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WO2024228907A1 - Préparation de carbonate de lithium et d'hydroxyde de lithium - Google Patents

Préparation de carbonate de lithium et d'hydroxyde de lithium Download PDF

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Publication number
WO2024228907A1
WO2024228907A1 PCT/US2024/026320 US2024026320W WO2024228907A1 WO 2024228907 A1 WO2024228907 A1 WO 2024228907A1 US 2024026320 W US2024026320 W US 2024026320W WO 2024228907 A1 WO2024228907 A1 WO 2024228907A1
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WO
WIPO (PCT)
Prior art keywords
lithium
column
sodium
hydroxide
hydroxide solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/US2024/026320
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English (en)
Inventor
John L. Burba
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
International Battery Metals Ltd
Original Assignee
International Battery Metals Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US18/644,735 external-priority patent/US20240367989A1/en
Application filed by International Battery Metals Ltd filed Critical International Battery Metals Ltd
Publication of WO2024228907A1 publication Critical patent/WO2024228907A1/fr
Anticipated expiration legal-status Critical
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

Definitions

  • the present disclosure generally relates to preparing lithium carbonate and lithium hydroxide.
  • aspects of the present disclosure relate to preparing battery-grade lithium carbonate and lithium hydroxide using an ion exchange resin.
  • Geothermal brines which are hot water or steam containing dissolved minerals that are extracted from the Earth’s subsurface during geothermal energy production, offer several benefits.
  • geothermal brines can be a source of renewable energy.
  • geothermal brines can be a potential source of lithium, which may be used in batteries for electric vehicles, electronics, and energy storage systems.
  • some geothermal brines can contain dissolved lithium, which can be extracted through a series of extraction and purification steps.
  • FIG. 1 illustrates an example system for preparing lithium carbonate and lithium hydroxide, according to some examples of the present disclosure
  • FIG. 2 illustrates an example workflow for preparing lithium carbonate and lithium hydroxide, according to some examples of the present disclosure.
  • lithium carbonate can be prepared from lithium-containing brines or lithium minerals through a series of chemical processes.
  • lithium-containing brines or minerals that are mined can be processed at high temperatures to produce lithium oxide (Li2O).
  • the resulting lithium oxide can then be reacted with water to form lithium hydroxide (LiOH), which can be treated with sodium carbonate (soda ash) in solution such as a lithium chloride solution (LiCl).
  • LiOH lithium hydroxide
  • sodium carbonate sodium carbonate
  • LiCl lithium chloride solution
  • the sodium carbonate reagent is derived from Trona (Na3H(CO3)2-H2O), which is a naturally occurring mineral that contains impurities such as calcium, magnesium, sulfate, and so on. Due to such impurities, the crude lithium carbonate product needs to be filtered with substantial washing to remove soluble salts. As such, it is necessary for lithium carbonate to undergo multiple washings to improve the purity.
  • the lithium carbonate from the above-described process can be slurried in water and pumped into a pressure vessel where CO2 is injected. This induces a reaction in which the CO2 reacts with the carbonate ions, forming lithium bicarbonate (LiHCC ), which is very soluble.
  • This solution can be passed through ion exchange columns under pressure. Impurities such as calcium and magnesium are exchanged for sodium and removed from the solution.
  • Impurities such as calcium and magnesium are exchanged for sodium and removed from the solution.
  • purified lithium carbonate precipitates When the CO2 gas is vented from the vessel and as the CO2 leaves the vessel, purified lithium carbonate precipitates. The lithium carbonate precipitates can be then filtered, washed, dried, sized, and/or packaged.
  • this process involves numerous steps and can be expensive.
  • lithium carbonate in order to produce lithium hydroxide, lithium carbonate can be mixed in boiling water under pressure with slaked lime (e.g., calcium hydroxide). Calcium from the lime may react with carbonate from the lithium carbonate to produce impure lithium hydroxide and calcium carbonate waste.
  • the impure slurry can be filtered and washed with water to capture residual lithium hydroxide.
  • the lithium hydroxide solution is then evaporated and crystallized to remove the impurities. The process of evaporation, crystallization, and filtration can be repeated multiple times to acquire battery-grade lithium hydroxide. If the lithium carbonate and lime have poor quality, it may be necessary to recrystallize lithium hydroxide numerous times to produce lithium hydroxide monohydrate (LiOH H2O) of battery-quality.
  • LiOH H2O lithium hydroxide monohydrate
  • Described herein are systems, processes (also referred to as methods), and techniques for preparing purified lithium salts such as lithium carbonate and/or lithium hydroxide from a lithium-containing solution.
  • the systems and techniques of the present disclosure can prepare, from a lithium-containing solution (e.g., geothermal brines), purified lithium carbonate and/or lithium hydroxide using an ion exchange resin.
  • the present disclosure can add an aqueous composition comprising lithium ions (e.g., a lithium-based solution such as lithium chloride solution) into a column, which contains ion exchange resins saturated with sodium.
