造纸废水中木素的酶催化聚合的研究
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摘要
造纸废水是我国水体污染的主要污染源之一,已成为制约我国造纸工业发展和水污染治理的难题。本论文提出了酶催化体系中,利用木素前驱物聚合废水中的难降解木素及其衍生物的方法,先通过木素前驱物和木素模型物的反应分析该聚合反应的机理和处理脱木素效果,然后应用于处理废水中木素聚合絮凝的研究中,并取得了理想的处理效果。
本文首先合成了一种酚型的木素模型化合物(愈创木基丙三醇-β-愈创木基醚)。采用改良的方法成功地合成了得率和纯度比较好的愈创木基丙三醇-β-愈创木基醚化合物,用乙醇代替三氯甲烷和乙酸乙酯做反应溶剂,对关键的中间产物4-(α-溴代乙酰基)-愈创木酚的合成方法进行了改良,使其得率可以稳定的达到80%。利用红外光谱、核磁共振谱(1H-NMR)分析等手段对其化学结构进行了分析确认。
本论文采用木素化学领域最新技术之一—13C同位素示踪技术,结合13C-NMR技术来探讨产物结构及其形成机理。合成木素前驱物—松柏醇葡萄糖苷-[α-13C]、利用熔点测定、TLC分离、13C-NMR分析及FT-IR对产物进行定性分析,并发现在合成中间产物阿魏酸葡萄糖苷过程中,由于溶剂吡碇的碱性作用,使之与阿魏酸葡萄糖苷形成比较稳定的吡碇盐结构,并在一定程度上干扰产物鉴定和后续反应。本实验中采用酸性水洗涤干燥后,多次用乙醚对反应产物进行多次洗涤处理以除去游离的吡啶可以确保产物的纯度。
本文利用合成出来的愈创木基丙三醇-β-愈创木基醚作为木素模型化合物,在漆酶作用下用木素前驱物松柏醇葡萄糖苷(coniferin)对其进行酶催化聚合处理,然后利用核磁共振(13C-NMR)和红外光谱(FT-IR)凝胶渗透色谱(GPC)等分析手段对反应的产物进行了分析。研究发现:漆酶催化聚合产物有比较高的分子量,证明以β-O-4型结构为代表的木素片段能在漆酶的催化下与木素前驱物(coniferin)能继续进行脱氢聚合反应,生成的聚合物(dehydrogenation polymer;简称DHP)的主要结构有β-O-4结构、苯基香豆满结构和松脂酚结构、松柏醇结构等,还存在少量的香草醛及α位带有亚甲基结构的苯丙烷结构,因此木素前驱物松柏醇葡萄糖苷能与β-O-4型木素模型化合物发生聚合反应,从而可使废水中难降解木素小分子聚合成木素大分子,从而絮凝沉淀脱除。
研究发现:木素前驱物松柏醇-β-D-葡萄糖苷处理废水后,废水中木素的浓度大约下降了10倍,由原来的0.73g/L降到0.078g/L,色度大约降低了27.8倍,由废水的500降到处理后的18。本研究从机理上验证了木素前驱物处理造纸废水的可行性,并在实验中取得了一定的效果。
As one of the main pollution sources of water, pulping and papermaking effluent has become a serious problem in the development of papermaking industry. In this paper, a new method was developed. It was confirmed that coniferin could polymerize with lignin model compound. Coniferin could also used to treat wastewater of paper mill successfully.
In this research work,β-O-4 type lignin model compound (i.e. guaiacyglycerol-β-guaiacyl ether) was synthesized with a modified method. The synthesis method of an important intermediate,i.e. 4-(α-bromoactyl)-guaiacol was improved.β-O-4 type lignin model compound (i.e. guaiacyglycerol-β-guaiacyl ether) yield reached 80%. The combination of infrared spectra, 1H-NMR analysis was used to identify the chemical structure of the product and related precursors.
This paper adopted Stable isotope(13C) enrichment technique and combining with nuclear magnetic resonance (13C-) to discover the structure of lignin and its biosynthesis mechanism. First, we synthesized coniferins-[α-13C] which are lignin precursors: The structure was confirmed by its melting point, NMR analysis and FT-IR spectra. It was found that acetylated Glucoferulic acid as intermediate could react with pyridine solvent to form a relative stable salt because of alkaline characteristic of pyridine.
The lignin model compound of guaiacylglycerol-β-guaiacyl ether was treated with coniferin catalyzed by laccase. The reaction products were analyzed by 13C-NMR, FT-IR and GPC. The formation mechanism of the products structure was also explored. It was found number average molecular weight (Mn) was increased from 420 to 3200~8670 and the main structures wereβ-O-4, coniferyl alcohol etc. There were some minor substructures such as vanillin, phenylpropane units withα-methylene. It was proved that coniferin could polymerize with lignin model and become macromolecule products. As a result the lignin can be removed though precipitate and flocculation.
