(19)
(11)EP 3 296 411 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
18.03.2020 Bulletin 2020/12

(21)Application number: 15891987.8

(22)Date of filing:  31.12.2015
(51)Int. Cl.: 
C22B 60/02  (2006.01)
C22B 59/00  (2006.01)
C22B 3/32  (2006.01)
G21F 9/12  (2006.01)
(86)International application number:
PCT/RU2015/000967
(87)International publication number:
WO 2016/182472 (17.11.2016 Gazette  2016/46)

(54)

METHOD FOR ISOLATING AMERICIUM FROM LIQUID RADIOACTIVE WASTE AND FOR SEPARATING AMERICIUM FROM RARE EARTH ELEMENTS

VERFAHREN ZUR ISOLIERUNG VON AMERICIUM AUS FLÜSSIGEM RADIOAKTIVEM ABFALL UND ZUR TRENNUNG VON AMERICIUM AUS SELTENERDELEMENTEN

PROCÉDÉ D'EXTRACTION D'AMÉRICIUM À PARTIR DE DÉCHETS RADIOACTIFS LIQUIDES ET DE SA SÉPARATION DES ÉLÉMENTS DES TERRES RARES


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 13.05.2015 RU 2015117911

(43)Date of publication of application:
21.03.2018 Bulletin 2018/12

(73)Proprietor: State Atomic Energy Corporation "Rosatom" on Behalf of The Russian Federation
Moscow 119017 (RU)

(72)Inventors:
  • ALYAPYSHEV, Mihail Yurievich
    St.Petersburg 194021 (RU)
  • BABAIN, Vasily Aleksandrovich
    Sankt-Peterburg 194021 (RU)
  • KENF, Ekaterina Vladimirovna
    Respublika Komi g. Uhta 169302 (RU)
  • TKACHENKO, Ludmila Igorevna
    St.Petersburg 194295 (RU)
  • LOGUNOV, Mihail Vasilievich
    Chelyabinskaya Obl. g. Ozersk 456783 (RU)
  • VOROSHILOV, Yuriy Arkadievich
    Chelyabinskaya Obl. g. Ozersk 456790 (RU)
  • HASANOV, Rinat Nailevich
    Chelyabinskaya Obl. g. Ozersk 456790 (RU)
  • SHADRIN, Andrey Yurievich
    Moscow 125367 (RU)
  • VIDANOV, Vitaliy Lvovich
    Moscow 115580 (RU)

(74)Representative: Dentons UK and Middle East LLP 
One Fleet Place
London EC4M 7WS
London EC4M 7WS (GB)


(56)References cited: : 
EP-A1- 1 664 359
FR-A1- 2 810 679
RU-C2- 2 544 716
WO-A1-02/28778
RU-C2- 2 335 554
US-A1- 2012 152 059
  
  • BABAIN V A ET AL: "Extraction of Am and Eu with N,N'-substituted pyridine-2,6-dicarboxamides in fluorinated diluents", RADIOCHEMISTRY, NAUKA/INTERPERIODICA, MO, vol. 48, no. 4, 1 July 2006 (2006-07-01), pages 369-373, XP019406273, ISSN: 1608-3288, DOI: 10.1134/S1066362206040102
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description


[0001] The proposed invention relates to the processes of extraction and concentration of radio nuclides and can be used in radiochemical technologies when processing liquid radioactive wastes.

[0002] In up-to-date processes of nuclear fuel radioactive wastes of several compositions are formed. When processing raffinates of PUREX-process it is reasonable to extract americium for its subsequent burning up. One of the most difficult chemical tasks is separation of minor actinides (americium, curium) from accompanying fission products - rare-earth elements (lanthanides and yttrium).

[0003] There are methods known for extraction of Americium together with rare-earth elements. These are TRUEX [US 5708958 (A) B01D11/04]; TRPO [Lui X., Liang J., Xu J./Solv. Extr. Ion Exch., 2004, 22(2) 163-173], published on 13.01.2013; DIAMEX [Courson O., Leburn M., Malmbeck R., Pagliosa G., Romer K., Satmark B., Glatz J.P./Radiochim. Acta., 2000, V. 88 (12), 857-863]; and others.

