U.S. patent number 10,648,090 [Application Number 16/366,697] was granted by the patent office on 2020-05-12 forintegrated system for lithium extraction and conversion. This patent grant is currently assigned to LILAC SOLUTIONS, INC.. The grantee listed for this patent is Lilac Solutions, Inc.. Invention is credited to Alexander John Grant, David Henry Snydacker, Ryan Ali Zarkesh.
| United States Patent | 10,648,090 |
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| Snydacker , et al. | May 12, 2020 |
Integrated system for lithium extraction and conversion
AbstractThe present invention relates to the extraction of lithium from liquid resources, such as natural and synthetic brines, leachate solutions from clays and minerals, and recycled products.
| Inventors: | Snydacker; David Henry(San Francisco, CA), Grant; Alexander John(San Francisco, CA), Zarkesh; Ryan Ali(Richmond, CA) |
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| Applicant: | | Name | City | State | Country | Type |
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Lilac Solutions, Inc. |
Middletown |
RI |
US |
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| Assignee: | LILAC SOLUTIONS, INC.(Middletown, RI) |
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| Family ID: | 67617630 |
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| Appl. No.: | 16/366,697 |
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| Filed: | March 27, 2019 |
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Prior Publication Data
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| Document Identifier | Publication Date |
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| US 20190256987 A1 | Aug 22, 2019 |
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Related U.S. Patent Documents
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| Application Number | Filing Date | Patent Number | Issue Date |
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| PCT/US2019/017885 | Feb 13, 2019 |
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| 62781515 | Dec 18, 2018 |
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| 62631688 | Feb 17, 2018 |
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| Current U.S. Class: | 1/1 |
| Current CPC Class: | B01D 9/0018 (20130101); B01J 39/12 (20130101); B01J 39/10 (20130101); B01D 9/0054 (20130101); C01D 15/02 (20130101); B01D 9/0004 (20130101); B01J 39/07 (20170101); B01D 61/422 (20130101); B01J 39/19 (20170101); C25B 9/10 (20130101); B01D 61/58 (20130101); C01D 15/08 (20130101); B01D 9/0059 (20130101); B01D 15/362 (20130101); B01J 39/09 (20170101); B01J 39/05 (20170101); B01D 61/44 (20130101); B01J 47/016 (20170101); C25B 1/46 (20130101); B01J 39/02 (20130101); B01D 2311/04 (20130101); B01D 61/025 (20130101); B01D 9/0063 (20130101); B01D 2311/2642 (20130101); B01D 2311/2669 (20130101); C01P 2004/61 (20130101); B01D 2311/2623 (20130101); B01D 2009/0086 (20130101); B01D 2311/2673 (20130101); B01D 2311/2684 (20130101); B01D 9/0036 (20130101) |
| Current International Class: | B01D 15/36 (20060101); B01J 39/09 (20170101); B01J 39/02 (20060101); B01D 9/00 (20060101); B01D 61/42 (20060101); B01J 39/10 (20060101); B01J 39/05 (20170101); B01J 47/016 (20170101); B01J 39/19 (20170101); B01J 39/07 (20170101); C01D 15/02 (20060101); C25B 1/46 (20060101); C25B 9/10 (20060101); B01J 39/12 (20060101); B01D 61/02 (20060101) |
References Cited[Referenced By]U.S. Patent DocumentsForeign Patent Documents
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| 101961634 |
| Feb 2011 |
| CN |
| 102872792 |
| Jan 2013 |
| CN |
| 103794779 |
| May 2014 |
| CN |
| 3034781 |
| Oct 2014 |
| FR |
| 5898021 |
| Apr 2016 |
| JP |
| WO-2016064689 |
| Apr 2016 |
| WO |
| WO-2016172017 |
| Oct 2016 |
| WO |
| WO-2017005113 |
| Jan 2017 |
| WO |
| WO-2017020090 |
| Feb 2017 |
| WO |
| WO-2017137885 |
| Aug 2017 |
| WO |
| WO-2018089932 |
| May 2018 |
| WO |
| WO-2019028148 |
| Feb 2019 |
| WO |
| WO-2019028174 |
| Feb 2019 |
| WO |
|
Other References
Chitrakar et al. Lithium recovery from salt lake brine by H2TiO3. Dalton Trans 43:8933-8939 (2014). cited by applicant .
Chitrakar et al. Selective Uptake of Lithium Ion from Brine by H1.33Mn1.67O4 and H1.6Mn1.6O4. Chem Lett 41:1647-1649 (2012). cited by applicant .
