Inorganic ion-exchanger for selective extraction of lithium from lithium-containing natural and industrial brines

1. An inorganic ion-exchanger in the form of solid particles, which comprises a non-stoichiometric compound in the form of a polymeric aqua-oxo-hydroxo complex intended for selective extraction of lithium from lithium-containing natural and industrial brines, and which is represented by the following general formula:

H a NbO (2.5+0.5·a) .c ZrO 2 .d H 2 O,

wherein:

“a” is a number ranging from 0.5 to 1.5,

“c” is a number ranging from 0.01 to 1.0

“d” is a number ranging from 0.1 to 2.0.

2. The inorganic ion-exchanger according to claim 1 , wherein the polymeric aqua-oxo-hydroxo complex is a polymeric aqua-oxo-hydroxo complex of niobium and zirconium in the form of solid particles.

3. The inorganic ion-exchanger according to claim 2 , wherein the polymeric aqua-oxo-hydroxo complex of niobium and zirconium is a mixed polynuclear complex.

4. The inorganic ion-exchanger according to claim 1 , which has a total ion exchange capacity of at least 3.5 meq/g and an ion-exchange capacity specifically to lithium of at least 2.5 meq/g.

5. The inorganic ion-exchanger according to claim 2 , which has a total ion exchange capacity of at least 3.5 meq/g and an ion-exchange capacity specifically to lithium of at least 2.5 meq/g.

6. The inorganic ion-exchanger according to claim 3 , which has a total ion exchange capacity of at least 3.5 meq/g and an ion-exchange capacity specifically to lithium of at least 2.5 meq/g.

7. The inorganic ion-exchanger of claim 1 , wherein the solid particles have dimensions in the range of 0.1 to 2.0 mm.

8. The inorganic ion-exchanger of claim 2 , wherein the solid particles have dimensions in the range of 0.1 to 2.0 mm.

9. The inorganic ion-exchanger of claim 4 , wherein the solid particles have dimensions in the range of 0.1 to 2.0 mm.

10. The inorganic ion-exchanger of claim 6 , wherein the solid particles have dimensions in the range of 0.1 to 2.0 mm.

11. The inorganic ion-exchanger of claim 1 prepared by a method comprising the steps of:

interacting a soluble niobate (V) with an acid that contains at least one zirconium (IV) thus forming a hydrated niobium (V) oxide and a hydrated zirconium (IV) oxide which co-precipitate and form a mixed hydrated niobium mixed hydrated niobium (V) and zirconium (IV) oxide (V) and zirconium (IV) oxide;

granulating the mixed hydrated niobium (V) and zirconium (IV) oxide by freezing with subsequent defreezing thus obtaining a granulated mixed hydrated niobium (V) and zirconium (IV) oxide;

converting the granulated mixed hydrated niobium (V) and zirconium (IV) oxide into a lithium form by treating thereof with a lithium-containing compound selected from the group consisting of an aqueous solution of lithium hydroxide and an aqueous solution of lithium carbonate;

calcining the lithium form of the granulated mixed hydrated niobium (V) and zirconium (IV) oxide to obtain a mixed granulated tripled mixed lithium, niobium (V) and zirconium (IV) oxide which constitutes a lithium-form of the inorganic ion-exchanger; and

converting the lithium-form of the inorganic ion-exchanger into an H-form of the inorganic ion-exchanger by treating thereof with an acid solution.

12. The inorganic ion-exchanger of claim 3 prepared by a method comprising the steps of:

interacting a soluble niobate (V) with an acid that contains at least one zirconium (IV) thus forming a hydrated niobium (V) oxide and a hydrated zirconium (IV) oxide which co-precipitate and form a mixed hydrated niobium mixed hydrated niobium (V) and zirconium (IV) oxide (V) and zirconium (IV) oxide;

granulating the mixed hydrated niobium (V) and zirconium (IV) oxide by freezing with subsequent defreezing thus obtaining a granulated mixed hydrated niobium (V) and zirconium (IV) oxide;

converting the granulated mixed hydrated niobium (V) and zirconium (IV) oxide into a lithium form by treating thereof with a lithium-containing compound selected from the group consisting of an aqueous solution of lithium hydroxide and an aqueous solution of lithium carbonate;

calcining the lithium form of the granulated mixed hydrated niobium (V) and zirconium (IV) oxide to obtain a mixed granulated tripled mixed lithium, niobium (V) and zirconium (IV) oxide which constitutes a lithium-form of the inorganic ion-exchanger; and

converting the lithium-form of the inorganic ion-exchanger into an H-form of the inorganic ion-exchanger by treating thereof with an acid solution.

