壳聚糖、壳聚糖/氧化石墨有序多孔材料的制备及性能研究
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摘要
近年来,随着工业生产的发展,产生了大量的重金属离子以及染料废水。相应的,各种废水处理技术也应运而生。这其中,吸附分离技术有了很大的发展,展现出广阔的应用前景。因此,开发一种高效、廉价、无毒害的吸附材料,使它具有高比表面积、高吸附性能来应用于废水处理的是可行的。
壳聚糖由于其本身的特性,如具有絮凝作用,分子中含有大量的氨基、羟基具有很强的与金属离子的络合作用以及原料本身的来源丰富,天然无污染等,是一种理想的吸附材料。本文采用定向冷冻干燥法,制备壳聚糖多孔材料。采用IR、SEM等对多孔材料进行结构和形貌分析,同时通过加入造孔剂乙酸乙酯来增加多孔材料的孔隙率,最大限度的增加材料的比表面积,提高吸附效率。为提高壳聚糖多孔材料在水溶液中的力学性能,在壳聚糖中加入氧化石墨,研究了加入不同量的氧化石墨对壳聚糖多孔材料的影响,分析了这种复合材料相对于单纯壳聚糖支架材料的优越性。同时,在室温下,研究了壳聚糖有序多孔材料及其有序复合多孔材料对金属离子Cu(Ⅱ)和染料二甲酚橙(XO)的吸附性能,并重点研究了壳聚糖有序多孔材料的用量、溶液的pH值、吸附时间、壳聚糖的交联度二甲酚橙吸附率和吸附量的影响。
实验结果表明:加入乙酸乙酯造孔剂后制备的多孔材料孔隙率明显增加,氧化石墨的加入明显增强了多孔材料在水中的力学性能。壳聚糖有序多孔材料对二甲酚橙和Cu(Ⅱ)都具有良好的吸附性能。其中,温度、pH值是影响对二甲酚橙吸附的主要因素。整体而言,与壳聚糖多孔材料相比,CS/GO复合多孔材料具有较高的稳固性,在水溶液中能够保持原来的形状,有一定的韧性,使用寿命会较长。
Recently, large amount of heavy metal ions and organics was produced following with the development of the industrial production. Correspondingly, many kinds of wastewater treatment technology emerge. Among them, the adsorption separation technology gets a great development and displays a wide application prospect. So, developing an adsorption material with high efficiency, cheap and nontoxic for wastewater treatment is feasible.
Chitosan displays many special properties. For example, it has lots of amino and hydroxyl on the chitosan molecule which can complex with the metal ions or be used for flocculation. The chitosan is a abundant natural resource, and approved to be an ideal adsorption material. In this article, we use the unidirectional freeze-drying method to prepare the chitosan porous material, and then analysis the structure and the morphology of the chitosan porous materials by the method of IR and SEM. In order to increase the porosity and the specific surface area of the chitosan porous material, ethyl acetate is added to the chitosan solution before it is frozen. While, for strengthening the mechanical property of the porous material, the graphite oxide is added to the chitosan solution before it is frozen. Meanwhile, the absorbing ability of the porous materials for the metallic ions (Cu2+) and dye (XO) was investigated and some factors such as amount, pH, time, amount of crosslingking agent et al for absorbing ability were confirmed.
The results appeared that the porosity of the porous material increases after ethyl acetate was added, and the GO can strength the mechanical property of the porous material in wet state. The chitosan porous material has a good absorption to the XO and Cu2+. The temperature and the pH are the main factors for controlling the adsorption ability of the chitosan to XO and Cu2+. Since the CS/GO composite is stable and can keep the initial form, it will be a potential absorbing material in waste water treatment.
壳聚糖由于其本身的特性,如具有絮凝作用,分子中含有大量的氨基、羟基具有很强的与金属离子的络合作用以及原料本身的来源丰富,天然无污染等,是一种理想的吸附材料。本文采用定向冷冻干燥法,制备壳聚糖多孔材料。采用IR、SEM等对多孔材料进行结构和形貌分析,同时通过加入造孔剂乙酸乙酯来增加多孔材料的孔隙率,最大限度的增加材料的比表面积,提高吸附效率。为提高壳聚糖多孔材料在水溶液中的力学性能,在壳聚糖中加入氧化石墨,研究了加入不同量的氧化石墨对壳聚糖多孔材料的影响,分析了这种复合材料相对于单纯壳聚糖支架材料的优越性。同时,在室温下,研究了壳聚糖有序多孔材料及其有序复合多孔材料对金属离子Cu(Ⅱ)和染料二甲酚橙(XO)的吸附性能,并重点研究了壳聚糖有序多孔材料的用量、溶液的pH值、吸附时间、壳聚糖的交联度二甲酚橙吸附率和吸附量的影响。
实验结果表明:加入乙酸乙酯造孔剂后制备的多孔材料孔隙率明显增加,氧化石墨的加入明显增强了多孔材料在水中的力学性能。壳聚糖有序多孔材料对二甲酚橙和Cu(Ⅱ)都具有良好的吸附性能。其中,温度、pH值是影响对二甲酚橙吸附的主要因素。整体而言,与壳聚糖多孔材料相比,CS/GO复合多孔材料具有较高的稳固性,在水溶液中能够保持原来的形状,有一定的韧性,使用寿命会较长。
Recently, large amount of heavy metal ions and organics was produced following with the development of the industrial production. Correspondingly, many kinds of wastewater treatment technology emerge. Among them, the adsorption separation technology gets a great development and displays a wide application prospect. So, developing an adsorption material with high efficiency, cheap and nontoxic for wastewater treatment is feasible.