The results showed that both the concentration of lignin and chroma were reduced significant. The concentration of lignin decreased from 0.73g/L to 0.078g/L and the chroma from 500 to 18.
本文首先合成了一种酚型的木素模型化合物(愈创木基丙三醇-β-愈创木基醚)。采用改良的方法成功地合成了得率和纯度比较好的愈创木基丙三醇-β-愈创木基醚化合物,用乙醇代替三氯甲烷和乙酸乙酯做反应溶剂,对关键的中间产物4-(α-溴代乙酰基)-愈创木酚的合成方法进行了改良,使其得率可以稳定的达到80%。利用红外光谱、核磁共振谱(1H-NMR)分析等手段对其化学结构进行了分析确认。
本论文采用木素化学领域最新技术之一—13C同位素示踪技术,结合13C-NMR技术来探讨产物结构及其形成机理。合成木素前驱物—松柏醇葡萄糖苷-[α-13C]、利用熔点测定、TLC分离、13C-NMR分析及FT-IR对产物进行定性分析,并发现在合成中间产物阿魏酸葡萄糖苷过程中,由于溶剂吡碇的碱性作用,使之与阿魏酸葡萄糖苷形成比较稳定的吡碇盐结构,并在一定程度上干扰产物鉴定和后续反应。本实验中采用酸性水洗涤干燥后,多次用乙醚对反应产物进行多次洗涤处理以除去游离的吡啶可以确保产物的纯度。
本文利用合成出来的愈创木基丙三醇-β-愈创木基醚作为木素模型化合物,在漆酶作用下用木素前驱物松柏醇葡萄糖苷(coniferin)对其进行酶催化聚合处理,然后利用核磁共振(13C-NMR)和红外光谱(FT-IR)凝胶渗透色谱(GPC)等分析手段对反应的产物进行了分析。研究发现:漆酶催化聚合产物有比较高的分子量,证明以β-O-4型结构为代表的木素片段能在漆酶的催化下与木素前驱物(coniferin)能继续进行脱氢聚合反应,生成的聚合物(dehydrogenation polymer;简称DHP)的主要结构有β-O-4结构、苯基香豆满结构和松脂酚结构、松柏醇结构等,还存在少量的香草醛及α位带有亚甲基结构的苯丙烷结构,因此木素前驱物松柏醇葡萄糖苷能与β-O-4型木素模型化合物发生聚合反应,从而可使废水中难降解木素小分子聚合成木素大分子,从而絮凝沉淀脱除。
研究发现:木素前驱物松柏醇-β-D-葡萄糖苷处理废水后,废水中木素的浓度大约下降了10倍,由原来的0.73g/L降到0.078g/L,色度大约降低了27.8倍,由废水的500降到处理后的18。本研究从机理上验证了木素前驱物处理造纸废水的可行性,并在实验中取得了一定的效果。
As one of the main pollution sources of water, pulping and papermaking effluent has become a serious problem in the development of papermaking industry. In this paper, a new method was developed. It was confirmed that coniferin could polymerize with lignin model compound. Coniferin could also used to treat wastewater of paper mill successfully.
In this research work,β-O-4 type lignin model compound (i.e. guaiacyglycerol-β-guaiacyl ether) was synthesized with a modified method. The synthesis method of an important intermediate,i.e. 4-(α-bromoactyl)-guaiacol was improved.β-O-4 type lignin model compound (i.e. guaiacyglycerol-β-guaiacyl ether) yield reached 80%. The combination of infrared spectra, 1H-NMR analysis was used to identify the chemical structure of the product and related precursors.
This paper adopted Stable isotope(13C) enrichment technique and combining with nuclear magnetic resonance (13C-) to discover the structure of lignin and its biosynthesis mechanism. First, we synthesized coniferins-[α-13C] which are lignin precursors: The structure was confirmed by its melting point, NMR analysis and FT-IR spectra. It was found that acetylated Glucoferulic acid as intermediate could react with pyridine solvent to form a relative stable salt because of alkaline characteristic of pyridine.
The lignin model compound of guaiacylglycerol-β-guaiacyl ether was treated with coniferin catalyzed by laccase. The reaction products were analyzed by 13C-NMR, FT-IR and GPC. The formation mechanism of the products structure was also explored. It was found number average molecular weight (Mn) was increased from 420 to 3200~8670 and the main structures wereβ-O-4, coniferyl alcohol etc. There were some minor substructures such as vanillin, phenylpropane units withα-methylene. It was proved that coniferin could polymerize with lignin model and become macromolecule products. As a result the lignin can be removed though precipitate and flocculation.
The results showed that both the concentration of lignin and chroma were reduced significant. The concentration of lignin decreased from 0.73g/L to 0.078g/L and the chroma from 500 to 18.
引文
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