N,N,N,,N,-四己基丁二酰胺萃取铀、钍及硝酸的机理

合成了 N,N,N?N?四己基丁二酰胺(THSA)。以正十二烷为稀释剂研究了THSA萃取硝酸的平衡,认为在低酸度下主要形成THSA·HNO3加合物,在高酸度下主要形成加合物THSA·HNO3和THSA·(HNO3)2;还研究了THSA从硝酸介质中萃取铀、钍的机理,通过考察 HNO3浓度、THSA浓度及温度对铀和钍分配比的影响,得出了萃合物的组成为UO2(NO3)2·THSA和Th(NO3)4·2THSA,并计算出萃取反应的表观平衡常数及热焓。实验结果表明THSA具有较强的对铀、钍萃取能力,并有望实现铀、钍分离。     

Extraction of Actinide Ion by Asymmetrical N,N′-dimethyl-N,N′-dioctyl-diglycolamide

正In order to develop sustainable nuclear energy,agreat effort has been made for designing new extractants to selectively separate all actinides from nitric acid solutions of dissolution of spent fuel. Among those,tetraalkyldiglyco-     

N,N,N‘,N’—四已基丁二酰胺萃取铀、钍及硝酸的机理

合成了N,N,N     

N,N,N‘,N’—四丁基己二酰胺在硝酸介质中萃取铀,钍及硝酸的研究

研究了Ｎ，Ｎ，Ｎ’，Ｎ’－四丁基己二酰胺（ＴＢＡＡ）从硝酸介质中萃取铀，钍及硝酸的机理，考究了ＨＮＯ３浓度，ＴＢＡＡ浓度，温度及盐析（ＬｉＮＯ３）对铀和钍分配系数的影响，还对铀，钍的反萃进行了研究，得出萃合物的组成的ＵＯ２（ＮＯ３）２．ＴＢＡＡ和Ｔｈ（ＮＯ３）２．ＴＢＡＡ。在低酸度下，ＴＢＡＡ与硝酸主要以ＴＢＡＡ．ＨＮＯ３的形式存在，在高酸度下，ＴＢＡＡ与硝酸的加合物不但有（ＴＢＡＡ）２．ＨＮＯ３     

Extraction of lanthanide ions with N,N,N′,N′-tetrabutyl-3-oxadiglycolamide from nitric acid media

Extractability and extraction mechanism of lanthanide ions were investigated by using a new extractant,N,Nn,N′,N′-tetrabutyl-3-oxa-diglycolamide(TBDGA),in toluene from nitric acid media.The effects of HNO_3 and TBDGA concentrations,and temperature,on extraction of lanthanide ions were studied.Stoichiometrics of the main extracted species were HNO_3·TBDGA and M(NO_3)_3-3TBDGA(M = Er,Dy,Tb,Gd,La,Ce,Nd,Sm and Eu).The extracted species for metal ions were established to be ionic complex.In this complex,nitrate anion was not coordinated to the central ion.The extraction pattern increased gradually across the lanthanide ions series,showing enhanced affinity of TBDGA toward heavy lanthanide ions.Thermodynamic parameters were investigated for the exothermic extraction reaction.     

Solvent extraction of nitric acid,uranium（VI） and thorium（IV） by N,N,N‘,N’—tetrahexylsuccinylamide

A new kind of diamide N,N,N‘,N‘-tetrahexylsuccinylamide(THSA) was synthesized,characterized and used for the extraction of HNO3,U(VI)and Th(IV) in a diluent composed of 0.5 volume fraction 1,2,4-trimethy benzene(TMB) and 0.5 volume fraction kerosene(OK),Extraction distribution coefficients of U(VI) and Th(IV) as functions of aqueous nitric acid concentation,extractant concentration.temperature and salting-out agent (LiNO3) have been studied,and it is found that THSA as an extractant is superior to TBP for extraction of U(VI) and Th(IV),Back Extraction was also studied.At low acidity,the main adduct of THSA and NHO3 is HNO3 is HNO3.THSA,THSA.(HNO3)2 and THSA.(HNO3)3 are also found at high acidity.The compositions of extracted species.apparent equilibrium constants and enthalpies of extraction reactions have also been calculated.     