[0004] Disadvantage of the above mentioned methods is simultaneous (collective) extraction of americium and the rare-earth elements.

[0005] There is a method known for separation of americium and curium from the rare-earth elements with the use of extraction mixture on the basis of dialkyl-phosphoric acids - TALSPEAK [E.D. Collins, D.E. Benker, P.D. Bailey, et al. / Proc. Int. Conf. Global 2005, Tsukuba, Japan, Oct. 9-13, 2005, paper # 186; Nilsson M., Nash K.L. /Solv. Extr. Ion Exch., 2007, 25(6), 665-701].

[0006] Disadvantage of the above mentioned method is low effectiveness of americium and curium extraction from solutions with concentration of nitric acid above 1 mol/L.

[0007] There is a method known for separation of americium and curium from the rare-earth elements with the use of extraction mixture of di(2-etholhexyl)phosphate or mono(2-ethylhexyl)-2-ethylhexyl phosphonate / N,N,N,N-tetra-2-ethylhexyl diglycol amide or N,N,N',N'-tetraoktyl-diamide of diglycolic acid in n-dodecane - ALSEP (US 8354085 B1 C22B 60/00, published on 15.01.2013).

[0008] Disadvantages of the proposed in the method extraction mixture is low extraction ability towards americium. Usage of saturated hydrocarbons (n-dodecane) as a diluent leads to the organic phase that has low capacity by metals. Moreover, usage of solution with high concentration of complexones for back extraction of americium and curium complicates further processing of re-extracts.

[0009] There is a method known for separation of americium from the rare-earth elements with the use of mixtures of N,N,N',N'-tetraoktyl-diamide of diglycolic acid and 1-octanol in hydrocarbonic diluent - innovative SANEX [M.Sypula, A, Wilden, C. Schreinemachers, G. Modolo /Proceedings of the First ACSEPT International Workshop, Lisbon, Portugal, 31 March - 2 April 2010, http://www.acsept.org/AIWOproc/AIWO 1 -PR08-Sypula.pdf].

[0010] Disadvantage of this method is using for selective back extraction of americium of solution containing sodium nitrate the presence of which complicates further processing of re-extracts.

[0011] There is a method known for separation of americium from the rare-earth elements, curium and fission products by binary extraction mixture of a neutral and acid extractant (US 2012/152059 A1 C22B 60/02, published on 21.06.2012).

[0012] Disadvantage of this method is using of generally two extraction systems within one cycle. Thus, a neutral extractant is used for americium extraction, and an acid extractant is added during the americium back extraction process, which makes it necessary to separate the extraction mixture before further use. When only a binary mixture is used in the extraction cycle, the extraction of zirconium, iron and molybdenum increases noticeably, which, in addition to a significant decrease in the extraction system capacity, leads to contamination of the target product.

[0013] There is a method known for separation of americium and curium from the rare-earth elements with the use of extraction mixture on the basis of carbamoyl-phosphinoxides - SETFICS [Y.Koma, M. Watanabe, S. Nemoto, Y. Tanaka//Solv. Extr.Ion Exch., 1998, V. 16, N 6, 1357-1367].

[0014] Disadvantage of the above mentioned method is impossibility of separation of americium and curium from all rare-earth elements - the product of actinides (III) contains samarium, europium and gadolinium. Usage of saturated hydrocarbons (n-dodecane) as a diluent leads to the organic phase that has low capacity by metals. Moreover, usage of solution with high concentration of sodium nitrate for back extraction of americium and curium complicates further handling of re-extracts.

[0015] Usage of polar fiuorinated diluent in SETFICS-process [RU 2273507 CI B01D11/00,10.04.2006] increases capacity of the extraction system by metals and prevents formation of third phase.

