Carbamides for separating uranium(VI) and plutonium(IV) without reducing the plutonium(IV)
The use of carbamides as extractants for fully or partially separating uranium(VI) from plutonium(IV) in an aqueous solution obtained by dissolving a spent nuclear fuel in nitric acid, by method of liquid-liquid extraction, without carrying out any reduction of the plutonium(IV) to plutonium(III). The invention also relates to new carbamides. Uses are the processing of spent nuclear fuels based on uranium (especially uranium oxides—UOX) or uranium and plutonium (especially mixed uranium and plutonium oxides—MOX).
1. A method for totally or partially separating uranium(VI) from plutonium(IV), without reducing plutonium(IV) to plutonium(III), from an aqueous solution A1 issued from the dissolution of a spent nuclear fuel in nitric acid, comprising:
a) a co-extraction of uranium(VI) and plutonium(IV) from the aqueous solution A1, the co-extraction comprising at least one contacting, in an extractor, of the aqueous solution with an organic solution S1 comprising a carbamide as an extractant in an organic diluent, followed by separating the aqueous solution from the organic solution, the carbamide being of formula(I):
wherein:
R 1 , R 2 and R 3 , identical or different, represent a linear or branched alkyl group, comprising from 1 to 12 carbon atoms, a cycloalkyl group comprising from 3 to 12 carbon atoms or a cycloalkylalkyl group comprising from 4 to 13 carbon atoms;
R 4 represents a hydrogen atom, a linear or branched alkyl group, comprising from 1 to 12 carbon atoms, a cycloalkyl group comprising from 3 to 12 carbon atoms or a cycloalkylalkyl group comprising from 4 to 13 carbon atoms;
b) a stripping of plutonium(IV) and a fraction of uranium(VI) from the organic solution issued from a), the stripping comprising at least one contacting, in an extractor, of the organic solution with an aqueous solution A2 comprising from 0.1 mol/L to 0.5 mol/L of nitric acid, followed by separating the organic solution from the aqueous solution; and
c) an extraction of all or part of the uranium(VI) fraction present in the aqueous solution issued from b), the extraction comprising at least one contacting, in an extractor, of the aqueous solution with an organic solution S2 comprising the carbamide in an organic diluent, followed by separating the aqueous solution from the organic solution;
whereby an aqueous solution comprising plutonium(IV) without uranium(VI) or a mixture of plutonium(IV) and uranium(VI), and an organic solution comprising uranium(VI) without plutonium(IV) are obtained.
2. The method of claim 1 , in which the carbamide comprises a total number of carbon atoms between 17 and 25.
3. The method of claim 1 , in which R 1 , R 2 , R 3 and R 4 represent a linear or branched alkyl group, comprising from 1 to 12 carbon atoms.
4. The method of claim 1 , in which R 1 and R 2 are identical and represent a linear or branched alkyl group, comprising from 1 to 5 carbon atoms, R 3 and R 4 are identical and represent a linear or branched alkyl group, comprising from 6 to 10 carbon atoms, and the carbamide comprises a total number of carbon atoms equal to 19, 21 or 23.
5. The method of claim 1 , in which R 1 and R 4 are identical and represent a linear or branched alkyl group, comprising from 1 to 5 carbon atoms, R 2 and R 3 are identical et represent a linear or branched alkyl group, comprising from 6 to 10 carbon atoms, and the carbamide comprises a total number of carbon atoms equal to 19, 21 or 23.
6. The method of claim 1 , in which R 1 , R 2 , R 3 and R 4 are identical and represent a linear or branched alkyl group comprising from 4 to 8 carbon atoms.
7. The method of claim 1 , in which R 1 , R 2 and R 3 represent a linear or branched alkyl group, comprising from 1 to 12 carbon atoms and R 4 represents a hydrogen atom.
8. The method of claim 1 , in which R 1 , R 2 and R 3 are identical and represent a linear or branched alkyl group, comprising from 6 to 8 carbon atoms.
9. The method of claim 1 , in which the carbamide is N,N,N′-tri-n-octylurea, N,N,N′-tri(2-ethylhexyl)urea, N,N-di(2-ethylhexyl)-N′-n-octylurea, N,N,N′,N′-tetra-n-butylurea, N,N,N′,N′-tetra-n-pentylurea, N,N,N′,N′-tetra-n-hexylurea, N,N,N′,N′-tetra-n-octylurea, N,N′-di-n-butyl-N,N′-di-n-hexylurea, N,N′-di-n-heptyl-N,N′-di-n-propylurea, N,N′-diethyl-N,N′-di-n-octylurea or N,N′-dimethyl-N,N′-di-n-nonylurea.
10. The method of claim 1 , in which the organic solutions S1 and S2 comprise from 0.5 mol/L to 2 mol/L of the carbamide.
11. The method of claim 1 , in which a) further comprises a decontamination of the organic solution issued from the co-extraction of uranium(VI) and plutonium(IV) with respect of americium, curium and fission products, the decontamination comprising at least one contacting, in an extractor, of the organic solution with an aqueous solution A3 comprising from 1 mol/L to 6 mol/L of nitric acid, followed by separating the organic solution from the aqueous solution.
12. The method of claim 1 , in which the contacting, in the extractor of b), of the organic solution issued from a) with the aqueous solution A2 comprises a counterflow circulation of the organic solution and the aqueous solution A2 with a flow rate ratio O/A which is greater than 1.
13. The method of claim 1 , which further comprises a stripping of uranium(VI) from the organic solution issued from c), the stripping comprising at least one contacting of the organic solution with an aqueous solution A5 comprising at most 0.05 mol/L of nitric acid, followed by separating the organic solution from the aqueous solution.