Synthesis of N,N＇-dimethyl-N,N＇-didecyl-3-oxa-diglycolamide for extraction of lanthanides

A novel extractant,N,N'-dimethyl-N,N'-didecyl-3-oxa-diglycolamide(DMDDDGA),was designed and synthesized for extraction of lanthanides in the nuclear fuel reprocessing.The extraction behaviors of Gd,Dy,Er and Ho from nitric acid solution were investigated using DMDDDGA in chloroform.The effects of nitric acid concentration,extractant concentration,and temperature on the extraction were investigated.The distribution ratio of lanthanides increases with concentrations of the extractant and nitric acid,but decreases with increasing temperature,which indicates that the extraction process is exothermic.FT-IR spectra indicated that the C=0 in DMDDDGA is coordinated with metal ion in the extracted species and the stoichiometries of lanthanides(Ⅲ)complex are Gd(NO_3)_3·3DMDDDGA,Dy(NO_3)_3·4DMDDDGA,Er(NO_3)_3·4DMDDDGA,and Ho(NO_3)_3·4DMDDDGA.     

Solvent extraction of nitric acid,uranium(VI) and thorium(IV) by N,N,N＇,N＇-tetrahexylsuccinylamide

A new kind of diamideN,N,N＇,N＇-tetrahexylsuccinylamide (THSA)wassynthesized,characterized and used for the extraction of HNO₃,U(VI) and Th(IV)in a diluent composed of 0.5 volume fraction1,2,4-trimethy benzene(TMB) and 0.5 volume fraction kerosene(OK).Extraction distribution coefficients of U(VI) and Th(IV) as functionsof aqueous nitric acid concentration, extractant concentration,temperature and salting-out agent (LiNO₃) have been studied, and it is found that THSA as an extractant is superior to TBP for extraction ofU(VI) and Th(IV). Back extraction was also studied. At low acidity, themain adduct of THSA and HNO₃ is HNO₃^.THSA. THSA^.(HNO₃)₂ and THSA^.(HNO₃)₃ are also found at high acidity. The compositions of extracted species, apparent equilibrium constants and enthalpies ofextraction reactions have also been calculated.     

Extraction Performance of Np(Ⅳ) with N,N′-dimethyl-N,N′-dioctyl-3-oxa-glutaramide

<正>N,N′-dimethyl-N,N′-dioctyl-3-oxa-glutaramide(DMDODGA),due to the advantages of enduring radiation,difficult hydrolysis,no-toxicity and being burnt off,has a broad application prospect.Diamidespod-ether compounds as tridentateligands have gained more attention in actinide separation.In the present work,by using n-octanol(40%)-kerosen as diluent,the extraction per-     

Solvent extraction of uranium（VI） and thorium（IV） in nitric acid solution by N,N,N‘,N’—tetrabutyladipicamide

N,N,N‘N‘-tetrabutyladipicamide(TBAA) has been synthesized,and applied to the extraction of U(VI) and Th(IV) from nitric acid solutions in a diluent composed of 0.50 volume fraction 1,2,4-trimethyl benzene (TMA) and 0.50 volume fraction kerosene(OK),The effects of the aueous nitric acid concentration,extractant concentration,slating-out agent (LiNO3) and temperature on extraction ability of TBAA for U(VI) and Th(IV) have been studied.Back Extraction of U(VI) and Th (IV) from organic phases were performed by dilute nitric acid.The compositions of extracted complexes,equilibrium constants and enthalpies of extraction reactions have also been estimated.The IR spectra of extraction of U(VI) and Th(IV) have been studied.     

