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US-20260124556-A1 - LITHIUM RECOVERY USING AQUEOUS SOURCES

US20260124556A1US 20260124556 A1US20260124556 A1US 20260124556A1US-20260124556-A1

Abstract

Described herein are methods of recovering lithium from dilute lithium sources. The methods include concentrating a dilute aqueous lithium source to yield an extraction feed having an extraction lithium concentration; extracting lithium from the extraction feed using direct lithium extraction in an extraction stage to yield a lithium intermediate; concentrating a stream obtained from the lithium intermediate in a concentration stage to yield a lithium concentrate; and converting lithium in the lithium concentrate to lithium hydroxide.

Inventors

  • Gary W. Sams
  • Dominic Vincent PERRONI
  • Prasanna Nirgudkar
  • Florence Binet
  • Rod William Shampine
  • Sandeep Verma
  • Wenlin Zhang

Assignees

  • SCHLUMBERGER TECHNOLOGY CORPORATION

Dates

Publication Date
20260507
Application Date
20251217
Priority Date
20221201

Claims (17)

  1. 1 - 13 . (canceled)
  2. 14 . A method of recovering lithium from an aqueous lithium source, comprising: separating lithium using a lithium selective electrochemical separation process; and concentrating lithium using a concentration process comprising counter-flow reverse osmosis operation.
  3. 15 . The method of claim 14 , wherein the counter-flow reverse osmosis operation receives an effluent of the lithium selective electrochemical separation process or a derivative thereof.
  4. 16 . The method of claim 14 , including concentrating the aqueous lithium source using the concentration process to obtain an extraction feed, wherein the lithium selective electrochemical separation process receives the extraction feed or a derivative thereof.
  5. 17 . The method of claim 14 , wherein the counter-flow reverse osmosis process comprises flowing a stream to be concentrated into a plurality of units in series, each unit having a semi-permeable membrane defining a first volume where first material collects and a second volume where second material collects, wherein material from the first volume of a first unit is routed to the first volume of a second unit in series with the first unit, and material from the second volume of the first unit is routed to a third unit in series with the first unit in a counter-flow direction with the material from the first volume.
  6. 18 . The method of claim 14 , further comprising, prior to concentrating lithium using a counter-flow reverse osmosis process, forming a preconcentrated lithium stream and a low TDS stream using a reverse osmosis process, and routing the preconcentrated lithium stream to the counter-flow reverse osmosis operation.
  7. 19 . The method of claim 20 , including recycling the low TDS stream to the lithium selective electrochemical separation process.
  8. 20 . The method of claim 18 , including recycling the low TDS stream.
  9. 21 . The method according to claim 14 , wherein the concentration process is configured so that the lithium concentrate has a TDS over 120,000 mg/l.
  10. 22 . The method according to claim 14 , wherein the concentration process is configured so that the lithium concentrate has a TDS over 200,000 mg/l
  11. 23 . The method according to claim 14 , including treating an effluent of the lithium selective electrochemical separation process or a derivative thereof in an impurity stage to remove impurities and to form a purified lithium stream.
  12. 24 . The method according to claim 23 , wherein the impurity stage includes one or more of the following operations: impurity precipitation, solids removal and divalent impurity selective removal.
  13. 25 . The method of claim 14 , further comprising converting lithium in an effluent of the separation or concentration process or a derivative thereof to form a lithium product.
  14. 26 . The method of claim 18 , wherein the low TDS stream has TDS below 2,000 mg/l.
  15. 27 . The method of claim 14 , wherein the counterflow reverse osmosis process includes flowing a first stream to be concentrated into a plurality of units in series, each unit having a semi-permeable membrane defining a first volume and a second volume, wherein a second stream flows sequentially into the second volume of each unit counter-current to the first stream.
  16. 28 . The method of claim 28 in combination with claim 18 , wherein the second stream exiting the plurality of second volumes is a dilute brine stream, the method comprising recycling the dilute brine stream into a reverse osmosis operation.
