Compounds with phosphine oxide and amine functions, useful as uranium (VI) ligands, and uses thereof, in particular for extracting uranium(VI) from aqueous solutions of sulphuric acid

Patent metadata

Field	Value
Publication number	US-10183959-B2
Application number	US-201615564053-A
Country	US
Kind code	B2
Filing date	Apr 1, 2016
Priority date	Apr 3, 2015
Publication date	Jan 22, 2019
Grant date	Jan 22, 2019

Abstract

The invention relates to compounds which correspond to the general formula (I) below:

in which: R 1 and R 2 represent, independently of one another, a C 4 to C 12 acyclic hydrocarbon group; R 3 represents H; a C 1 to C 12 acyclic hydrocarbon group with optionally one or more heteroatoms; a C 5 or C 6 cyclic hydrocarbon group; or a 5- or 6-membered heterocyclic group; R 4 represents H or a C 1 to C 12 acyclic hydrocarbon group with optionally one or more heteroatoms; R 5 and R 6 represent, independently of one another, H; a C 1 to C 12 acyclic hydrocarbon group with optionally one or more heteroatoms; a C 5 or C 6 cyclic hydrocarbon group; or a 5- or 6-membered heterocyclic group; on the condition however that R 5 and R 6 do not each represent H.

The invention also relates to the uses of these compounds as uranium(VI) ligands, in particular for extracting uranium(VI) from an aqueous solution of sulphuric acid, and also to a method that makes it possible to recover the uranium(VI) present in an aqueous solution of sulphuric acid resulting from the attack of a uranium ore by sulphuric acid and using said the compounds.

First claim

The invention claimed is:

1. A method for extracting uranium(VI) from an aqueous solution of sulphuric acid, comprising contacting the aqueous solution with an organic solution comprising a compound of formula (I):

in which:
R 1 and R 2 represent, independently of one another, a saturated or unsaturated, acyclic hydrocarbon group comprising 4 to 12 carbon atoms;
R 3 represents a hydrogen atom; a saturated or unsaturated, acyclic hydrocarbon group comprising 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated, cyclic hydrocarbon group with 5 or 6 carbon atoms; or a saturated or unsaturated, 5- or 6-membered heterocyclic group;
R 4 represents a hydrogen atom or a saturated or unsaturated, acyclic hydrocarbon group comprising 1 to 12 carbon atoms and optionally one or more heteroatoms;
R 5 and R 6 represent, independently of one another, a hydrogen atom; a saturated or unsaturated, acyclic hydrocarbon group comprising 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated, cyclic hydrocarbon group with 5 or 6 carbon atoms; or a saturated or unsaturated, 5- or 6-membered heterocyclic group; wherein R 5 and R 6 do not each represent a hydrogen atom;
and then separating the aqueous solution from the organic solution.

2. The method of claim 1 , in which R 1 and R 2 each represent a linear or branched alkyl group comprising 6 to 12 carbon atoms.

3. The method of claim 2 , in which R 1 and R 2 are identical to each other and each represent a linear or branched alkyl group comprising 8 to 10 carbon atoms.

4. The method of claim 1 , in which R 3 represents a linear or branched alkyl group comprising 1 to 12 carbon atoms.

5. The method of claim 1 , in which R 4 represents a hydrogen atom or a linear or branched alkyl group comprising 1 to 12 carbon atoms.

6. The method of claim 1 , in which R 5 and R 6 each represent a linear or branched alkyl group comprising 1 to 12 carbon atoms, or a cycloalkyl group.

7. The method of claim 1 , in which:
R 1 , R 2 and R 3 each represent an n-octyl group, R 4 represents a hydrogen atom and R 5 and R 6 each represent a 2-ethylhexyl group; or
R 1 and R 2 each represent a 2-ethylhexyl group, R 3 represents an n-octyl group, R 4 represents a hydrogen atom and R 5 and R 6 each represent a 2-ethylhexyl group; or
R 1 , R 2 and R 3 each represent an n-octyl group, R 4 represents a hydrogen atom and R 5 and R 6 each represent an n-octyl group; or
R 1 and R 2 each represent an n-octyl group, R 3 represents a 2,4,4-trimethylpentyl group, R 4 represents a hydrogen atom and R 5 and R 6 each represent an n-octyl group; or
R 1 and R 2 each represent an n-octyl group, R 3 represents a 2,4,4-trimethylpentyl group, R 4 represents a hydrogen atom and R 5 and R 6 each represent a 2-ethylhexyl group.

8. The method of claim 1 , in which the aqueous solution comprises 0.01 mol/L to 2 mol/L of sulphuric acid.

9. The method of claim 1 , in which the organic solution comprises 0.01 mol/L to 0.25 mol/L of the compound in an organic diluent.

