NOVEL ORGANIC MATERIAL FOR EXTRACTING THE URANIUM FROM AN AQUEOUS SOLUTION OF PHOSPHORIC ACID, ASSOCIATED METHODS FOR EXTRACTING AND RETRIEVING THE URANIUM AND A PRECURSOR OF SUCH AN ORGANIC MATERIAL

Abstract

An organic material which includes a solid polymer substrate onto which molecules having the following general formula (I) are grafted:

##STR00001##

The invention also relates to the use of the organic material to extract the uranium (VI) from an aqueous acid solution, to associated methods for extracting and retrieving uranium (VI) as well as to a molecule which is a precursor of the organic material. The disclosure also relates to the use of the organic material to extract the uranium (VI) from an aqueous acid solution, to associated methods for extracting and retrieving uranium (VI) as well as to a molecule which is a precursor of the organic material.

Claims

1. Organic material comprising a solid polymeric substrate on which is covalently grafted a plurality of molecules having the general following (I) below: ##STR00030## where: m is an integer of 0, 1 or 2; R.sup.1 and R.sup.2, the same or different, are a linear or branched, saturated or unsaturated hydrocarbon group having 6 to 12 carbon atoms; R.sup.3 is: a hydrogen atom; a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated hydrocarbon group comprising one or more rings of 3 to 8 carbon atoms, the ring(s) optionally comprising one or more heteroatoms; or an aryl group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; or else R.sup.2 and R.sup.3 together form a group (CH.sub.2).sub.n where n is an integer ranging from 1 to 4; R.sup.4 is: a linear or branched, saturated or unsaturated hydrocarbon group having 2 to 8 carbon atoms; a saturated or unsaturated hydrocarbon group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; or an aromatic group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; and R.sup.5 is: a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated hydrocarbon group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; or a hydrocarbon group comprising an aryl group possibly formed of one or more rings, the ring(s) optionally comprising one or more heteroatoms; R.sup.5 being attached to at least one group G, the group G itself being attached to the solid polymeric substrate by at least one covalent bond (represented by the dotted line), the group G being selected from among an amide group, alkenyl group, alkynyl group, amine group, thioether group, ether-oxide group and 1,2,3-triazole group.

2. The organic material according to claim 1, wherein the plurality of molecules meets the following particular formula (I-a): ##STR00031## where: R.sup.2 is a linear or branched, saturated or unsaturated hydrocarbon group having 6 to 12 carbon atoms; and R.sup.3 is: a hydrogen atom; a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated hydrocarbon group comprising one or more rings of 3 to 8 carbons atoms, the ring(s) optionally comprising one or more heteroatoms; or an aryl group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms.

3. The organic material according to claim 2, wherein the plurality of molecules meets the particular formula (I-a) where m=0 and R.sup.3 is a hydrogen atom.

4. The organic material according to claim 3, wherein the plurality of molecules meets the following particular formula (I-d): ##STR00032## where: n is an integer ranging from 4 to 8 carbon atoms; R.sup.1 and R.sup.2, the same or different, are a linear or branched alkyl group having 6 to 12 carbon atoms; and R.sup.4 is a linear or branched alkyl group having 3 to 6 carbon atoms.

5. The organic material according to claim 1, wherein R.sup.1 and R.sup.2 are each the same and represent a branched alkyl group having 8 to 10 carbon atoms.

6. The organic material according to claim 5, wherein the plurality of molecules meets the following particular formula (I-e): ##STR00033##

7. The organic material according to claim 1, wherein the solid polymeric substrate is formed of a polymer comprising at least one repeat unit selected from among an olefin unit, a unit comprising an aromatic group, an acrylic ester unit and mixtures of these units, this polymer advantageously being a divinylbenzene/styrene copolymer or an acrylic ester polymer.

8. Use of an organic material according to claim 1, to extract uranium(VI) from an aqueous solution comprising phosphoric acid, in particular from a solution resulting from attack of a natural phosphate by sulfuric acid.

9. Method for extracting uranium(VI) from an aqueous solution comprising phosphoric acid, which comprises placing the aqueous solution in contact with an organic material according to claim 1, followed by separation of the aqueous solution and the organic material.

