預(yù)組織構(gòu)象雙酰胺類萃取劑的合成及其性能的研究
發(fā)布時間：2018-11-17 16:46
【摘要】：在新材料開發(fā)、特質(zhì)材料制備等領(lǐng)域有著極其重要價值的稀有金屬元素的分離提純回收不僅能夠滿足科技發(fā)展需求,而且還能減少對環(huán)境的污染。目前溶劑萃取技術(shù)是高放廢物的后處理方法中最符合可持續(xù)發(fā)展要求的。新型萃取劑和工藝流程的研發(fā)設(shè)計一直是溶劑萃取的兩個重要環(huán)節(jié)。因此優(yōu)化萃取劑結(jié)構(gòu)和萃取條件對萃取化學學科的發(fā)展具有重要意義。在稀土分離領(lǐng)域,酰胺類萃取劑具有能夠完全燃盡、后處理簡單、綠色環(huán)保等優(yōu)點備受關(guān)注;而對鋯、鉿的萃取未見報道。由于鋯鉿共生,性質(zhì)極其相似,因而鋯鉿的分離成為原子能級的鋯、鉿材料的制備的難題。因此研發(fā)一種新型綠色環(huán)保型萃取劑具有重要的戰(zhàn)略性意義。在現(xiàn)有萃取劑結(jié)構(gòu)理論的基礎(chǔ)上,本文合成了一種雙酰胺類萃取劑—N,N,N',N'-四辛基-3-氧戊二酰胺(TODGA)萃取劑,研究其對鋯鉿的萃取分離性能,拓展雙酰胺類萃取劑在分離稀土以外的應(yīng)用領(lǐng)域;與此同時本文還探索性的合成一種苯并5,6-雙環(huán)二酰亞胺結(jié)構(gòu)的萃取劑,進一步完善雙酰胺類萃取劑在稀土分離領(lǐng)域的發(fā)展歷程。主要研究內(nèi)容如下:一、合成N,N,N',N'-四辛基-3-氧-戊二酰胺,通過減壓蒸餾、柱層析等分離方法進行提純,并通過利用高效液相色譜、傅里葉紅外光譜、核磁共振等方法對產(chǎn)品的純度和結(jié)構(gòu)進行了檢測表征。通過考察水相酸度、萃取劑濃度及溫度因素的影響,研究不同稀釋劑TODGA從鹽酸介質(zhì)中對鋯鉿萃取分離性能的影響。結(jié)果表明一定酸度范圍內(nèi),鋯、鉿的萃取分配比、分離因數(shù)都隨鹽酸濃度的增大而增大,以脂肪烷烴為稀釋劑,TODGA對鋯、鉿的萃取分配比、分離因數(shù)隨著碳鏈的增長而增大,而且與稀釋劑的極性有關(guān);在一定萃取劑濃度范圍內(nèi),隨濃度的增加分配比逐漸增加,而分離因數(shù)不發(fā)生變化,當萃取劑濃度大于0.4 mol·dm-3時,分離因數(shù)急劇上升,表明萃取機理發(fā)生變化;在一定溫度范圍內(nèi),升高溫度有利于萃取反應(yīng),表明萃取過程為吸熱過程,并計算出熱力學函數(shù)。二、探索性設(shè)計合成路線并制備苯并5,6-雙環(huán)亞酰胺萃取劑。采用鄰甲苯胺為原料,與水合三氯乙醛、鹽酸羥胺反應(yīng);在濃硫酸的作用下,發(fā)生貝克曼重排反應(yīng)生成7-甲基靛紅,以醋酸作溶劑,進行親電取代反應(yīng)生成5-溴-7-甲基靛紅;通過紫外光引發(fā),進行自由基反應(yīng)生成5-溴-7溴甲基靛紅,然后與丙二酸二甲酯進行親核取代,利用低價鈦的強還原性進行羰基還原,最后通過脂解、脫羧,在醋酸酐中加熱回流合成最終產(chǎn)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.
【學位授予單位】：濟南大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TQ028.32
本文編號：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.
【學位授予單位】：濟南大學
【學位級別】：碩士
【學位授予年份】：2015
【分類號】：TQ028.32
【參考文獻】
相關(guān)期刊論文 前1條
1 賈瓊,李德謙,牛春吉;1-苯基-3-甲基-4-苯甲�；�-吡唑酮-5與中性磷(膦)萃取劑協(xié)同萃取鑭B[J];分析化學;2004年11期
，本文編號：2338475
本文鏈接：http://sikaile.net/kejilunwen/huagong/2338475.html
教材專著
