预组织构象双酰胺类萃取剂的合成及其性能的研究
发布时间：2018-11-17 16:46
【摘要】：在新材料开发、特质材料制备等领域有着极其重要价值的稀有金属元素的分离提纯回收不仅能够满足科技发展需求,而且还能减少对环境的污染。目前溶剂萃取技术是高放废物的后处理方法中最符合可持续发展要求的。新型萃取剂和工艺流程的研发设计一直是溶剂萃取的两个重要环节。因此优化萃取剂结构和萃取条件对萃取化学学科的发展具有重要意义。在稀土分离领域,酰胺类萃取剂具有能够完全燃尽、后处理简单、绿色环保等优点备受关注;而对锆、铪的萃取未见报道。由于锆铪共生,性质极其相似,因而锆铪的分离成为原子能级的锆、铪材料的制备的难题。因此研发一种新型绿色环保型萃取剂具有重要的战略性意义。在现有萃取剂结构理论的基础上,本文合成了一种双酰胺类萃取剂—N,N,N',N'-四辛基-3-氧戊二酰胺(TODGA)萃取剂,研究其对锆铪的萃取分离性能,拓展双酰胺类萃取剂在分离稀土以外的应用领域;与此同时本文还探索性的合成一种苯并5,6-双环二酰亚胺结构的萃取剂,进一步完善双酰胺类萃取剂在稀土分离领域的发展历程。主要研究内容如下:一、合成N,N,N',N'-四辛基-3-氧-戊二酰胺,通过减压蒸馏、柱层析等分离方法进行提纯,并通过利用高效液相色谱、傅里叶红外光谱、核磁共振等方法对产品的纯度和结构进行了检测表征。通过考察水相酸度、萃取剂浓度及温度因素的影响,研究不同稀释剂TODGA从盐酸介质中对锆铪萃取分离性能的影响。结果表明一定酸度范围内,锆、铪的萃取分配比、分离因数都随盐酸浓度的增大而增大,以脂肪烷烃为稀释剂,TODGA对锆、铪的萃取分配比、分离因数随着碳链的增长而增大,而且与稀释剂的极性有关;在一定萃取剂浓度范围内,随浓度的增加分配比逐渐增加,而分离因数不发生变化,当萃取剂浓度大于0.4 mol·dm-3时,分离因数急剧上升,表明萃取机理发生变化;在一定温度范围内,升高温度有利于萃取反应,表明萃取过程为吸热过程,并计算出热力学函数。二、探索性设计合成路线并制备苯并5,6-双环亚酰胺萃取剂。采用邻甲苯胺为原料,与水合三氯乙醛、盐酸羟胺反应;在浓硫酸的作用下,发生贝克曼重排反应生成7-甲基靛红,以醋酸作溶剂,进行亲电取代反应生成5-溴-7-甲基靛红;通过紫外光引发,进行自由基反应生成5-溴-7溴甲基靛红,然后与丙二酸二甲酯进行亲核取代,利用低价钛的强还原性进行羰基还原,最后通过脂解、脱羧,在醋酸酐中加热回流合成最终产物。
[Abstract]:The separation, purification and recovery of rare metal elements, which are of great value in the development of new materials and the preparation of special materials, can not only meet the needs of the development of science and technology, but also reduce the pollution to the environment. At present, solvent extraction is the most suitable reprocessing method for high-level radioactive waste. The R & D and design of new extractant and technological process are two important links of solvent extraction. Therefore, the optimization of extractant structure and extraction conditions is of great significance to the development of extraction chemistry. In the field of rare earth separation, amides have the advantages of complete burnout, simple post-treatment and environmental protection, but the extraction of zirconium and hafnium has not been reported. Because zirconium and hafnium are symbiotic and have similar properties, the separation of zirconium and hafnium becomes a difficult problem in the preparation of atomic grade zirconium and hafnium. Therefore, it is of strategic significance to develop a new green environmental-friendly extractant. On the basis of the existing extractant structure theory, a bisamide extractant, N (N) (N) -tetraoctyl -3-oxyglutaramide (TODGA) extractant, was synthesized and its separation performance for zirconium and hafnium was studied. To expand the application of bisamide extractants in the separation of rare earths; At the same time, an extractant with the structure of benzo _ 5o _ 6-bicyclic diimide was synthesized and the development process of bisamide extractant in the field of rare earth separation was further improved. The main contents of the study are as follows: 1. The synthesis and purification of NZN, N-, and tetraoctyl-3-oxy-pentanediamide, by means of vacuum distillation, column chromatography, and Fourier transform infrared spectroscopy (FTIR). The purity and structure of the product were characterized by NMR. The effects of aqueous acidity, extractant concentration and temperature on the separation of zirconium and hafnium from hydrochloric acid solution by different diluent TODGA were investigated. The results show that the extraction partition ratio and separation factor of zirconium and hafnium increase with the increase of hydrochloric acid concentration in a certain range of acidity, and the extraction and distribution ratio of zirconium and hafnium by TODGA increases with the increase of carbon chain, using aliphatic alkane as diluent, the extraction and distribution ratio of TODGA to zirconium and hafnium increases. And it is related to the polarity of diluent. In a certain range of extractant concentration, the partition ratio increases gradually with the increase of concentration, but the separation factor does not change. When the concentration of extractant is greater than 0.4 mol dm-3, the separation factor increases sharply, which indicates that the extraction mechanism has changed. It is shown that the extraction process is endothermic and the thermodynamic function is calculated by increasing the temperature in a certain temperature range. Secondly, the route of synthesis was designed and the extraction agent of benzo 5 n 6-dicyclic amide was prepared. O-toluidine was used as raw material to react with trichloroacetaldehyde hydrate and hydroxylamine hydrochloride. In the presence of concentrated sulfuric acid, a Beckmann rearrangement reaction was carried out to produce 7-methylindirubin, and the electrophilic substitution reaction was carried out with acetic acid as solvent to produce 5-bromo-7-methylindirubin. 5- bromo-7 bromomethyl indirubin was synthesized by radical reaction initiated by ultraviolet light, then nucleophilic substitution with dimethyl malonate was carried out, carbonyl reduction was carried out by the strong reductive property of low-valence titanium, and decarboxylation was carried out by lipid hydrolysis, decarboxylation of 5-bromo-7 bromomethyl indirubin and dimethyl malonate. The final product was synthesized by heating reflux in acetic anhydride.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ028.32