  17. 29 . The method of claim 14 , wherein the concentration process includes pressurizing the input stream to the counter-flow reverse osmosis operation.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This patent application claims benefit of United States Provisional Patent Application Ser. No. 63/364,142 filed May 4, 2022, which is entirely incorporated herein by reference, and from Application Serial No. 63/374,441 filed Sep. 2, 2022, which is entirely incorporated herein by reference, and from International Application No. PCT/US 2022/051500, filed Dec. 1, 2022, which is entirely incorporated herein by reference. FIELD This patent application describes methods and apparatus for lithium recovery from aqueous sources. Specifically, effective processes for concentrating and recovering lithium from dilute sources are described. BACKGROUND Lithium is a key element in energy storage. Electrical storage devices, such as batteries, supercapacitors, and other devices commonly use lithium to mediate the storage and release of chemical potential energy as electrical current. As demand for renewable, but non-transportable, energy sources such as solar and wind energy grows, demand for technologies to store energy generated using such sources also grows. According to the United States Geological Survey, global reserves of lithium total 22 million tons (metric) of lithium content, with Chile, Australia, Argentina, and China accounting for about 85% of global reserves. U.S. Geological Survey, Mineral Commodity Summaries, January 2022. According to S&P Global Market Intelligence, lithium supply is forecast to be 636 kT LCE in 2022, up from 497 kT in 2021. Global consumption was estimated at 64 kT in 2021, putting current lithium supplies in deficit. Global consumption and is expected to reach 2 MTa by 2030 for an average annual growth in demand of approximately 13.5%. Supply is currently forecast to run behind demand, and lithium prices currently outstrip even the most optimistic forecasts. While lithium prices are quite volatile as the global market develops, lithium prices are expected to remain high through 2030. The incentive for more lithium production could not be clearer. Lithium extraction from brine has become a favored method of lithium recovery. Heretofore, most development has been focused on brine sources with relatively high concentrations of lithium, but other more dilute sources are also plentiful. Effective and efficient processes for recovering lithium from dilute sources are needed. SUMMARY The disclosure relates to a method of recovering lithium from a lithium source, comprising extracting lithium from an extraction feed using direct lithium extraction in an extraction stage to yield a lithium intermediate; concentrating the lithium intermediate in an impurity preparation stage to yield an impurity stage feed; and treating the impurity stage feed in an impurity stage to remove impurities and to form a purified lithium stream. The disclosure also relates to a method of recovering lithium from an aqueous lithium source, comprising separating lithium using a lithium selective electrochemical separation process; and concentrating lithium using a concentration process comprising counter-flow reverse osmosis operation. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic process diagram of a lithium recovery process according to one embodiment. FIG. 2 is a schematic diagram of a vaporizer usable during a concentration stage of the process shown in FIG. 1 FIG. 3 is a schematic process diagram of a concentration stage of a lithium recovery process according to one embodiment. FIG. 4 is a schematic process diagram of a portion of a concentration stage of a lithium recovery process according to another embodiment. FIG. 5 is a schematic process diagram of an extraction stage according to one embodiment. FIG. 6A-6C are schematic process diagrams of a lithium recovery process according to additional embodiments. FIG. 7 is a schematic process diagram of a portion of a lithium recovery process. DETAILED DESCRIPTION Direct extraction of lithium is commonly used in lithium recovery from aqueous lithium sources. Some direct extraction processes employ a solid material to withdraw lithium selectively from a lithium source onto or into the withdrawal material. A recovery fluid is then contacted with the loaded withdrawal material to remove the lithium from the withdrawal material to form a lithium intermediate stream. The quantity of recovery fluid generally determines the concentration of lithium in the lithium intermediate stream, but unloading rate of ions from the withdrawal material can provide an effective upper limit to the concentration achievable. In ion withdrawal, the withdrawal material is generally chosen to be selective to lithium. That may mean that many types of cations are removed from the source, but lithium is removed more readily than other cations. Thus, the ions removed by the withdrawal material include lithium possibly along with other impurities, such as monovalent cations sodium and potassium and divalent cations calcium and magnesium. Longer recov