吡啶类氮氧化物配合物的合成及其催化染料脱色性能研究

发布时间：2018-03-25 16:22

本文选题：吡啶氮氧化物　切入点：金属配合物　出处：《东华大学》2017年硕士论文

【摘要】：随着我国经济高速发展,印染行业废水排量大幅度增长,占综合排水量60%左右。根据具体印染工艺,对印染废水的处理方法主要有物理法、生物法和化学法。物理法一般指简单的界面吸附;化学法一般指加入强氧化剂对有机污染物进行氧化降解;生物法主要利用好氧生物酶和厌氧生物酶对废水中有机污染物进行氧化脱色,效果好,但是由于其生物活性难以保证,且使用条件较为苛刻,因此研究应用人工合成的仿酶催化剂,用于化学法中催化氧化处理印染废水是一种趋势。均相催化剂使用便捷,催化效率高,但是回收困难,容易产生二次污染。因此,催化剂固化技术近年来受到广泛关注。吡啶类氮氧化物中与杂环N原子直接相连的氧原子电子云密度较大,易与金属离子配位形成新颖的结构,且金属配合物具有更好的催化活性。本文首先合成了三种同分异构体配体1,4-二(2-N氧化吡啶)甲氧基苯(L_1),1,4-二(3-N氧化吡啶)甲氧基苯(L_2),1,4-二(4-N氧化吡啶)甲氧基苯(L_3)作为配体,分别与CuCl_2、CoCl_2、MnCl_2配位合成了9种金属配合物。并通过核磁、红外、元素分析确定了配体和配合物的结构。在此基础上,以过氧化氢为氧化剂,比较了9种配合物对于活性蓝-19的催化脱色效果,研究配合物的活性和配体结构及金属种类的关系。结果表明,与配体L_3配位的金属配合物具有较高的活性,而三种不同的金属中,Co盐活性最高,所以得到金属配合物CoL_3的催化效率最高。以此配合物为研究对象,研究了催化剂用量,pH值,过氧化氢用量,底物浓度对染料降解效果的影响。得到最佳催化降解条件:30 mL染料溶液(浓度500 mg/L),56 mL蒸馏水,14 mL 1 mol/L Na_2CO_3/NaHCO_3缓冲溶液(pH=10.2),加入过氧化氢使其浓度为0.1 mol/L,CoL_3 10 mg,室温下进行反应,15 min脱色率可达到95%以上。采用微胶囊技术对选出的最优催化剂CoL_3进行负载,将催化剂和磁性粉末包覆在明胶壁材中,使用戊二醛交联,得到了包覆配合物的磁性微胶囊。催化活性测试实验表明,包覆CoL_3的磁性配合物微胶囊依然能够很好地催化降解活性蓝19。溶液中的磁性配合物微胶囊可通过外加磁场进行回收,并且可以重复利用。通过循环实验可知循环使用5次后,其脱色率仍保持到90%以上;重复使用8次后,其脱色率仍保持到60%以上。
[Abstract]:With the rapid development of China's economy, the discharge of printing and dyeing wastewater has increased by a large margin, accounting for about 60% of the comprehensive discharge. According to the specific printing and dyeing process, the main treatment methods for printing and dyeing wastewater are physical methods. Biological and chemical methods. Physical methods generally refer to simple interfacial adsorption. Chemical methods generally refer to the oxidation and degradation of organic pollutants by adding strong oxidants. The biological method mainly uses aerobic and anaerobic biological enzymes to decolorize organic pollutants in wastewater, but its biological activity is difficult to guarantee, and the application conditions are harsh. Therefore, it is a trend to study the application of synthetic imitating enzyme catalyst to the treatment of printing and dyeing wastewater by catalytic oxidation in chemical method. The homogeneous catalyst is convenient to use, the catalytic efficiency is high, but the recovery is difficult, and it is easy to produce secondary pollution. In recent years, the curing technology of catalyst has attracted wide attention. The electron cloud of oxygen atoms directly connected with heterocyclic N atoms in pyridine nitrogen oxides has a high density and is easily coordinated with metal ions to form novel structures. The metal complexes have better catalytic activity. Firstly, three isomer ligands, 1H 4- dioxy 2-N oxide pyridine) methoxy benzene-L _ 1C _ (1) -dioxy _ 3-N pyridine) were synthesized as ligands, and their ligands were used as ligands, and their ligands were as follows: (1) the ligands of the three isomer ligands, 1 ~ (4) -dioxy (2-N) pyridine) were synthesized as ligands, and (1) methoxybenzenes were synthesized as ligands. Nine metal complexes were synthesized by coordination with CuCl2COCl2MnCl2 respectively. The structures of ligand and complexes were determined by NMR, IR and elemental analysis. On this basis, hydrogen peroxide was used as oxidant. The catalytic decolorization effects of 9 complexes on active blue 19 were compared, and the relationship between the activity of the complexes, the structure of ligands and the kinds of metals was studied. The results showed that the metal complexes coordinated with ligand L3 had higher activity. The catalytic efficiency of the metal complex CoL_3 was the highest because of its highest activity among the three different metals. The amount of catalyst, pH and hydrogen peroxide were studied. Effect of substrate concentration on the degradation of dyes. The optimum catalytic degradation conditions were obtained: 30 mL dye solution (500mg 路L ~ (-1) L ~ (-1)) distilled water (#number0# mg 路L ~ (-1)) distilled water / 1 mol/L Na_2CO_3/NaHCO_3 buffer solution (pH = 10.2), adding hydrogen peroxide to 0.1 mol / L CoL3 ~ (10 mg / L), at room temperature. The decolorization rate of 15 min can reach more than 95%. The optimum catalyst CoL_3 was supported by microencapsulation technique. The magnetic microcapsules coated with catalyst and magnetic powder were prepared by glutaraldehyde crosslinking. The magnetic complex microcapsules coated with CoL_3 can still catalyze the degradation of active blue 19.The magnetic complex microcapsules in the solution can be recovered by external magnetic field and can be reused. The decolorization rate remained above 90%, and the decolorization rate remained above 60% after repeated use for 8 times.
【学位授予单位】：东华大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O643.36;X791

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