Me-TODGA与TODGA萃取锶性能对比
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摘要
以N,N,N′,N′-四辛基-2-甲基-3-氧戊二酰胺(Me-TODGA)或N,N,N′,N′-四辛基-3-氧戊二酰胺(TODGA)为萃取剂、磷酸三丁酯(TBP)为相改良剂、煤油为稀释剂,对比研究了水相酸度、萃取剂浓度、锶浓度、温度对Me-TODGA-TBP体系和TODGA-TBP体系萃取Sr~(2+)的影响,并采用斜率法确定了萃合物的组成。结果表明,2种酰胺荚醚萃取Sr~(2+)的分配比(D_(Sr))随HNO_3浓度(c(HNO_3)=0.1～2.7 mol/L)、萃取剂浓度(c(萃取剂)=0.05～0.3 mol/L)的增加而增大,随Sr~(2+)浓度的升高略有下降,随温度的升高而下降。2种萃取剂的萃合物组成分别为Sr(NO_3)_2·3Me-TODGA和Sr(NO_3)_2·2TODGA。萃取反应的ΔH分别为-69.46 kJ/mol和-51.39 kJ/mol,ΔS分别为-190.5 J/(mol·K)和-128.4 J/(mol·K),ΔG分别为-12.68 kJ/mol和-13.12 kJ/mol。相比之下,Me-TODGA萃取Sr~(2+)的分配比不到TODGA的1/5。
The extraction of Sr~(2+) from aqueous nitric acid solutions with Me-TODGA(N,N,N′,N′-tetraoctyl-2-methyl-3-oxapentanediamide) was studied to compare with that of TODGA(N,N,N′,N′-tetraoctyl-3-oxapentanediamide). The effect of acidity of aqueous phase, extractant concentration, Sr~(2+) concentration and temperature on distribution ratio was investigated. In order to prevent the formation of third phase, TBP was added as phase modifier and kerosene was used as diluent. A slope method was used to determine the compositions of the extracted species. The results show that the distribution ratio of Sr~(2+)(D_(Sr)) increases with nitric acid or the extractant concentration(c(HNO_3)=0.1-2.7 mol/L, c(extractant)=0.05-0.3 mol/L), and decreases with the increase of the concentration of Sr~(2+) or temperature. The extracted species are Sr(NO_3)_2·3 Me-TODGA and Sr(NO_3)_2·2 TODGA. The ΔH is -69.46 kJ/mol and-51.39 kJ/mol, ΔS is-190.5 J/(mol·K) and-128.4 J/(mol·K), and ΔG is -12.68 kJ/mol and -13.12 kJ/mol for Me-TODGA and TODGA respectively. The D_(Sr) in Me-TODGA is only one-fifth of that in TODGA.
The extraction of Sr~(2+) from aqueous nitric acid solutions with Me-TODGA(N,N,N′,N′-tetraoctyl-2-methyl-3-oxapentanediamide) was studied to compare with that of TODGA(N,N,N′,N′-tetraoctyl-3-oxapentanediamide). The effect of acidity of aqueous phase, extractant concentration, Sr~(2+) concentration and temperature on distribution ratio was investigated. In order to prevent the formation of third phase, TBP was added as phase modifier and kerosene was used as diluent. A slope method was used to determine the compositions of the extracted species. The results show that the distribution ratio of Sr~(2+)(D_(Sr)) increases with nitric acid or the extractant concentration(c(HNO_3)=0.1-2.7 mol/L, c(extractant)=0.05-0.3 mol/L), and decreases with the increase of the concentration of Sr~(2+) or temperature. The extracted species are Sr(NO_3)_2·3 Me-TODGA and Sr(NO_3)_2·2 TODGA. The ΔH is -69.46 kJ/mol and-51.39 kJ/mol, ΔS is-190.5 J/(mol·K) and-128.4 J/(mol·K), and ΔG is -12.68 kJ/mol and -13.12 kJ/mol for Me-TODGA and TODGA respectively. The D_(Sr) in Me-TODGA is only one-fifth of that in TODGA.
引文
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[17] 叶国安,罗方祥,姜永青,等.酰胺荚醚对锶的萃取行为研究[J].原子能科学技术,2001,35(4):344-350.YE Guoan,LUO Fangxiang,JIANG Yongqing,et al.Study on the extraction of strntium with amid podand[J].Atomic Energy Science and Technology,2001,35(4):344-350(in Chinese).
[2] GIUSEPPE M,HANNA A,SCHREINEMACHERS C,et al.Development of a TODGA based process for partitioning of actinides from a Purex raffinate,Part Ⅰ:Batch extraction optimization studies and stability tests[J].Solvent Extraction and Ion Exchange,2007,25:703-721.