Chitosan displays many special properties. For example, it has lots of amino and hydroxyl on the chitosan molecule which can complex with the metal ions or be used for flocculation. The chitosan is a abundant natural resource, and approved to be an ideal adsorption material. In this article, we use the unidirectional freeze-drying method to prepare the chitosan porous material, and then analysis the structure and the morphology of the chitosan porous materials by the method of IR and SEM. In order to increase the porosity and the specific surface area of the chitosan porous material, ethyl acetate is added to the chitosan solution before it is frozen. While, for strengthening the mechanical property of the porous material, the graphite oxide is added to the chitosan solution before it is frozen. Meanwhile, the absorbing ability of the porous materials for the metallic ions (Cu2+) and dye (XO) was investigated and some factors such as amount, pH, time, amount of crosslingking agent et al for absorbing ability were confirmed.
The results appeared that the porosity of the porous material increases after ethyl acetate was added, and the GO can strength the mechanical property of the porous material in wet state. The chitosan porous material has a good absorption to the XO and Cu2+. The temperature and the pH are the main factors for controlling the adsorption ability of the chitosan to XO and Cu2+. Since the CS/GO composite is stable and can keep the initial form, it will be a potential absorbing material in waste water treatment.
引文
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[2]张林生,蒋岚岚,肖璐宁,活性炭纤维处理染料废水脱色性能的研究,东南大学学报,2001,31(l):100~102
[3]陈中颖,余刚,蒋展鹏,活性炭纤维对染料的吸附性能研究,环境污染与防治,2001,23(4):151~152
[4]蒋兰宏,马子川,董丽丽,新生MnO2对直接染料废水的脱色作用,城市环境与城市生态,2002,15(2):10~13
[5]嵇雅颖,乌锡康,多菌灵生产废水中污染成分的分析研究,上海环境科学, 1990,19(8):8~11
[6]高宝玉,岳钦文,岳钦艳,化学氧化法和化学混凝法用于染料废水的脱色研究,环境科学, 1999,12(l):5~9
[7]高华星,陆兴章,赵德仁,阳离于高分子絮凝剂用于印刷油墨废水处理,环境污染与防治, 1995, 17(3):9~12
[8]庄源益,戴树桂,宋文华,新型絮凝剂凝集水中染料的研究,城市环境与城市生态, 1997,10(2):1~3
[9]孙平,陈景文,全燮,部分水溶性偶氮染料的光催化降解研究,环境化学, 1999,18(3):254~257
[10]王相承,龚小平,活性染料K-2BP在环境水体中的光解效应,环境污染与防治, 1999,21(5):12~14
[11]尹晓红,张敏莉,张艳芳,二氧化钛悬浆体系光催化降解4BS染料的研究,工业水处理,2000,20(10):15~17
[12]杨水,凌艳,光催化法处理活性绿染料废水,湖北化工,1997,(l):53~55
[13]阎怀国,张俊贞,赵惠敏,活性碳纤维的应用,城市环境与城市生态,1998,11(3):5~7
[14]杨贯羽,李宏魁,李延虎,天然沸石对甲基橙的吸附研究,河南科学,2006,24(3):350~352
[15]高湘,张涛,陈平,有机蛭石处理染料废水研究,论文集粹,2007, 23(96) 48~49
[16]裘祖楠,陈明礼,同步吸附─混凝─氧化法处理染色废水,环境工程,1994,12(5):5~7
[17]谈辉明,杨启文,重金属废水处理技术现状与展望,环境科学与技术,1997,1:35~36
[18]李定龙,江晟,重金属废水处理的方案比较研究,工业安全与环保,2005,12:18~19
[19]马士军,微生物絮凝剂的开发及应用,工业处理,1997,12(1):7~10
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