[0016] The closest prior art to the proposed method is a method of simultaneous extraction of americium and the rare-earth elements and their subsequent separation at the stage of back extraction - modified SETFICS [A.Shadrin, V.Kamachev, I. Kvasnitzky, et al./Proc. Int.Conf. Global 2005, Tsukuba, Japan, Oct. 9-13, paper #129] which is chosen as a prototype method.

[0017] The prototype method comprises simultaneous (collective) extraction of actinides and the rare-earth elements from nitric (nitric acid or nitro acid) radioactive solution with neutral organic compound (extraction agent) solution in polar fiuorinated organic solvent, washing of saturated with metals organic phase, selective back extraction of actinides (III) (americium and curium) and back extraction of the rare-earth metals. Diphenyl-N,N-dibutyl-carbamoyl-methylene-phosphinoxide is used as an extraction agent, meta-nitrobensotrifluoride - as a diluent, and solution composed from 0,05 mol/L complexone and 3 mol/L of salting-out agent - as a solution for back extraction of actinides (III). Diethylene-triamine-pentaacetic acid is used as a complexone and sodium nitrate as a salting-out agent.
Table 1. Results of testing by the prototype method.
ElementConcentration in the product, mg/L
 Initial solutionRaffinateWashing solutionRe-extract TPERe-extract REE
Nd 940 <0.1 6.2 <5 820
Pr 450 <5 5.8 <5 410
EU 28 <1.3 <1.3 90 <1.3
Sm 350 <1.3 3.5 1310 5.5
Gd 480 <1.3 4.8 1720 <2
Ce 930 <1.2 5.4 <5 830
Y 190 <1.2 2.4 710 <2
La 540 <1.3 2.1 <1.3 470
Consumption of the product, ml/h 250±25 325±25 185±15 90±5 390±10


[0018] Disadvantage of the prototype method is incomplete separation of americium and curium from the rare-earth elements. The re-extract of trans-plutonium elements (TPE) contains almost all samarium, europium, gadolinium and yttrium (table 1). Moreover, usage of solution with high concentration of sodium nitrate for back extraction of TPE complicates further handling of re-extracts.

[0019] The problem to be solved by the present invention is ensuring extraction of americium and its full separation from all rare-earth elements in one extraction cycle.

[0020] The corresponding technical effect is the extraction of americium from liquid radioactive solutions and its separation from all rare-earth elements in one extraction cycle.

[0021] The above mentioned technical effect is achieved in a method for extraction of americium from liquid radioactive wastes and its separation from all rare-earth elements that involves simultaneous (collective) extraction of americium and the rare-earth elements from radioactive nitro-acid (nitric) solution with solution of neutral organic extraction agent in polar fluorinated organic solvent, washing of saturated with metals organic phase, selective back extraction of americium. This method is notable for using of N,N,N',N'-tetraalkyl-amide of diglycolic acid as an extraction agent and of solution containing 5-20 g/L of a complexone, 5-60 g/L nitrogen-containing organic acid and 60-240 g/L salting-out agent as a solution for back extraction of americium.

[0022] According to the invention, meta-nitrobenzotrifluoride or trifiuoromethyl phenyl sulfone is used as a polar fluorinated organic solvent.

[0023] According to the invention, as a complexone are used aminopolycarbon acids from the range: diethylene-triamine-pentaacetic acid, ethylene-diamine-tetraacetic acid, nitrilotriacetic acid.

[0024] According to the invention, nitrogen-containing organic acid is chosen from the range of: aminoacetic acid, picolinic acid, nicotinic acid, a-alanine, (3-alanine, valine, norleucine.

[0025] According to the invention, ammonium nitrate is used as a salting-out agent.

[0026] Formulation of the solution for back extraction of americium is chosen on the basis of optimal concentration of a complexone, nitrogen-containing organic acid and salting-out agent in water phase.

[0027] If the concentration of a complexone is less than 5 g/L, of nitrogen-containing organic acid - less than 5 g/L and of salting-out agent - less than 60 g/L, full separation of americium from all rare-earth elements cannot be achieved.

[0028] Increasing of concentration up to 20 g/L of a complexone, 60 g/L of nitrogen-containing organic acid and 240 g/L of salting-out agent, is not reasonable.

