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US-12623914-B2 - Process for selective adsorption and recovery of lithium from natural and synthetic brines

US12623914B2US 12623914 B2US12623914 B2US 12623914B2US-12623914-B2

Abstract

This invention relates generally to a process for selective adsorption and recovery of lithium from natural and synthetic brines, and more particular to a process for recovering lithium from a natural or synthetic brine solution by passing the brine solution through a lithium selective adsorbent in a continuous countercurrent adsorption and desorption circuit.

Inventors

  • Charles R. Marston
  • Michael J. Garska

Assignees

  • ILIAD IP COMPANY, LLC

Dates

Publication Date
20260512
Application Date
20250118

Claims (20)

  1. 1 . A process for recovering lithium from a brine solution, the process comprising: concentrating the lithium in the brine solution by cyclically and sequentially flowing the brine solution through a continuous countercurrent adsorption and desorption (CCAD) circuit to form an enhanced lithium product stream, wherein the CCAD circuit comprises a plurality of process zones, each process zone comprises an adsorbent bed or column containing a lithium selective adsorbent; recovering the enhanced lithium product stream using a lithium-containing eluant solution or a portion of a lithium product eluate; and recycling heat from one or more heat exchangers or steam to the CCAD circuit.
  2. 2 . The process of claim 1 further comprising passing the eluant solution or the product eluate through the process zones and stripping a portion of the lithium from the lithium selective adsorbent.
  3. 3 . The process of claim 1 , wherein the eluant solution is a fresh eluant solution or a recycled eluant solution.
  4. 4 . The process of claim 1 , wherein the eluant solution or the portion of the lithium product eluate comprises LiCl and water at a concentration of up to about 1000 mg/kg lithium and at temperatures of about 5° C. to about 100° C.
  5. 5 . The process of claim 1 , wherein the lithium-containing eluant solution or the portion of the lithium product eluate has a lithium concentration of between about 100 mg/kg and about 300 mg/kg in water.
  6. 6 . The process of claim 1 , wherein the CCAD circuit further comprises a rotary multi-port valve system having the plurality of process zones.
  7. 7 . The process of claim 6 , wherein fluid flow through the CCAD circuit is controlled by pumping flow rates, predetermined indexing, or a combination of both of the multi-port valve system.
  8. 8 . The process of claim 7 , wherein the fluid flow through the CCAD circuit is in a direction countercurrent to the adsorbent beds or columns.
  9. 9 . The process of claim 1 further comprising dewatering and concentrating the enhanced lithium product stream to produce a concentrated enhanced lithium product stream and a recycled eluant solution.
  10. 10 . The process of claim 9 further comprising: selectively softening the enhanced lithium product stream to form a softened enhanced lithium product stream; selectively dewatering the softened enhanced lithium product stream to form a partially concentrated enhanced lithium product stream and a permeate solution; and selectively concentrating the partially concentrated enhanced lithium product stream to form the concentrated enhanced lithium product stream and a condensate solution.
  11. 11 . The process of claim 10 , wherein the concentrated enhanced lithium product stream has a concentration from about 5000 to about 30,000 mg/kg lithium.
  12. 12 . The process of claim 10 further comprising: selectively removing calcium, magnesium, and/or boron from the enhanced lithium product stream to form the softened enhanced lithium product stream; selectively concentrating the softened enhanced lithium product stream using reverse osmosis to form the partially concentrated enhanced lithium product stream and the permeate solution; and selectively concentrating the partially concentrated enhanced lithium product stream using evaporation to form the concentrated enhanced lithium product stream and the condensate solution.
  13. 13 . The process of claim 10 further comprising selectively converting the lithium in the concentrated enhanced lithium product stream to lithium carbonate, lithium hydroxide, or both.
  14. 14 . The process of claim 10 further comprising evaporating the partially concentrated enhanced lithium product stream using a portion of the heat from the heat exchangers or the steam to form the concentrated enhanced lithium product stream and the condensate solution.
  15. 15 . The process of claim 14 further comprising supplying the steam from geothermal operations and/or a boiler.
  16. 16 . The process of claim 1 further comprising the step of recycling at least a portion of one or more of the enhanced lithium product stream, a concentrated enhanced lithium product stream, a recycled eluant solution, the lithium product eluate, a permeate solution, a condensate solution, a mother liquor, a centrate solution, or a combination or mixture thereof to one or more of the process zones.
  17. 17 . The process of claim 16 , wherein the condensate solution is a heated steam condensate solution and/or the permeate solution is a heated reverse osmosis permeate solution.
  18. 18 . The process of claim 1 , wherein the plurality of process zones are configured in parallel, in series, or in combinations of parallel and series, flowing either in up flow or down flow modes.
