Lithium extraction with coated ion exchange particles
The present invention relates to the extraction of lithium from liquid resources such as natural and synthetic brines, leachate solutions from minerals, and recycled products.
1. A method of extracting lithium from a liquid resource, comprising:
(a) contacting a coated ion exchange particle comprising an ion exchange material and a coating material, with a liquid resource to produce lithiated coated ion exchange particles; and
(b) treating the lithiated coated ion exchange particles with an acid solution to produce a salt solution comprising lithium ions,
wherein the ion exchange material is selected from the group consisting of Li 4 Mn 5 O 12 , Li 4 Ti 5 O 12 , Li 2 TiO 3 , Li 2 MnO 3 , Li 2 SnO 3 , LiMn 2 O 4 , Li 1.6 Mn 1.6 O 4 , LiAlO 2 , LiCuO 2 , LiTiO 2 , Li 4 TiO 4 , Li 7 Ti 11 O 24 , Li 3 VO 4 , Li 2 Si 3 O 7 , LiFePO 4 , LiMnPO 4 , Li 2 CuP 2 O 7 , Al(OH) 3 , LiCl.xAl(OH) 3 .yH 2 O, SnO 2 .xSb 2 O 5 .yH 2 O, TiO 2 .xSb 2 O 5 .yH 2 O, solid solutions thereof, and combinations thereof; wherein x is from 0.1-10; and y is from 0.1-10; and
wherein the coating material comprises TiO 2 , ZrO 2 , MoO 2 , SnO 2 , Nb 2 O 5 , Ta 2 O 5 , Li 2 TiO 3 , SiO 2 , Li 2 ZrO 3 , Li 2 MoO 3 , LiNbO 3 , LiTaO 3 , AlPO 4 , LaPO 4 , ZrSiO 4 , ZrP 2 O 7 , MoP 2 O 7 , Mo 2 P 3 O 12 , BaSO 4 , AlF 3 , SiC, TiC, ZrC, Si 3 N 4 , ZrN, BN, carbon, graphitic carbon, amorphous carbon, solid solutions thereof, or a combination thereof.
2. The method of claim 1 , wherein the salt solution further comprises an impurity derived from the coated ion exchange particle.
3. The method of claim 2 , wherein the impurity is present in a concentration of about 1 ppb to about 10 ppm.
4. The method of claim 1 , wherein the liquid resource is a natural brine, a dissolved salt flat, seawater, concentrated seawater, a desalination effluent, a concentrated brine, a processed brine, an oilfield brine, a liquid from an ion exchange process, a liquid from a solvent extraction process, a synthetic brine, a leachate from an ore or combination of ores, a leachate from a mineral or combination of minerals, a leachate from a clay or combination of clays, a leachate from recycled products, a leachate from recycled materials, or combinations thereof.
5. The method of claim 1 , wherein the acid solution comprises hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, chloric acid, perchloric acid, nitric acid, formic acid, acetic acid, or combinations thereof.
6. The method of claim 1 , wherein the coating material limits dissolution of the ion exchange material.
7. The method of claim 1 , wherein the coating material allows diffusion of lithium ions and hydrogen ions to and from the ion exchange material.
8. The method of claim 1 , wherein the ion exchange material is selected from the group consisting of Li 4 Mn 5 O 12 , Li 4 Ti 5 O 12 , Li 2 TiO 3 , Li 2 MnO 3 , Li 2 SnO 3 , LiMn 2 O 4 , Li 1.6 Mn 1.6 O 4 , LiTiO 2 , Li 4 TiO 4 , Li 7 Ti 11 O 24 , LiFePO 4 , and LiMnPO 4 .
9. The method of claim 1 , wherein the ion exchange material is selected from the group consisting of Li 4 Mn 5 O 12 , Li 2 MnO 3 , LiMn 2 O 4 , Li 1.6 Mn 1.6 O 4 , and LiMnPO 4 .
10. The method of claim 1 , wherein the ion exchange material is selected from the group consisting of Li 4 Ti 5 O 12 , Li 2 TiO 3 , LiTiO 2 , Li 4 TiO 4 , and Li 7 Ti 11 O 24 .
11. The method of claim 1 , wherein the ion exchange material is selected from the group consisting of Li 2 SnO 3 and LiFePO 4 .
12. The method of claim 1 , wherein the coating material comprises TiO 2 , ZrO 2 , MoO 2 , Li 2 TiO 3 , SiO 2 , Li 2 ZrO 3 , Li 2 MoO 3 , LiNbO 3 , ZrSiO 4 , AlF 3 , SiC, Si 3 N 4 , graphitic carbon, amorphous carbon, solid solutions thereof, or a combination thereof.
13. The method of claim 1 , wherein the coating material comprises TiO 2 , ZrO 2 , or SiO 2 .
14. The method of claim 1 , wherein the ion exchange material is selected from the group consisting of Li 4 Mn 5 O 12 , Li 4 Ti 5 O 12 , Li 2 TiO 3 , Li 2 MnO 3 , Li 2 SnO 3 , LiMn 2 O 4 , Li 1.6 Mn 1.6 O 4 , LiTiO 2 , Li 4 TiO 4 , Li 7 Ti 11 O 24 , LiFePO 4 , and LiMnPO 4 , and the coating material comprises TiO 2 , ZrO 2 , or SiO 2 .
15. The method of claim 1 , wherein the ion exchange material is selected from the group consisting of Li 4 Mn 5 O 12 , Li 2 MnO 3 , LiMn 2 O 4 , Li 1.6 Mn 1.6 O 4 , and LiMnPO 4 , and the coating material comprises TiO 2 , ZrO 2 , or SiO 2 .
16. The method of claim 1 , wherein the ion exchange material is selected from the group consisting of Li 4 Ti 5 O 12 , Li 2 TiO 3 , LiTiO 2 , Li 4 TiO 4 , and Li 7 Ti 11 O 24 , and the coating material comprises TiO 2 , ZrO 2 , or SiO 2 .
17. The method of claim 1 , wherein the ion exchange material is selected from the group consisting of Li 2 SnO 3 and LiFePO 4 , and the coating material comprises TiO 2 , ZrO 2 , or SiO 2 .
18. The method of claim 1 , wherein the coated ion exchange particle has an average diameter from about 20 μm to about 200 μm.
19. The method of claim 1 , wherein the coated ion exchange particle has an average diameter of less than 100 μm.
20. The method of claim 1 , wherein the coated ion exchange particle has an average diameter of less than 60 μm.
21. The method of claim 1 , wherein the coated ion exchange particle has an average diameter of less than 30 μm.
22. The method of claim 1 , wherein the coated ion exchange particle has an average diameter of less than 20 μm.