[0029] The following examples illustrate the possibilities of applying the proposed method.

Example 1



[0030] Simultaneous extraction of americium and rare-earth elements is carried out as follows. Nitric solution, formulation of which is given in table 2, containing 3 mol/L of nitric acid, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitro-benzo-trifluoride. Phases are separated and factors (coefficients) of distribution of metals are determined. Distribution factors (coefficients) are presented in table 3.
Table 2. Composition of model solution.
MetalLaCePrNdSmEuGdYAm
Concentration, g/L 0.36 0.58 0.06 1.0 0.24 0.06 0.08 0.11 Indicator amounts
Table 3. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 2 5.6 11 20 70 260 110 700 34

Example 2



[0031] Washing of saturated with metals organic phase is carried out to remove the excess of nitric acid. Extract obtained in the example 1 comes into contact with solution containing 240 g/L of ammonium nitrate and 15 g/L of aminoacetic acid. Phases are separated and factors (coefficients) of distribution of metals are determined. Distribution factors (coefficients) are presented in table 4.
Table 4. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 5.0 15 32 54 172 650 270 1450 80

Example 3



[0032] Solution containing 10 g/L of diethylene-triamine-pentaacetic acid, 120 g/L of ammonium nitrate, 60 g/L of picolinic acid, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitro-benzo-trifiuoride. Phases are separated and factors (coefficients) of distribution of metals are determined. Distribution factors are presented in table 5 and separation factors are presented in table 6.
Table 5. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 6.5 7 5 4 5 5.5 7.5 45 0.6
Table 6. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
11 12 9 6 8 9 12 73

Example 4



[0033] Solution containing 10 g/L of diethylene-triamine-pentaacetic acid, 120 g/L of ammonium nitrate, 12 g/L of picolinic acid, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 7 and separation factors are presented in table 8.
Table 7. Factors (coefficients) of distribution of metals
MetalLaCePrNdSmEuGdYAm
D 17 14 8.3 4.2 4.8 5.5 8.1 47 0.7
Table 8. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
24 20 12 6 7 8 12 67

Example 5



[0034] Solution containing 10 g/L of diethylene-triamine-pentaacetic acid, 120 g/L of ammonium nitrate, 7.5 g/L of aminoacetic acid, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 9 and separation factors are presented in table 10.
Table 9. Factors(coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 19.9 14.8 7.5 4.3 4.0 4.5 6.5 35.0 0.7
Table 10. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
27.1 20.1 10.2 5.8 5.4 6.1 8.9 47.5

Example 6



[0035] Solution containing 10 g/L of diethylene-triamine-pentaacetic acid, 120 g/L of ammonium nitrate, 12 g/L of nicotinic acid, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 11 and separation factors are presented in table 12.
Table 11. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 19.6 16.2 8.5 4.8 4.8 5.3 7.5 43.0 0.7
Table 12. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
26.2 21.7 11.4 6.4 6.4 7/1 10.1 57.6

Example 7



[0036] Solution containing 10 g/L of diethylene-triamine-pentaacetic acid, 120 g/L of ammonium nitrate, 15 g/L of ammonium nitrate, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in trifluoromethyl phenyl sulphone. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 13 and separation factors are presented in table 14.
Table 13. Factors (coefficients) of distribution of metals.
MetalYLaCePrNdSmEuGdAm
D 11.5 7.0 5.1 3.3 2.4 1.4 1.5 2.1 0.6
Table 14. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
13 9.1 5.9 4.2 2.5 2.7 3.7 21

Example 8



[0037] Solution containing 5 g/L of diethylene-triamine-pentaacetic acid, 240 g/L of ammonium nitrate, 5 g/L of picolinic acid, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 15 and separation factors are presented in table 16.
Table 15. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 50 58 33 18 15 14 20 115 3.6
Table 16. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
14 16 9 5 4 4 6 32