  19. 19 . The process of claim 18 , wherein the plurality of process zones further comprises: a brine displacement zone positioned upstream with respect to fluid flow of a lithium loading zone; said lithium loading zone positioned upstream with respect to said fluid flow of and in fluid communication with a strip displacement zone; said strip displacement zone positioned upstream with respect to fluid flow of and in fluid communication with a lithium strip zone; and said lithium strip zone in fluid communication with said brine displacement zone.
  20. 20 . The process of claim 19 further comprising passing the brine solution through the loading zone for a predetermined amount of contact time.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to and is a continuation application of U.S. patent application Ser. No. 18/603,997, filed Mar. 13, 2024, which is a divisional application of U.S. patent application Ser. No. 18/191,152, filed Mar. 28, 2023, now U.S. Pat. No. 11,958,753, issued on Apr. 16, 2024, which claims priority to and is a continuation application of U.S. patent application Ser. No. 17/844,689, filed Jun. 20, 2022, which claims priority to and is a divisional application of U.S. patent application Ser. No. 16/402,931, filed May 3, 2019, now U.S. Pat. No. 11,365,128, issued Jun. 21, 2022, which claims the benefit of U.S. Provisional Patent Application No. 62/671,489 filed on May 15, 2018 and also is a continuation-in-part of U.S. patent application Ser. No. 16/010,286 filed on Jun. 15, 2018, now U.S. Pat. No. 10,604,414, issued on Mar. 31, 2020, which claims the benefit of U.S. Provisional Patent Application No. 62/520,024 filed on Jun. 15, 2017 and the benefit of U.S. Provisional Patent Application No. 62/671,489 filed on May 15, 2018. This application incorporates each of the foregoing applications by reference into this document as if fully set out at this point. BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates generally to a process for selective adsorption and recovery of lithium from natural and synthetic brines, and more particular to a process for recovering lithium from a natural or synthetic brine solution by contacting the brine solution with a lithium selective adsorbent using a continuous countercurrent adsorption and desorption (“CCAD”) process. 2. Description of the Related Art Seawater contains about 0.17 mg/kg, and subsurface brines may contain up to 4,000 mg/kg, more than four orders of magnitude greater than sea water. Typical commercial lithium concentrations are between 200 and 1,400 mg/kg. In 2015, subsurface brines yielded about half of the world's lithium production. The Salton Sea Known Geothermal Resource Area (“SSKGRA”) has the most geothermal capacity potential in the United States. Geothermal energy, the harnessing of heat radiating from the beneath the Earth's crust, is a renewable resource that is capable of cost-effectively generating large amounts of power. In addition, the SSKGRA has the potential to become North America's prime sources of alkali metals, alkaline earth metals and transition metals, such as lithium, potassium, rubidium, iron, zinc and manganese. Brines from the Salton Sea Known Geothermal Resource Area are unusually hot (up to at least 390° C. at 2 km depth), hypersaline (up to 26 wt. %), and metalliferous (iron (Fe), zinc (Zn), lead (Pb), copper (Cu)). The brines are primarily sodium (Na), potassium (K), calcium (Ca) chlorides with up to 25 percent of total dissolved solids. While the chemistry and high temperature of the Salton Sea brines have led to the principal challenges to the development of the SSKGA, lithium and other brine elements typically maintain high commodity value and are used in a range of industrial and technological applications. The “lithium triangle” of Chile, Argentina and Bolivia is where approximately 75% of the world's lithium comes from. Chile is currently the second largest producer of lithium carbonate and lithium hydroxide, which are key raw materials for producing lithium-ion batteries, behind only Australia. Salar de Atacama is one of the hottest, driest, windiest and most inhospitable places on Earth, and the largest operations are in the shallow brine beneath the Salar de Atacama dry lakebed in Chile, which as of 2015, yielded about a third of the world's supply. The Atacama in Chile is ideal for lithium mining because the lithium-containing brine ponds evaporate quickly, and the solution is concentrated into high-grade lithium products like lithium carbonate and lithium hydroxide. Mining lithium in the salars of Chile and Argentina is much more cost-effective than hard rock mining where the lithium is blasted from granite pegamite orebodies containing spodumene, apatite, lepidolite, tourmaline and amblygonite. The shallow brine beneath the Salar de Uyuni in Bolivia is thought to contain the world's largest lithium deposit, often estimated to be half or more of the world's resource; however, as of 2015, no commercial extraction has taken place, other than a pilot plant. The mining of lithium from brine resources in the “lithium triangle” historically depends upon easy access to large amounts of fresh water and very high evaporation rates. With the declining availability of fresh water and climate change, the economic advantage of conventional processing techniques is disappearing. Fixed-bed and continuous countercurrent ion exchange (“CCIX”) systems have been used to recover metals, such as nickel (Ni) and cobalt (Co), from ore leach solutions. While fixed-bed systems are generally used in recovery projects, they are known to require relatively large am