用气相色谱法测定N,N,N’,N’-四丁基-3-氧戊二酰胺在HNO_3中的溶解度

研究了用气相色谱法测定0.2 mol/LN,N,N’,N’-四丁基-3-氧戊二酰胺(TBOPDA)/40%辛醇-煤油中的TBOPDA在不同浓度HNO3中的溶解度的分析方法。首先取过量的0.2 mol/L TBOPDA/40%辛醇-煤油和不同浓度HNO3振荡40 min后,用甲苯萃取水相中的TBOPDA后进行气相色谱测量。采用选择性检测器氢火焰离子化检测器进行测定,0.2 mol/L TBOPDA/40%辛醇-煤油中的TBOPDA在1、2、3 mol/L HNO3中的溶解度分别为0.702、0.723、0.735 g/L。     

Solvent extraction of U（VI） and Th（IV） ions with N,N,N‘,N’—tetrabutylsuccinylamide from nitric acid solutions

The solvent extraction of U(VI) and Th(IV) from nitric acid medium by N,N,N‘,N‘-tetrabutylsuccinylamide(TBSA) in a diluent composed of 0.5 volume fraction trimethyl benzene(TMB) and 0.5 volume fraction kerosene(OK) has been studied.The distribution ratios of U(VI) and Th(IV) as a function of aqueous HON3 concentration,extractant concentration and temperature have been measured.From the data,the composition of extracted species,equilibrium constants and enthapies of extraction reaction are also calculated.     

N，N,N‘,N’—tetrabutylmalonamide as a new extractant for extraction of nitric acid and uranium（VI）

N,N,N‘,N‘-tetrabutylmalonamide(TBMA) is synthesized and used for extraction of uranyl(Ⅱ） ion from nitric acid media in a diluent composed of 50% 1,2,4-trimethyl benzene (TMB) and 50% kerosene(OK),The effects of nitric acid concentration,extractant concentration,temperature,slating-out agent (LiNO3) and back extraction on distribution coefficients of uranyl(Ⅱ） ion have been studied.The extraction of nitric acid is also studied.The main adduct of TBMA and HNO3 is HNO3.TBMA,and there are more than two kinds of adducts in 3.0mol/L nitric acid solutions,such as HNO3.TBMA,(HNO3)2,TBMA and (NHO3)3.TBMA.The complex formation of uranyl(Ⅱ） ion,nitrate ion and TBMA(1:2:1) as extracted species is further confirmed by IR spectra of the saturated extraction of uranyl(Ⅱ） ion with TBMA,and the values of thermodynamic parameters have also been calculated.     

Solvent extraction of U(Ⅵ) by N,N-dimethyl-N',N'-dioctylsuccinylamide and N,N-dimethyl-N',N'-didecylsuccinylamide in cyclohexane

The extraction of uranyl nitrate by novel extractants of N,N-dimethyl-N',N'-dioctylsuccinylamide(DMDOSA)and N,N-dimethyl-N',N'-didecylsuccinylamide(DMDDSA) from aqueous nitric/nitrate solutions was investigated.It was found both the concentration of HNO_3 and extractants had an effect on the U(Ⅵ) extraction distribution.The extraction mechanism was established,and stoichiometry of the main extracted species was confirmed to be UO_2(NO_3)_2·2DMDOSA and UO_2(NO_3)_2·2DMDDSA,respectively.Both of the extraction reactions are exothermic.FTIR spectral study of the U(Ⅵ) extracted species was also made.     