10. Method for recovering uranium(VI) from an aqueous solution comprising phosphoric acid, which comprises: (a) extracting uranium(VI) from the aqueous solution, extraction comprising the placing of the aqueous solution in contact with an organic material according to claim 1, followed by separation of the aqueous solution and the organic material; and (b) stripping the uranium(VI) from the organic material obtained after step (a), stripping comprising the placing in contact of the organic material obtained after step (a) with a basic aqueous solution, followed by separation of the organic material and the basic aqueous solution.

11. The extraction method according to claim 9, wherein the aqueous solution is a solution resulting from attack of a natural phosphate by sulfuric acid.

12. Molecule meeting the following general formula (II): ##STR00034## where: m is an integer of 0, 1 or 2; R.sup.1 and R.sup.2, the same or different, are a linear or branched, saturated or unsaturated hydrocarbon group having 6 to 12 carbon atoms; R.sup.3 is: a hydrogen atom; a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated hydrocarbon group comprising one or rings of 3 to 8 carbon atoms, the ring(s) optionally comprising one or more heteroatoms; or an aryl group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; or else R.sup.2 and R.sup.3 together form a group (CH.sub.2).sub.n where n is an integer ranging from 1 to 4; R.sup.4 is: a linear or branched, saturated or unsaturated hydrocarbon group having 2 to 8 carbons atoms; a saturated or unsaturated hydrocarbon group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; or an aromatic group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; and R.sup.5 is: a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated hydrocarbon group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; or a hydrocarbon group comprising an aryl group possibly formed of one or more rings, the ring(s) optionally comprising one or more heteroatoms; R.sup.5 being attached to at least one group G selected from among a thiol, azide, aldehyde, acyl chloride, alkene group, acetylene group, amine group, hydroxyl group and halide group.

13. The molecule according to claim 12, meeting the following particular formula (II-a): ##STR00035## where: R.sup.2 is a linear or branched, saturated or unsaturated hydrocarbon group having 6 to 12 carbon atoms; and R.sup.3 is: a hydrogen atom; a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated hydrocarbon group comprising one or more rings of 3 to 8 carbon atoms, the ring(s) optionally comprising one or more heteroatoms; or an aryl group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms.

14. The molecule according to claim 13 meeting the particular formula (II-a) where m=0 and R.sup.3 is a hydrogen atom.

15. The molecule according to claim 14 meeting the following particular formula (II-d): ##STR00036## where: n is an integer ranging from 4 to 8 carbon atoms; R.sup.1 and R.sup.2, the same or different, are a linear or branched alkyl group having 6 to 12 carbon atoms; and R.sup.4 is a linear or branched alkyl group having 3 to 6 carbon atoms.

16. The molecule according to claim 12, wherein R.sup.1 and R.sup.2 are each the same and represent a branched alkyl group having 8 to 10 carbon atoms.

17. The molecule according to claim 16 meeting the following particular formula (II-e): ##STR00037##

18. Use of a molecule meeting the following general formula (III): ##STR00038## where: m is an integer of 0, 1 or 2; R.sup.1 and R.sup.2, the same or different, are a linear or branched, saturated or unsaturated hydrocarbon carbon group having 6 to 12 carbon atoms; R.sup.3 is: a hydrogen atom; a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated hydrocarbon group comprising one or more rings of 3 to 8 carbon atoms, the ring(s) optionally comprising one or more heteroatoms; or an aryl group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; or else R.sup.2 and R.sup.3 together form a group (CH.sub.2).sub.n where n is an integer ranging from 1 to 4; R.sup.4 is: a linear or branched, saturated or unsaturated hydrocarbon group having 2 to 8 carbon atoms; a saturated or unsaturated hydrocarbon group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; or an aromatic group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; and R.sup.5 is: a linear or branched, saturated or unsaturated hydrocarbon group having 1 to 12 carbon atoms and optionally one or more heteroatoms; a saturated or unsaturated hydrocarbon group comprising one or more rings, the ring(s) optionally comprising one or more heteroatoms; or a hydrocarbon group comprising an aryl group possibly being formed of one of more rings, the ring(s) optionally comprising one or more heteroatoms; R.sup.5 being attached to at least one group G selected from among a thiol, azide, aldehyde, carboxylic acid, acyl chloride, alkene group, acetylene group, amine group, hydroxyl group and halide group as synthesis precursor of the organic material according to claim 1.