Example 9



[0038] Solution containing 20 g/L of diethylene-triamine-pentaacetic acid, 240 g/L of ammonium nitrate, 5 g/L of picolinic acid, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 17 and separation factors are presented in table 18.
Table 17. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 27 20 10 5 4 5 7 41 0.9
Table 16. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
30 22 11 6 4 6 8 46

Example 10



[0039] Solution containing 10 g/L of diethylene-triamine-pentaacetic acid, 60 g/L of ammonium nitrate, 5 g/L of picolinic acid, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 19 and separation factors are presented in table 20.
Table 19. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 2.8 2.2 1.1 0/7 0.5 0.6 0.9 5.8 0.1
Table 20. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
28 22 11 7 5 6 9 58

Example 11



[0040] Solution containing 10 g/L of diethylene-triamine-pentaacetic acid, 120 g/L of ammonium nitrate, 9 g/L of a-alanine, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 21 and separation factors are presented in table 22.
Table 21. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 18 4.8 5.5 3.7 2.4 2.8 4.1 22 0.4
Table 22. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
45 12 14 9 6 7 10 55

Example 12



[0041] Solution containing 10 g/L of diethylene-triamine-pentaacetic acid, 120 g/L of ammonium nitrate, 9 g/L of (3-alanine, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 23 and separation factors are presented in table 24.
Table 23. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 25 6.3 6.3 4.2 2.7 3.1 4.6 26 0.5
Table 20. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
50 13 13 8 5 6 9 52

Example 13



[0042] Solution containing 10 g/L of diethylene-triamine-pentaacetic acid, 120 g/L of ammonium nitrate, 12 g/L of valine, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 25 and separation factors are presented in table 26.
Table 25. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 22 6.7 5.4 3.5 2.2 2.6 3.9 21 0.4
Table 26. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
55 17 14 9 6 7 10 53

Example 14



[0043] Solution containing 10 g/L of diethylene-triamine-pentaacetic acid, 120 g/L of ammonium nitrate, 13 g/L of norleucine, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 27 and separation factors are presented in table 28.
Table 27. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 17 5.5 4.4 2.9 1.9 2.1 3.2 18 0.3
Table 28. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
57 18 15 10 6 7 11 60

Example 15



[0044] Solution containing 7 g/L of ethylene-diamine-tetraacetic acid, 120 g/L of ammonium nitrate, 12 g/L of picolinic acid, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 29 and separation factors are presented in table 30.
Table 29. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 17 12 11 13 15 20 25 12 4.3
Table 30. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
4 3 3 3 3 5 6 3

Example 16



[0045] Solution containing 5g/L of nitrilotriacetic acid, 120 g/L of ammonium nitrate, 12 g/L of picolinic acid, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L ofN,N,N',N'-tetraoctyl-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors of distribution of metals are determined. Distribution factors are presented in table 31 and separation factors are presented in table 32.
Table 31. Factors (coefficients) of distribution of metals.
MetalLaCePrNdSmEuGdYAm
D 4.5 5.9 6.0 7.4 10 15 20 42 3.9
Table 32. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
1.2 1.5 1.5 2 3 4 5 11

Example 17



[0046] Solution containing 10 g/L of diethylene-triamine-pentaacetic acid, 120 g/L of ammonium nitrate, 12 g/L of picolinic acid, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, yttrium (10-4 mol/L of each metal) and indicator amounts of americium, pH=2.05, comes into contact with solution containing 0.1 mol/L of N,N,N',N'-tetrabutil-diamide of diglycolic acid in meta-nitrobenzotrifluoride. Phases are separated and factors (coefficients) of distribution of metals are determined. Distribution factors are presented in table 33 and separation factors are presented in table 34.
Table 33. Factors (coefficients) of distribution of rare-earth elements (REE), Am.
MetalLaCePrNdSmEuGdYAm
D 17 9.5 5.3 4.3 3.1 3.7 5.2 28 0.45
Table 34. Separation factors (coefficients).
D(La)/D(Am)D(Ce)/D(Am)D(Pr)/D(Am)D(Nd)/D(Am)D(Sm)/D(Am)D(Eu)/D(Am)D(Gd)/D(Am)D(Y)/D(Am)
34 19 11 9 6 7 10 56


[0047] These examples demonstrate the possibility of applying the proposed method to separate americium from all lanthanides.