Cho et al. High-Performance ZrO2-Coated LiNiO2 Cathode Material. Electrochem Solid-State Lett 4(10):A159-A161 (2001). cited by applicant .
Department of Energy. Ion Exchange Materials for Lithium Extraction (Topic: 15, Subtopic:e)--Abstract. Available at https://www.sbir.gov/sbirsearch/detail/1307793 (3 pgs.) (2017). cited by applicant .
Larumbe et al. Effect of a SiO2 coating on the magnetic properties of Fe3O4 nanoparticles. JPhys: Condens Matter 24(26):266007 (2012). cited by applicant .
Nishihama et al. Selective recovery process of lithium from seawater using integrated ion exchange methods. Solvent Extraction and Ion Exchange 29:421-431 (2011). cited by applicant .
Oh et al. Double Carbon Coating of LiFePO4 as High Rate Electrode for Rechargeable Lithium Batteries. Adv. Mater. 22:4842-4845 (2010). cited by applicant .
Pareja et al. Corrosion behaviour of zirconia barrier coatings on galvanized steel. Surface and Coatings Technology 200(22-23):6606-6610 (2006). cited by applicant .
Patel et al. Ionic and electronic conductivities of atomic layer deposition thin film coated lithium ion battery cathode particles. RSC Advances 6:98768-98776 (2016). cited by applicant .
PCT/US2017/061384 International Search Report and Written Opinion dated Feb. 14, 2018. cited by applicant .
PCT/US2018/044821 International Search Report and Written Opinion dated Oct. 12, 2018. cited by applicant .
PCT/US2018/044868 International Search Report and Written Opinion dated Mar. 6, 2019. cited by applicant .
Tarakina et al. Defect crystal structure of new TiO(OH)2 hydroxide and related lithium salt Li2TiO3. Dalton Trans 39:8168-8176 (2010). cited by applicant .
U.S. Appl. No. 15/811,415 Office Action dated May 24, 2018. cited by applicant .
U.S. Appl. No. 16/052,381 Office Action dated Nov. 1, 2018. cited by applicant .
Co-pending U.S. Appl. No. 16/409,643, filed May 10, 2019. cited by applicant .
PCT/US2019/017885 International Search Report and Written Opinion dated Jun. 14, 2019. cited by applicant .
PCT/US2019/019780 International Search Report and Written Opinion dated Jun. 14, 2019. cited by applicant. |
Primary Examiner:Jain; Salil
Attorney, Agent or Firm:Wilson Sonsini Goodrich & Rosati
Parent Case TextCROSS-REFERENCE
This application is a continuation of International Application No. PCT/US2019/017885, which claims the benefit of U.S. Provisional Application Ser. No. 62/631,688, filed Feb. 17, 2018; and U.S. Provisional Application Ser. No. 62/781,515, filed Dec. 18, 2018; each of which is incorporated herein by reference in its entirety.
ClaimsWhat is claimed is:
1. An integrated process for generating a lithium salt from a liquid resource, comprising: (a) providing an ion exchange unit, wherein said ion exchange unit comprises ion exchange particles comprising hydrogen ions; (b) contacting said ion exchange particles in said ion exchange unit with said liquid resource, wherein hydrogen ions from said ion exchange particles are exchanged with lithium ions from said liquid resource to produce lithium-enriched ion exchange particles in said ion exchange unit; (c) treating said lithium-enriched ion exchange particles with an acid solution, wherein lithium ions from said lithium-enriched ion exchange particles are exchanged with hydrogen ions from said acid solution to produce a lithium eluate; (d) optionally providing a first crystallizer to treat said lithium eluate of step (c) with a precipitant to precipitate said lithium salt and create a residual eluate; (e) providing an electrolysis system in fluid communication with said ion exchange unit or in fluid communication with said first crystallizer, wherein said electrolysis system comprises (A) one or more electrochemically reducing electrodes, (B) one or more electrochemically oxidizing electrodes, and (C) one or more ion-conducting membranes; (f) (i) passing said lithium eluate from step (c) to said electrolysis system, or (ii) passing said residual eluate from step (d) to said electrolysis system; (g) (i) subjecting said lithium eluate from step (c) in said electrolysis system of step (e) to an electric current, wherein said electric current causes electrolysis of said lithium eluate from step (c) to produce an acidified solution and a lithium salt solution, or (ii) subjecting said residual eluate from step (d) to said electrolysis system of step (e) to an electric current, wherein said electric current causes electrolysis of said residual eluate to produce an acidified solution and a basified solution; and (h) optionally providing a second crystallizer to crystallize said lithium salt solution of step (g)(i) to form said lithium salt; wherein said ion exchange particles comprise coated ion exchange particles and said coated ion exchange particles comprise an ion exchange material and a coating material comprising a chloro-polymer, a fluoro-polymer, a chloro-fluoro-polymer, a hydrophilic polymer, a hydrophobic polymer, co-polymers thereof, mixtures thereof, or combinations thereof.
