one of the renewable resources. Due to the molecular of the lignin is large and there are plenty of substituent groups of benzene ring, industrialized utilization of EHL has been limited. This paper discusses the properties of EHL that was obtained from the lignocellulosic ethanol production processes. It also describes the preparation technology and physical and mechanical properties of the bio-composite product.
This thesis used EHL to manufacture plant fiber composite material without any synthetic resin and chemical auxiliaries and researched the manufacture technology of EHL/plant fiber composite material. And aiming at the problem of large lignin molecule and large number of substituent group, great steric hindrance and lack of activity of aromatic ring, we proposed the using of oxygen cold plasma to treat the active EHL, analyzed the influence of oxygen cold plasma treatment on the physical and mechanical property of EHL/composite material.
The results of the research are showed as follows:
1.The additives of EHL, hot-pressing temperature, moisture content of fiber and hot-pressing time can influence the physical and mechanical property of EHL/composite material. In this experiment scale, the better technology parameters are:10% additive amount of EHL,210℃hot-pressing temperature,20% moisture content of fiber and 90s/mm hot-pressing time.
2.Response Surface Methodology(RSM)is used to research the manufacture technology of oxygen plasma EHL/composite material. In this experiment scale, the better technology parameters are:210℃hot-pressing temperature,20% moisture content of fiber and 90s/mm hot-pressing time.
3.The oxygen plasma modified EHL can obviously increase the physical and mechanical property of EHL/composite material,21.8% increase of IB,41.3% decrease of TS,8.1% increase of MOR.
4.The oxygen cold plasma modified EHL can obviously increase the oxygen containing functional groups on the surface, with 20%,5%,7% increase of -OH,-C=O,-O-C=O respectively. Meanwhile, the surface free radicals density of EHL was increased to a certain degree. The increase of oxygen containing functional groups and free radicals density can improve the bond strength of plant fiber.
引文
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