[0048] In comparison with the prototype method purification of americium from neutron poisons - samarium, europium and gadolinium is achieved. Moreover, the obtained americium re-extract does not contain indestructible salts.


Claims

1. A method for extraction of americium from liquid radioactive wastes and its separation from rare-earth elements, comprising simultaneous extraction of americium and rare-earth elements from nitric acid radioactive solution with a neutral solution of an organic extracting agent in a polar fluorinated organic solvent, washing an organic phase which is saturated with metals, and selective back extraction of americium, characterized in that
the extracting agent is N,N,N',N'-tetraalkyl-amide of diglycolic acid in a polar fluorinated organic solvent,
the solvent is meta-nitrobenzotrifluoride or trifluoromethyl phenyl sulphone; and
a solution used for back extraction of americium, contains:

5-20 g/L of a complexone selected from diethylenetriamine pentaacetic acid, ethylenediamine tetraacetic acid and nitrilotriacetic acid;

5-60 g/L of a nitrogen containing organic acid selected from aminoacetic acid, picolinic acid, nicotinic acid, α-alanine, β-alanine, valine and norleucine; and

60-240 g/L of a salting-out agent the salting-out agent being ammonium nitrate.


 


Ansprüche

1. Verfahren zum Extrahieren von Americium aus flüssigen radioaktiven Abfällen und dessen Trennung von Seltenerdelementen, umfassend das gleichzeitige Extrahieren von Americium und Seltenerdelementen aus radioaktiver Salpetersäurelösung mit einer neutralen Lösung eines organischen Extraktionsmittels in einem polaren fluorierten organischen Lösungsmittel, Waschen einer mit Metallen gesättigten organischen Phase und selektive Reextraktion von Americium, dadurch gekennzeichnet, dass das Extraktionsmittel N,N,N',N'-Tetraalkylamid der Diglykolsäure in einem polaren fluorierten organischen Lösungsmittel ist, das Lösungsmittel Meta-Nitrobenzotrifluorid oder Trifluormethylphenylsulfon ist; und
eine Lösung, die für die Reextraktion von Americium verwendet wird, enthält:

5-20 g/L eines Komplexons, ausgewählt aus Diethylentriaminpentaessigsäure, Ethylendiamintetraessigsäure und Nitrilotriessigsäure;

5-60 g/L einer stickstoffhaltigen organischen Säure, ausgewählt aus Aminoessigsäure, Picolinsäure, Nikotinsäure, α-Alanin, β-Alanin, Valin und Norleucin; und

60-240 g/L eines Salzagens, wobei das Salzagens Ammoniumnitrat ist.


 


Revendications

1. Procédé d'extraction d'américium de déchets radioactifs liquides et de sa séparation de terres rares, comprenant l'extraction simultanée d'américium et d'éléments de terres rares d'une solution radioactive d'acide nitrique avec une solution neutre d'un agent d'extraction organique dans un solvant organique fluoré polaire, le lavage d'une phase organique qui est saturée de métaux et une rétroextraction sélective d'américium, caractérisé en ce que l'agent d'extraction est le N,N,N',N'-tétraalkylamide de l'acide diglycolique dans un solvant organique fluoré polaire, le solvant est le méta-nitrobenzotrifluorure ou la trifluorométhylphénylsulfone ; et
une solution utilisée pour la rétroextraction d'américium, contient :

5 à 20 g/L d'une complexone choisie parmi l'acide diéthylènetriaminepentaacétique, l'acide éthylènediamine tétraacétique et l'acide nitrilotriacétique ;

5 à 60 g/L d'un acide organique contenant de l'azote choisi parmi l'acide aminoacétique, l'acide picolinique, l'acide nicotinique, l'a-alanine, la β-alanine, la valine et la norleucine ; et

60 à 240 g/L d'un agent de relargage, l'agent de relargage étant du nitrate d'ammonium.


 




REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description




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