2. The integrated process of claim 1, wherein step (b) further comprises pH modulation, wherein said pH modulation maintains an equilibrium in favor of hydrogen ions from said hydrogen-rich ion exchange particles being exchanged with lithium ions from said liquid resource.
3. The integrated process of claim 2, wherein said basified solution of step (g)(ii) is cycled back into the ion exchange unit of step (b) for pH modulation.
4. The integrated process of claim 1, wherein said acidified solution of step (g)(i) is cycled back into the ion exchange unit of step (c) to produce said lithium eluate.
5. The integrated process of claim 1, wherein said acidified solution of step (g)(ii) is cycled back into the ion exchange unit of step (c) to produce said lithium eluate.
6. The integrated process of claim 1, wherein said lithium salt is lithium carbonate, lithium bicarbonate, lithium hydroxide, lithium chloride, lithium bromide, lithium sulfate, lithium bisulfate, lithium phosphate, lithium hydrogen phosphate, lithium dihydrogen phosphate, or lithium nitrate.
7. The integrated process of claim 1, wherein said 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.
8. The integrated process of claim 1, wherein said ion exchange particles further comprise uncoated ion exchange particles and said uncoated ion exchange particles comprise an ion exchange material.
9. The integrated process of claim 8, wherein said ion exchange material of said coated ion exchange particles and said ion exchange material of said uncoated ion exchange particles are independently selected from the group consisting of LiFePO.sub.4, LiMnPO.sub.4, Li.sub.2TiO.sub.3, Li.sub.2MnO.sub.3, Li.sub.2SnO.sub.3, Li.sub.4Ti.sub.5O.sub.12, Li.sub.4Mn.sub.5O.sub.12, LiMn.sub.2O.sub.4, Li.sub.1.6Mn.sub.1.6O.sub.4, LiAlO.sub.2, LiCuO.sub.2, LiTiO.sub.2, Li.sub.4TiO.sub.4, Li.sub.7Ti.sub.11O.sub.24, Li.sub.3VO.sub.4, Li.sub.2Si.sub.3O.sub.7, Li.sub.2CuP.sub.2O.sub.7, Al(OH).sub.3, LiCl.xAl(OH).sub.3.yH.sub.2O, SnO.sub.2.xSb.sub.2O.sub.5.yH.sub.2O, TiO.sub.2.xSb.sub.2O.sub.5.yH.sub.2O, solid solutions thereof, and combinations thereof; wherein x is from 0.1-10 and y is from 0.1-10.
10. The integrated process of claim 1, wherein said one or more ion-conducting membranes are one or more cation-conducting membranes or one or more anion-conducting membranes.
11. The integrated process of claim 10, wherein said one or more cation-conducting membranes or said one or more anion-conducting membranes comprise sulfonated tetrafluoroethylene-based fluoropolymer-copolymer, sulfonated tetrafluoroethylene, sulfonated fluoropolymer, sulfonated styrene-divinylbenzene polymer, co-polymers thereof, or combinations thereof.
12. The integrated process of claim 10, wherein said one or more anion-conducting membranes comprise a functionalized polymer structure.
13. The integrated process of claim 1, wherein said polymer structure comprises polyarylene ethers, polysulfones, polyether ketones, polyphenylenes, perfluorinated polymers, polybenzimidazole, polyepichlorohydrins, unsaturated polypropylene, polyethylene, polystyrene, polyvinylbenzyl chlorides, polyphosphazenes, polyvinyl alcohol, polytetrafluoroethylene, polyvinyl chloride, polyvinylidene fluoride, alterations of these polymers or other kinds of polymers, or composites thereof.
14. The integrated process of claim 1, wherein said one or more ion-conducting membranes have a thickness from about 1 .mu.m to about 1000 .mu.m.
15. The integrated process of claim 1, wherein said one or more ion-conducting membranes have a thickness from about 1 mm to about 10 mm.
16. The integrated process of claim 1, wherein said one or more electrochemically reducing electrodes and said one or more electrochemically oxidizing electrodes are comprised of titanium, niobium, zirconium, tantalum, magnesium, titanium dioxide, oxides thereof, or combinations thereof.