  • lithium ions displace sodium in the column and therefore, sodium salts (e.g., sodium chloride) exit the column and the column is loaded with lithium.
  • the lithium-loaded column can be washed with water to remove any residual sodium salts from the column.
  • a concentrated sodium hydroxide solution can be introduced to the lithium-loaded column. Due to a high concentration of the sodium hydroxide solution, sodium ions start to displace lithium from the column. As such, the resulting output of the column includes a lithium hydroxide solution.
  • the resulting lithium hydroxide solution can be evaporated and crystallized to form high-purity lithium hydroxide monohydrate crystals.
  • the lithium hydroxide solution can be reacted with pure carbon dioxide to produce high-purity lithium carbonate.
  • the carbon dioxide can be supplied from CO2 emissions from gas-fired equipment.
  • aspects of the present disclosure can improve the extraction of lithium from lithium- containing brines/minerals and the preparation of lithium salts such as lithium carbonate and lithium hydroxide of sufficient purity to produce high-purity and battery-grade lithium metal. Since mineral reagents such as soda ash (sodium carbonate) and lime that contain impurities are not consumed in the present disclosure, the systems and technologies of the present disclosure can significantly avoid product contamination. Further, since membrane or electronic grade sodium hydroxide and pure CO2 are readily available. As such, the present disclosure can improve the efficiency and productivity of preparing lithium carbonate and lithium hydroxide.
  • the systems and technologies of the present disclosure can be modularized and incorporated in a mobile extraction train such as a modular system (e.g., a modular extraction system) for extracting desired chemical species including lithium, specific lithium species, and/or other chemical compounds from input flows in a modular unit.
  • a modular system e.g., a modular extraction system
  • desired chemical species including lithium, specific lithium species, and/or other chemical compounds from input flows in a modular unit.
  • the present disclosure has exemplary applicability in the Modular Extraction Apparatus described in U.S. Patent No. 11,229,880.
  • FIG. 1 illustrates an example system 100 for preparing lithium carbonate and lithium hydroxide.
  • system 100 includes a column 110 (also referred to as a resin column, an ion exchange resin bed, etc.).
  • the column 110 can be a pulsed column, separation column, or any applicable column that liquid can flow through.
  • column 110 can be prepared with a strong acid ion exchange resin (e.g., Dowex 50), which is saturated with sodium.
  • a lithium-based solution e.g., lithium chloride
  • lithium ions displace sodium.
  • sodium salts e.g., sodium chloride
  • the lithium-loaded column 110 can be washed with clean water to remove any residual sodium salts (e.g., sodium chloride).
  • any residual sodium salts e.g., sodium chloride.
  • a sodium hydroxide solution (concentrated) can be introduced into the lithium-loaded column 110.
  • a high concentration of the sodium hydroxide solution leads to sodium ions displacing lithium from column 110.
  • lithium hydroxide solution of high purity can be produced as an output of column 110.
  • the resulting lithium hydroxide solution can be evaporated and crystallized to form lithium hydroxide monohydrate crystals (LiOl I-I hO). Further, the lithium hydroxide solution can be reacted with carbon dioxide to produce lithium carbonate (IJ2C03).
  • system 100 can be incorporated into a modular system (e.g., a modular extraction system) for extracting desired chemical species including lithium, specific lithium species, and/or other chemical compounds from input flows in a modular unit.
  • column 100 can be included as part of a column array within a modular and mobile extraction system.
  • input to column 100 e.g., lithium-based solution, water, sodium-based solution, etc. as described herein
  • FIG. 2 illustrates an example process 200 for preparing lithium carbonate and lithium hydroxide according to some examples of the present disclosure.
  • the example process 200 depicts a particular sequence of operations, the sequence may be altered without departing from the scope of the present disclosure. For example, some of the operations depicted may be performed in parallel or in a different sequence that does not materially affect the function of process 200. In other examples, different components of an example device or system that implements process 200 may perform functions at substantially the same time or in a specific sequence.
  • process 200 includes adding lithium-based solution to a column (e.g., column 110 as illustrated in FIG. 1).
  • a column e.g., column 110 as illustrated in FIG. 1.
  • an aqueous composition comprising lithium ions e.g., a lithium-based solution such as lithium chloride solution
  • the ion exchange resins can be in the form of organic polymer beads, membranes, or other structures.
  • the ion exchange resins may include cation exchange resins that have functional groups that are strong acid groups. That is, the ion exchange resins can include strong acidic cation exchanger (e.g., Dowex 50).
  • column 110 can include ion exchange resins, which may be saturated with sodium.
  • Nonlimiting examples of ion exchange resins include sulphonic acid, sulfonate groups, or a combination thereof.
  • the ion exchange resins can be washed with water prior to the addition of lithium-based solution into column 110.
  • a lithium-based solution can be prepared by processing a lithium chloride-containing solution.
  • brine solution can be processed to prepare a lithium- based solution.