γ辐照对N,N,N′,N′-四丁基-3-氧-戊二酰胺萃取性能的影响

N,N,N′,N′-四丁基-3-氧-戊二酰胺(TBOPDA)对锕系和镧系元素具有较好的萃取性能和较高的辐照稳定性。本文主要研究了辐照对纯TBOPDA和稀释后的TBOPDA萃取性能的影响。研究结果表明,该萃取剂具有较强的辐照稳定性。纯萃取剂在辐照剂量达到1000kGy时,对铀的萃取分配比才有明显下降;;达到100kGy时对铕的萃取分配比有明显下降。稀释剂的加入会使萃取剂辐照稳定性有所下降。     

N,N,N′,N′-四异丁基-3-氧戊二酰胺对钼(Ⅵ)的萃取

研究了N，N，N′，N′－四异丁基－3－氧戊二酰胺（TiBOPDA)-40%正辛醇／煤油溶液从HNO3溶液中萃取Mo(Ⅵ）的行为。实验结果表明，温度对Mo(Ⅵ）的萃取分配比影响很小，萃取过程无明显热效应。在HNO3浓度为1mol/L时，Mo(Ⅵ）以MoO2^2 形式被萃取，MoO2(NO3)2与TiBOPDA形成配位比为1：2的配合物，TiBOPDA萃取Mo(Ⅵ）为中性配合萃取。文章给出了萃取平衡方程式。     

N,N,N’,N’-四丁基-3-氧-戊二酰胺辐解产物研究 Ⅰ.二丁胺的定性和定量分析

采用红外、顶空固相微萃取-气相色谱／质谱联用的方法，研究了萃取剂N，N，N'，N'-四丁基-3-氧-戊二酰胺(TBOPDA)的液相辐解产物，并通过与标准物质对照，确定TBOPDA的液相辐解产物中存在二丁胺和N，N-二正丁基甲酰胺。采用高效液相色谱、固相微萃取-气相色谱联用方法，定量分析了在辐照过程中TBOPDA的分解情况和二丁胺的产生情况，分别计算了两者的产额。提出了TBOPDA的3种可能断裂方式。     

N,N,N′,N′-四异丁基-3-氧杂戊二酰胺对超铀元素和锝的萃取

研究了N,N,N′,N′-四异丁基－3－氧杂戊二酰胺（TiBOGA)-40%正辛醇／煤油对超铀元素及Tc的萃取,研究结果表明,0．2mol/L,TiBOGA-40%正辛醇／煤油对Tc(Ⅶ）,Am（Ⅲ）,Np（Ⅳ）,Np(Ⅴ),Pu(Ⅲ),Pu(Ⅳ)均有一定萃取能力,在酸度为1mol/L HNO3的模拟料液中,其分配比分别为：2．25,＞2000,43,0．734,＞2000,34。TiBOGA-40%正辛醇／煤油对各种离子的萃取能力受酸度和盐析剂浓度影响较大,用0．1mol/L HNO3能将除Am(Ⅲ）以外的其它几种离子从有机相中反萃下来。0．6mol/L H2C2O4对超铀元素的反萃效果都很好,经过1次或2次反萃,反萃率均可达99％以上。     

在二乙撑三胺-N,N,N′,N″,N″五乙酸介质中铀与大量伴生元素的色层分离

基于在二乙撑三胺-N,N,N′,N″,N″五乙酸介质中,大量伴生离子中的铀酰离子在硅胶柱上的选择性吸附,提出了铀的分离和测定方法。过去已测定了在硅胶和聚酰氨羧酸体系中,铀和钍的分配系数。在二乙撑三胺-N,N,N′,N″,N″五乙酸(DTPA)和三乙撑四胺六乙酸(TTHA)介质中色层分离是非常有效的。所以,本报告探讨了在DTPA的介质中,痕量铀酰离子与大量伴生元素的色层分离。     

N,N—二乙基十八酰胺萃取铀的研究

以甲苯为稀释剂研究了Ｎ，Ｎ－二乙基十八酰胺（ＤＥＯＤＡ）从硝酸介质中萃取铀的可行性，考察了水相酸度、萃取剂浓度对萃取平衡的影响，救是了萃取平衡常数，借助红外光谱萃合物的组成和结构，考察了温度对以平衡的影响，得到了萃取化学反应的热力学常数。ＤＥＯＤＡ萃取体系不出现三相，是核燃料处理中有前任的一种萃取剂。