13. The inorganic ion-exchanger of claim 6 prepared by a method comprising the steps of:

interacting a soluble niobate (V) with an acid that contains at least one zirconium (IV) thus forming a hydrated niobium (V) oxide and a hydrated zirconium (IV) oxide which co-precipitate and form a mixed hydrated niobium mixed hydrated niobium (V) and zirconium (IV) oxide (V) and zirconium (IV) oxide;

granulating the mixed hydrated niobium (V) and zirconium (IV) oxide by freezing with subsequent defreezing thus obtaining a granulated mixed hydrated niobium (V) and zirconium (IV) oxide;

converting the granulated mixed hydrated niobium (V) and zirconium (IV) oxide into a lithium form by treating thereof with a lithium-containing compound selected from the group consisting of an aqueous solution of lithium hydroxide and an aqueous solution of lithium carbonate;

calcining the lithium form of the granulated mixed hydrated niobium (V) and zirconium (IV) oxide to obtain a mixed granulated tripled mixed lithium, niobium (V) and zirconium (IV) oxide which constitutes a lithium-form of the inorganic ion-exchanger; and

converting the lithium-form of the inorganic ion-exchanger into an H-form of the inorganic ion-exchanger by treating thereof with an acid solution.

14. The inorganic ion-exchanger of claim 8 prepared by a method comprising the steps of:

interacting a soluble niobate (V) with an acid that contains at least one zirconium (IV) thus forming a hydrated niobium (V) oxide and a hydrated zirconium (IV) oxide which co-precipitate and form a mixed hydrated niobium mixed hydrated niobium (V) and zirconium (IV) oxide (V) and zirconium (IV) oxide;

granulating the mixed hydrated niobium (V) and zirconium (IV) oxide by freezing with subsequent defreezing thus obtaining a granulated mixed hydrated niobium (V) and zirconium (IV) oxide;

converting the granulated mixed hydrated niobium (V) and zirconium (IV) oxide into a lithium form by treating thereof with a lithium-containing compound selected from the group consisting of an aqueous solution of lithium hydroxide and an aqueous solution of lithium carbonate;

calcining the lithium form of the granulated mixed hydrated niobium (V) and zirconium (IV) oxide to obtain a mixed granulated tripled mixed lithium, niobium (V) and zirconium (IV) oxide which constitutes a lithium-form of the inorganic ion-exchanger; and

converting the lithium-form of the inorganic ion-exchanger into an H-form of the inorganic ion-exchanger by treating thereof with an acid solution.

15. The inorganic ion-exchanger of claim 10 prepared by a method comprising the steps of:

interacting a soluble niobate (V) with an acid that contains at least one zirconium (IV) thus forming a hydrated niobium (V) oxide and a hydrated zirconium (IV) oxide which co-precipitate and form a mixed hydrated niobium mixed hydrated niobium (V) and zirconium (IV) oxide (V) and zirconium (IV) oxide;

granulating the mixed hydrated niobium (V) and zirconium (IV) oxide by freezing with subsequent defreezing thus obtaining a granulated mixed hydrated niobium (V) and zirconium (IV) oxide;

converting the granulated mixed hydrated niobium (V) and zirconium (IV) oxide into a lithium form by treating thereof with a lithium-containing compound selected from the group consisting of an aqueous solution of lithium hydroxide and an aqueous solution of lithium carbonate;

calcining the lithium form of the granulated mixed hydrated niobium (V) and zirconium (IV) oxide to obtain a mixed granulated tripled mixed lithium, niobium (V) and zirconium (IV) oxide which constitutes a lithium-form of the inorganic ion-exchanger; and

converting the lithium-form of the inorganic ion-exchanger into an H-form of the inorganic ion-exchanger by treating thereof with an acid solution.