10. The method of claim 1 , in which the aqueous solution is derived from the lixiviation of a uranium ore by sulphuric acid.

11. A method for recovering the uranium present in an aqueous solution of sulphuric acid derived from the lixiviation of a uranium ore by sulphuric acid, comprising:
a) an extraction of uranium, in oxidation state VI, from the aqueous solution, the extraction comprising contacting the aqueous solution with an organic phase comprising a compound of formula (I):

in which:
R 1 and R 2 represent, independently of one another, a saturated or unsaturated, acyclic hydrocarbon group comprising 4 to 12 carbon atoms;
R 3 represents a hydrogen atom; a saturated or unsaturated, acyclic hydrocarbon group comprising 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated, cyclic hydrocarbon group with 5 or 6 carbon atoms; or a saturated or unsaturated, 5- or 6-membered heterocyclic group;
R 4 represents a hydrogen atom or a saturated or unsaturated, acyclic hydrocarbon group comprising 1 to 12 carbon atoms and optionally one or more heteroatoms;
R 5 and R 6 represent, independently of one another, a hydrogen atom; a saturated or unsaturated, acyclic hydrocarbon group comprising 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated, cyclic hydrocarbon group with 5 or 6 carbon atoms; or a saturated or unsaturated, 5- or 6-membered heterocyclic group; wherein R 5 and R 6 do not each represent a hydrogen atom; then separating the aqueous solution from the organic phase; and
b) a stripping of uranium(VI) from the organic phase obtained at the end of a), the stripping comprising contacting the organic phase with an aqueous solution comprising at least one carbonate, then separating the organic phase from the aqueous solution.

12. The method of claim 11 , in which the organic phase of a) comprises 0.01 mol/L to 0.25 mol/L of the compound in solution in an organic diluent.

13. The method of claim 11 , in which the aqueous solution of sulphuric acid comprises 0.1 g/L to 8 g/L of uranium, 0.1 mol/L to 2 mol/L of sulphate ions and 0.01 mol/L to 2 mol/L of sulphuric acid.

14. The method of claim 11 , in which:
a volumetric ratio between the organic phase and the aqueous solution of sulphuric acid less than or equal to 1 is used at a); and/or
a volumetric ratio between the organic phase and the aqueous solution of carbonate greater than or equal to 1 is used at b).

15. A compound of formula (I):

in which:
R 1 and R 2 represent, independently of one another, a saturated or unsaturated, acyclic hydrocarbon group comprising 4 to 12 carbon atoms;
R 3 represents a saturated or unsaturated, acyclic hydrocarbon group comprising 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated, cyclic hydrocarbon group with 5 or 6 carbon atoms; or a saturated or unsaturated, 5- or 6-membered heterocyclic group;
R 4 represents a hydrogen atom or a saturated or unsaturated, acyclic hydrocarbon comprising 1 to 12 carbon atoms and optionally one or more heteroatoms;
R 5 and R 6 represent, independently of one another, a hydrogen atom; a saturated or unsaturated, acyclic hydrocarbon group comprising 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated, cyclic hydrocarbon group with 5 or 6 carbon atoms; or a saturated or unsaturated, 5- or 6-membered heterocyclic group; wherein R 5 and R 6 do not each represent a hydrogen atom.

16. The compound of claim 15 , in which R 1 and R 2 each represent a linear or branched alkyl group comprising 6 to 12 carbon atoms.

17. The compound of claim 16 , in which R 1 and R 2 are identical to each other and each represent a linear or branched alkyl group comprising 8 to 10 carbon atoms.

18. The compound of claim 15 , in which R 3 represents a linear or branched alkyl group comprising 1 to 12 carbon atoms.

19. The compound of claim 15 , in which R 4 represents a hydrogen a

Assignees

• Commissariat A Grave Over Lenergie Atomique Et Aux Energies Alternatives
• Centre Nat Rech Scient
• Univ Montpellier
• Commissariat Energie Atomique

Inventors

• Pellet-Rostaing Stéphane
• Leydier Antoine
• Arrachart Guilhem
• Turgis Raphaël
• Dubois Véronique

Classifications

• C22B60/0243

  phosphorated ion as active agent · CPC title

• C07F9/5304 Primary

  Acyclic saturated phosphine oxides or thioxides · CPC title

• C22B60/026

  liquid-liquid extraction with or without dissolution in organic solvents · CPC title

• Y02P10/234

  Cross-Sectional Technologies · mapped topic

• C22B3/0005

  Chemistry & Metallurgy · mapped topic