[3] WILDEN A,GIUSEPPE M,LANGE S,et al.Modified dglycolamides for the An(Ⅲ)+Ln(Ⅲ) co-separation:Evaluation by solvent extraction and time-resolved laser fluorescence spectroscopy[J].Solvent Extraction and Ion Exchange,2014,32:119-137.
[4] 宋崇立.分离法处理我国高放废液概念流程[J].原子能科学技术,1995,29(3):201-209.SONG Chongli.The concept flowsheet of partitioning process for the Chinese high-level liquid waste[J].Atomic Energy Science and Technology,1995,29(3):201-209(in Chinese).
[5] 叶国安,罗方祥,何建玉,等.酰胺类萃取剂从模拟高放废液中分离锕系和镧系元素的研究[J].原子能科学技术,2001,35(增刊):62-68.YE Guoan,LUO Fangxiang,HE Jianyu,et al.The separation of actinides and lanthanides from simulated high-level liquid waste using amide compounds as extractant[J].Atomic Energy Science and Technology,2001,35(Suppl.):62-68(in Chinese).
[6] 叶国安,何建玉,罗方祥.酰胺荚醚对Am(Ⅲ)和Eu(Ⅲ)的萃取行为研究,Ⅱ:萃取热力学和萃合物光谱研究[J].核化学与放射化学,2000,22(3):136-143.YE Guoan,HE Jianyu,LUO Fangxiang.Study on the extraction of Am(Ⅲ) and Eu(Ⅲ) with amid podand,Ⅱ:Etraction thermodynamics and absorption spectra[J].Journal of Nuclear and Radiochemistry,2000,22(3):136-143(in Chinese).
[7] 叶国安,罗方祥,姜永青,等.酰胺荚醚对Tc(Ⅶ)萃取行为研究[J].原子能科学技术,2000,34(6):528-533.YE Guoan,LUO Fangxiang,JIANG Yongqing,et al.Study on the extraction of technetium with amid podand[J].Atomic Energy Science and Technology,2000,34(6):528-533(in Chinese).
[8] SCHULZ W W,BRAY L A.Solvent extraction of by-product 137Cs and 90Sr from HNO3 solution:A technology review and assessment[J].Sep Sci Techol,1987,22(2):191-201.
[9] 朱文彬.TODGA和DHOA 对金属离子的基本萃取行为及其用于高放废液分离研究[D].北京:中国原子能科学研究院,2013.
[10] ANSARI S A,PATHAK P,HUSAIN M,et al.N,N,N′,N′-tetraoctyl diglycolamide (TODGA):A promising extractant for actinide-partitioning from high-level waste (HLW)[J].Solvent Extraction and Ion Exchange,2005,23:463-479.
[11] TACHIMORI S,SASAKIETAL Y,ICHISUZUKI S,et al.Modification of TODGA-n-dodecane solvent with a monoamide for high loading of lanthanides(Ⅲ) and actinides(Ⅲ)[J].Solvent Extraction and Ion Exchange,2002,20:687-699.
[12] MAGNUSSON D,CHRISTIANSEN B,GLATZ J P,et al.Demonstration of a TODGA based extraction process for the partitioning of minor actinides from a Purex raffinate,Part Ⅲ:Centrifugal contactor run using genuine fuel solution[J].Solvent Extraction and Ion Exchange,2009,27:26-35.
[13] GUJAR R B,ANSARI S A,PRABHU D R.Actinide partitioning with a TODGA solvent:Counter-current extraction studies with simulated high level waste[J].Solvent Extraction and Ion Exchange,2012,30:156-170.
[14] GIUSEPPE M,HANNA A.Demonstration of a TODGA based extraction process for the partitioning of minor actinides from a Purex raffinate,Part Ⅱ:Centrifugal contactor runs[J].Solvent Extraction and Ion Exchange,2008,26:62-76.
[15] MUDASSIR I,JURRIAAN H.Synthesis and Am/Eu extraction of novel TODGA derivatives[J].Supramolecular Chemistry,2010,22:827-837.
[16] 叶国安,何建玉,姜永青,等.酰胺荚醚对Am(Ⅲ)和Eu(Ⅲ)的萃取行为研究,Ⅰ:萃取机理研究[J].核化学与放射化学,2000,22(2):65-72.YE Guoan,HE Jianyu,JIANG Yongqing,et al.Study on the extraction of Am(Ⅲ) and Eu(Ⅲ) with amid podand,Ⅰ:Study on extraction mechanism[J].Journal of Nuclear and Radiochemistry,2000,22(2):65-72(in Chinese).
[17] 叶国安,罗方祥,姜永青,等.酰胺荚醚对锶的萃取行为研究[J].原子能科学技术,2001,35(4):344-350.YE Guoan,LUO Fangxiang,JIANG Yongqing,et al.Study on the extraction of strntium with amid podand[J].Atomic Energy Science and Technology,2001,35(4):344-350(in Chinese).