本文编号：2338475
[Abstract]:The separation, purification and recovery of rare metal elements, which are of great value in the development of new materials and the preparation of special materials, can not only meet the needs of the development of science and technology, but also reduce the pollution to the environment. At present, solvent extraction is the most suitable reprocessing method for high-level radioactive waste. The R & D and design of new extractant and technological process are two important links of solvent extraction. Therefore, the optimization of extractant structure and extraction conditions is of great significance to the development of extraction chemistry. In the field of rare earth separation, amides have the advantages of complete burnout, simple post-treatment and environmental protection, but the extraction of zirconium and hafnium has not been reported. Because zirconium and hafnium are symbiotic and have similar properties, the separation of zirconium and hafnium becomes a difficult problem in the preparation of atomic grade zirconium and hafnium. Therefore, it is of strategic significance to develop a new green environmental-friendly extractant. On the basis of the existing extractant structure theory, a bisamide extractant, N (N) (N) -tetraoctyl -3-oxyglutaramide (TODGA) extractant, was synthesized and its separation performance for zirconium and hafnium was studied. To expand the application of bisamide extractants in the separation of rare earths; At the same time, an extractant with the structure of benzo _ 5o _ 6-bicyclic diimide was synthesized and the development process of bisamide extractant in the field of rare earth separation was further improved. The main contents of the study are as follows: 1. The synthesis and purification of NZN, N-, and tetraoctyl-3-oxy-pentanediamide, by means of vacuum distillation, column chromatography, and Fourier transform infrared spectroscopy (FTIR). The purity and structure of the product were characterized by NMR. The effects of aqueous acidity, extractant concentration and temperature on the separation of zirconium and hafnium from hydrochloric acid solution by different diluent TODGA were investigated. The results show that the extraction partition ratio and separation factor of zirconium and hafnium increase with the increase of hydrochloric acid concentration in a certain range of acidity, and the extraction and distribution ratio of zirconium and hafnium by TODGA increases with the increase of carbon chain, using aliphatic alkane as diluent, the extraction and distribution ratio of TODGA to zirconium and hafnium increases. And it is related to the polarity of diluent. In a certain range of extractant concentration, the partition ratio increases gradually with the increase of concentration, but the separation factor does not change. When the concentration of extractant is greater than 0.4 mol dm-3, the separation factor increases sharply, which indicates that the extraction mechanism has changed. It is shown that the extraction process is endothermic and the thermodynamic function is calculated by increasing the temperature in a certain temperature range. Secondly, the route of synthesis was designed and the extraction agent of benzo 5 n 6-dicyclic amide was prepared. O-toluidine was used as raw material to react with trichloroacetaldehyde hydrate and hydroxylamine hydrochloride. In the presence of concentrated sulfuric acid, a Beckmann rearrangement reaction was carried out to produce 7-methylindirubin, and the electrophilic substitution reaction was carried out with acetic acid as solvent to produce 5-bromo-7-methylindirubin. 5- bromo-7 bromomethyl indirubin was synthesized by radical reaction initiated by ultraviolet light, then nucleophilic substitution with dimethyl malonate was carried out, carbonyl reduction was carried out by the strong reductive property of low-valence titanium, and decarboxylation was carried out by lipid hydrolysis, decarboxylation of 5-bromo-7 bromomethyl indirubin and dimethyl malonate. The final product was synthesized by heating reflux in acetic anhydride.
【学位授予单位】：济南大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ028.32
【参考文献】
相关期刊论文 前1条
1 贾琼,李德谦,牛春吉;1-苯基-3-甲基-4-苯甲酰基-吡唑酮-5与中性磷(膦)萃取剂协同萃取镧B[J];分析化学;2004年11期
，本文编号：2338475
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