17. The integrated process of claim 16, wherein said one or more electrochemically reducing electrodes and said one or more electrochemically oxidizing electrodes further comprise a coating of platinum, TiO.sub.2, ZrO.sub.2, Nb.sub.2O.sub.5, Ta.sub.2O.sub.5, SnO.sub.2, IrO.sub.2, RuO.sub.2, mixed metal oxides, graphene, derivatives thereof, or combinations thereof.
18. The integrated process of claim 1, wherein said electrolysis system comprises one or more electrochemical cells, one or more electrodialysis cells, or combinations thereof.
19. The integrated process of claim 1, wherein said electrolysis system further produces one or more gases that are processed into said acidified solution.
20. The integrated process of claim 1, wherein said electrolysis system further produces one or more gases that are combusted to generate heat.
DescriptionBACKGROUND OF THE INVENTION
Lithium is an essential element for high-energy rechargeable batteries and other technologies. Lithium can be found in a variety of liquid solutions, including natural and synthetic brines and leachate solutions from minerals and recycled products.
SUMMARY OF THE INVENTION
Lithium can be extracted from liquid resources using an ion exchange process based on inorganic ion exchange materials. Inorganic ion exchange materials absorb lithium ions from a liquid resource while releasing hydrogen ions, and then elute lithium ions in acid while absorbing hydrogen ions. The ion exchange process can be repeated to extract lithium ions from a liquid resource and yield a concentrated lithium ion solution. The concentrated lithium ion solution can be further processed into chemicals for the battery industry or other industries.
One aspect described herein is an integrated process for generating a purified lithium concentrate from a liquid resource, comprising: a) providing an ion exchange unit, wherein said ion exchange unit comprises an ion exchange material; b) contacting said ion exchange material in said ion exchange unit with said liquid resource, wherein hydrogen ions from said ion exchange material are exchanged with lithium ions from said liquid resource to produce a lithium-enriched ion exchange material in said ion exchange unit; c) treating said lithium-enriched ion exchange material with an acid solution, wherein said lithium ions from said lithium-enriched ion exchange material are exchanged with hydrogen ions from said acid solution to produce a lithium eluate; d) providing a membrane cell in fluid communication with said ion exchange unit, wherein said membrane cell comprises (i) a first compartment containing an electrochemically reducing electrode, (ii) a second compartment containing an electrochemically oxidizing electrode, and (iii) an ion-conducting membrane separating said first compartment from said second compartment; e) passing said lithium eluate to said membrane cell; f) subjecting said lithium eluate in said membrane cell to an electric current, wherein said electric current causes electrolysis of said lithium eluate to produce an acidified solution and said purified lithium concentrate; and g) recycling said acidified solution from said membrane cell to said ion exchange unit of c).
In one embodiment, said lithium-enriched ion exchange material is treated in said ion exchange unit. In one embodiment, said lithium eluate is produced in said ion exchange unit. In one embodiment, said lithium eluate is passed from said ion exchange unit to said membrane cell.
In one embodiment, wherein prior to b), said ion exchange material in said ion exchange unit is treated with an acid solution to produce a hydrogen-enriched ion exchange material in said ion exchange unit. In one embodiment, wherein b) further comprises pH modulation, wherein said pH modulation maintains an equilibrium in favor of hydrogen ions from said hydrogen-rich ion exchange material being exchanged with lithium ions from said liquid resource. In one embodiment, said process further comprises treating said lithium-enriched ion exchange material with a base in addition to said acid solution. In one embodiment, the base is Ca(OH).sub.2 or NaOH.
In one embodiment, said process further comprises providing a reverse osmosis unit in fluid communication with said ion exchange unit and said membrane cell, and said reverse osmosis unit comprises a water-permeable membrane. In one embodiment, wherein prior to d), said lithium eluate is passed into said reverse osmosis unit contacting said water-permeable membrane, and wherein water molecules from said lithium eluate pass through said water-permeable membrane to produce water and a concentrated lithium eluate. In one embodiment, said concentrated lithium eluate is further subjected to d) to g).
In one embodiment, said water-permeable membrane comprises polyamide, aromatic polyamide, polyvinylamine, polypyrrolidine, polyfuran, polyethersulfone, polysulfone, polypiperzine-amide, polybenzimidazoline, polyoxadiazole, acetylated cellulose, cellulose, a polymer with alternative functionalization of sulfonation, carboxylation, phosphorylation, or combinations thereof, other polymeric layer, or combinations thereof. In one embodiment, said water-permeable membrane further comprises a fabric, polymeric, composite, or metal support.