19. The recovery method according to claim 10, wherein the aqueous solution is a solution resulting from attack of a natural phosphate by sulfuric acid.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0167] FIG. 1 schematically illustrates the synthesis of a molecule, denoted 11, meeting general formula (III) where R.sup.1 and R.sup.2 are both a 2-ethylhexyl group denoted EtHex, R.sup.3 is H, R.sup.4 is an n-butyl group denoted Bu, R.sup.5 is a group (CH.sub.2).sub.5 and G is a carboxylic acid C(O)OH. It is specified that in FIG. 1 the methyl group is denoted Me.

[0168] FIG. 2 schematically illustrates the preparation of an organic material of the invention comprising a solid polymeric substrate formed of a functionalised divinylbenzene/styrene copolymer and on which the molecule 11 illustrated in FIG. 1 has been grafted.

DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS

Example 1: Synthesis of a Molecule of the Invention

[0169] The molecule 11 was synthesised in accordance with the reaction scheme illustrated in FIG. 1.

[0170] As illustrated in this FIG. 1, the synthesis of dibutyl 1-(N,N-diethylhexylcarbamoyl)methylphosphonate, on the one hand, and the synthesis of tert-butyl 6-bromohexanoate, on the other hand, were first performed.

[0171] 1.1 Synthesis of Dibutyl 1-(N,N-Diethylhexylcarbamoyl)-Methylphosphonate

[0172] The synthesis of dibutyl 1-(N,N-diethylhexylcarbamoyl)-methylphosphonate can be carried out in particular in accordance with the teaching of document WO 2013/167516, referenced [4], or by implementing steps A and then B of the protocol described in Chapter 1.1 of Example 1 with reference to FIG. 1, or by implementing steps A then B of the protocol described in Chapter 1.2 of this same Example 1 with reference to FIG. 2 of this document [4].

[0173] At a first step, denoted A, 2,2-dithylhexylamine, denoted 1, is caused to react with chloroacetyl chloride, denoted 2, to obtain 2-chloro-N,N-diethylhexylacetamide, denoted 3. This reaction A can particularly be conducted in the presence of dichloromethane and potassium carbonate.

[0174] At a second step, denoted B, 2-chloro-N,N-diethylhexylacetamide 3 is caused to react with tributylphosphite, denoted 4, to obtain dibutyl 1-(N,N-diethylhexylcarbamoyl)methylphosphonate, denoted 5.

[0175] 1.2 Synthesis of Tert-Butyl 6-Bromohexanoate

[0176] This synthesis is conducted in one step, denoted C, by causing 6-bromohexanoic acid, denoted 6, to react in the presence of tert-butanol, denoted 7, with dicyclohexylcarbodiimide (DCC) to obtain tert-butyl 6-bromohexanoate, denoted 8.

[0177] This step C provides protection of the carboxylic acid function of compound 6, thereby minimising secondary reactions.

[0178] 1.3 Synthesis of the Molecule 11

[0179] First, at an alkylation step denoted D, dibutyl 1-(N,N-diethylhexylcarbamoyl)methylphosphonate 5 is caused to react with tert-butyl 6-bromohexanoate 8, previously synthesised, to obtain tert-butyl 1-(N,N-diethylhexyl-7-dibutoxyphosphoryl)-8-oxooctanoate, denoted 9.

[0180] A first saponification step, denoted E, is then performed, to deprotect the carboxylic acid and to obtain 1-(N,N-diethylhexyl-7-dibutoxyphosphoryl)-8-oxooctanoic acid 10, followed by a second mono-saponification step, denoted F, allowing the molecule 11, which corresponds to 1-(N,N-diethylhexyl-7-butoxyhydroxyphosphoryl)-8-oxooctanoic acid, to be obtained.

Example 2: Preparation of an Organic Material of the Invention

[0181] A solid polymeric substrate formed by a divinylbenzene/styrene copolymer was first functionalised with amine functions to obtain the functionalised solid polymeric substrate denoted IV in FIG. 2.

[0182] The molecule 11 was then grafted via peptide coupling onto all or part of the amine functions of the functionalised solid polymeric substrate, to obtain an organic material conforming to the invention and denoted V in FIG. 2.

BIBLIOGRAPHY

[0183] [1] U.S. Pat. No. 4,599,221 [0184] [2] U.S. Pat. No. 4,402,917 [0185] [3] WO 2014/127860 A1 [0186] [4] WO2013/167516 A1