Organic-inorganic hybrid material of use for extracting uranium (VI) from aqueous media containing phosphoric acid, processes for preparing same and uses thereof

Patent metadata

Field	Value
Publication number	US-10130932-B2
Application number	US-201314769846-A
Country	US
Kind code	B2
Filing date	Nov 8, 2013
Priority date	Feb 25, 2013
Publication date	Nov 20, 2018
Grant date	Nov 20, 2018

Abstract

The invention relates to an organic-inorganic hybrid material which comprises an inorganic solid support on which are grafted organic molecules of the general formula (I) hereafter:

and relates to methods allowing preparation of this hybrid material as well as to the uses of the hybrid material for extracting uranium(VI) from an aqueous medium comprising phosphoric acid.

First claim

What is claimed is:

1. An organic-inorganic hybrid material, which comprises an inorganic solid support on which is covalently grafted a plurality of organic molecules of formula (I):

wherein:
x, y and z are equal to 0 or 1, with the proviso that at least one of x, y and z is equal to 1;
m is an integer ranging from 1 to 6;
v and w are equal to 0 or 1, with the proviso that v is equal to 1 when w is equal to 0 and v is equal to 0 when w is equal to 1;
if x is equal to 0, R 1 represents a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group comprising from 1 to 12 carbon atoms, and, if x is equal to 1, R 1 represents a group bound to the inorganic solid support through at least one covalent bond represented by the dotted line;
if y is equal to 0, R 2 represents a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group comprising from 1 to 12 carbon atoms, and, if y is equal to 1, R 2 represents a group bound to the inorganic solid support through at least one covalent bond represented by the dotted line;
if z is equal to 0, R 3 represents a hydrogen atom or a linear or branched, saturated or unsaturated hydrocarbon group comprising from 1 to 12 carbon atoms, and, if z is equal to 1, R 3 represents a group bound to the inorganic solid support through at least one covalent bond represented by the dotted line;
R 4 and R 5 represent, independently of each other, a hydrogen atom, a linear or branched, saturated or unsaturated hydrocarbon group comprising from 2 to 8 carbon atoms, or a monocyclic aromatic group.

2. The organic-inorganic hybrid material of claim 1 , wherein the inorganic solid support comprises a metal oxide, a mixed metal oxide, a mixture of metal oxides, or carbon.

3. The organic-inorganic hybrid material of claim 1 , wherein the inorganic solid support is a porous material.

4. The organic-inorganic hybrid material of claim 3 , wherein the porous material is a mesoporous or macroporous material.

5. The organic-inorganic hybrid material of claim 4 , wherein the porous material is a mesoporous silica, a mesoporous titanium oxide, a mesoporous zirconia or a mesoporous carbon.

6. The organic-inorganic hybrid material of claim 5 , wherein the inorganic solid support is a SBA mesoporous silica or a CMK mesoporous carbon.

7. The organic-inorganic hybrid material of claim 1 , wherein R 3 represents —(CH 2 ) q —X 1 — wherein q is an integer ranging from 0 to 12, and X 1 represents a group selected from the group consisting of:

and —CH═CH—.

8. The organic-inorganic hybrid material of claim 1 , wherein at least one of R 1 and R 2 represents a group of formula (a), (b), (c), (d), (e), (f) or (g):
—(CH 2 ) p —C(O)—NH—(CH 2 ) q —X 2 —  (a)

—(CH 2 ) p —NH—C(O)—(CH 2 ) q —X 2 —  (b)

—(CH 2 ) p —C(O)—O—(CH 2 ) q —X 2 —  (c)

—(CH 2 ) p —O—C(O)—(CH 2 ) q —X 2 —  (d)

—(CH 2 ) p —O—(CH 2 ) q —X 2 —  (e)

—(CH 2 ) p -triazole-(CH 2 ) q —X 2 —  (f)

—(CH 2 ) q —X 2 —  (g)

wherein p is an integer ranging from 1 to 6, q is an integer ranging from 0 to 12, and X 2 represents a group selected from the group consisting of:

and —CH═CH—.

9. The organic-inorganic hybrid material of claim 8 , wherein R 3 represents —(CH 2 ) q —X 1 — wherein q is an integer ranging from 0 to 12 and X 1 is identical with X 2 .

10. The organic-inorganic hybrid material of claim 1 , wherein the organic molecules have the formula (Ia):

11. The organic-inorganic hybrid material of claim 10 , wherein x and y are 0, R 1 and R 2 represent, independently of each other, a linear or branched alkyl group comprising from 1 to 12 carbon atoms; z is 1 and R 3 represents a group bound to the inorganic solid support through at least one covalent bond, and R 4 and R 5 represent, independently of each other, a hydrogen atom or a linear or branched alkyl group comprising from 2 to 8 carbon atoms.

12. The organic-inorganic hybrid material of claim 11 , wherein R 1 and R 2 are identical with each other and represent a branched alkyl group comprising from 6 to 12 carbon atoms.

13. The organic-inorganic hybrid material of claim 11 , wherein R 4 and R 5 represent, independently of each other, a hydrogen atom or a linear or branched alkyl group comprising from 2 to 4 carbon atoms.

14. The organic-inorganic hybrid material of claim 10 , wherein the inorganic solid support is based on a metal oxide, a mixed metal oxide or on a mixture of metal oxides and R 3 represents:

wherein q is 1 to 5.

15. The organic-inorganic hybrid material of claim 10 , wherein the inorganic solid support is based on carbon and R 3 represents:

wherein q is 1 to 5.

16. A method for extracting uranium(VI) from an aqueous medium comprising phosphoric acid comprising contacting the aqueous medium with the organic-inorganic hybrid material of claim 1 and then separating the aqueous medium and the organic-inorganic hybrid material.

17. The method of claim 16 , wherein the aqueous medium comprises from 0.012 mol/L to 9 mol/L of phosphoric acid.

18. The method of claim 17 , wherein the aqueous medium results from the attack of a phosphate ore with sulfuric acid.

19. A method for recovering uranium(VI) from an aqueous medium comprising phosphoric acid, comprising:
extraction of uranium(VI) from the aqueous medium, the extraction comprising contacting the aqueous medium with the organic-inorganic hybrid material of claim 1 , and then separating the aqueous medium and the organic-inorganic hybrid material; and
stripping of uranium(VI) from the organic-inorganic hybrid material obtained at the end of the extraction, the stripping comprising contacting the organic-inorganic hybrid material with a basic aqueous solution, and then separating the organic-inorganic hybrid material and the basic aqueous solution.

20. The method of claim 19 , wherein the aqueous medium results from the attack of a phosphate ore with sulfuric acid.

Assignees

• Commissariat Energie Atomique
• Centre Nat Rech Scient
• Univ Montpellier 2 Sciences Et Techniques
• Commissariat Energie Atomique
• Univ Montpellier

Inventors

• El Mourabit Sabah
• Goettmann Frédéric
• Turgis Raphaël
• Grandjean Agnès
• Arrachart Guilhem
• Pellet-Rostaing Stéphane

Classifications

• B01J20/3251 Primary

  comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulphur · CPC title

• B01J20/3259

  comprising at least two different types of heteroatoms selected from nitrogen, oxygen or sulfur with at least one silicon atom · CPC title

• C22B60/0273

  Extraction by titanium containing adsorbents, e.g. by hydrous titanium oxide (C22B60/0269 takes precedence) · CPC title

• B01J45/00

  Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties (ion-exchange chromatography processes B01D15/36) · CPC title

• C22B60/0269

  Extraction by activated carbon containing adsorbents · CPC title