  • Brines can be aqueous solutions that may include alkali metal or alkaline earth chlorides, bromides, sulfates, hydroxides, nitrates, and the like, as well as natural brines.
  • Brines can be obtained from natural sources, such as, Chilean brines or Salton Sea geothermal resource brines, geothermal brines, sea water, mineral brines (e.g., lithium chloride or potassium chloride brines), alkali metal salt brines, and industrial brines, for example, industrial brines recovered from ore leaching, mineral dressing, and so on.
  • natural sources such as, Chilean brines or Salton Sea geothermal resource brines, geothermal brines, sea water, mineral brines (e.g., lithium chloride or potassium chloride brines), alkali metal salt brines, and industrial brines, for example, industrial brines recovered from ore leaching, mineral dressing, and so on.
  • the lithium ions that are being pumped into the column 110 will displace sodium from the resin due to mass action.
  • a high concentration of lithium-based solution e.g., lithium chloride
  • the Li to Na ratio is very high (e.g., a fraction of Li to Na ratio is over 1).
  • lithium-based solution e.g., lithium chloride
  • sodium salts e.g., sodium chloride solution
  • process 200 includes rinsing/washing the column with water.
  • column 110 which is loaded with lithium from step 210, may be washed with clean water to remove any residual sodium salts such as sodium chloride.
  • process 200 includes adding sodium-based solution.
  • a concentrated solution of high-purity sodium hydroxide (NaOH) can be injected into column 110.
  • sodium ions from a sodium-based solution outnumber lithium ions in the column. For example, a number of sodium ions significantly exceeds a number of lithium ions. As follows, sodium ions displace lithium ions from column 110, and therefore, lithium hydroxide is produced as a resulting output.
  • process 200 includes evaporation and/or crystallization.
  • the lithium hydroxide solution produced from step 230 can be evaporated and crystallized to form high-purity lithium hydroxide monohydrate crystals (LiOH FbO).
  • the crystals can be washed, dried, and packaged for battery manufacturers.
  • process 200 includes adding carbon dioxide (CO2).
  • CO2 carbon dioxide
  • carbon dioxide can be injected into column 110.
  • lithium hydroxide solution can be reacted with carbon dioxide to produce lithium carbonate (IJ2C03) without the use of soda ash or lime.
  • carbon dioxide can be supplied from carbon dioxide emissions from gas-fired equipment such as a natural gas generator (e.g., boilers).
  • the purity of lithium carbonate can be: 99.99%.
  • the pure lithium carbonate produced in step 250 can contain lithium in excess of 99.999% purity.
  • a lithium-based solution can be added to concentrated sodium hydroxide, which causes precipitation of sodium salts.
  • Non-limiting examples of lithium-based solutions include lithium chloride, lithium sulfate, lithium acetate, lithium bromide, and so on.
  • the resulting sodium-lithium-chloride-hydroxide solution can be crystallized, precipitating sodium salts (e.g., sodium chloride). Further evaporation may lead to lithium hydroxide monohydrate (LiOH-HoO), which can be washed and dried, producing a high-purity product.
  • Claim language or other language in the disclosure reciting “at least one of’ a set and/or “one or more” of a set indicates that one member of the set or multiple members of the set (in any combination) satisfy the claim.
  • claim language reciting “at least one of A and B” or “at least one of A or B” means A, B, or A and B.
  • claim language reciting “at least one of A, B, and C” or “at least one of A, B, or C” means A, B, C, or A and B, or A and C, or B and C, or A and B and C.
  • Illustrative examples of the disclosure include:
  • a method comprising: adding an aqueous composition comprising lithium ions into a column, wherein the column comprises ion exchange resins saturated with sodium; adding water into the column to remove residual sodium salts; an adding a sodium hydroxide solution to the column to obtain lithium hydroxide.
  • Aspect 2 The method of Aspect 1, further comprising: evaporating the lithium hydroxide to produce lithium hydroxide monohydrate crystals.
  • Aspect 3 The method of Aspects 1 or 2, further comprising: reacting the lithium hydroxide with carbon dioxide to obtain lithium carbonate.
  • Aspect 4 The method of any of Aspects 1 to 3, wherein the ion exchange resin comprises an acidic cation exchanger.
  • Aspect 5. The method of any of Aspects 1 to 4, wherein the ion exchange rein comprises at least one of sulphonic acid, sulfonate groups, or a combination thereof.
  • Aspect 6 The method of any of Aspects 1 to 5, wherein the aqueous composition comprising lithium ions comprises a lithium chloride solution.
  • Aspect 7 The method of any of Aspects 1 to 6, wherein a number of sodium ions in the sodium hydroxide solution exceeds a number of lithium ions in the column when adding the sodium hydroxide solution to the column.
  • Aspect 8 The method of any of Aspects 1 to 7, further comprising: adding lithium chloride to the sodium hydroxide solution to obtain sodium lithium chloride hydroxide solution; and evaporating the sodium lithium chloride hydroxide solution to obtain lithium hydroxide monohydrate.
  • Aspect 9 The method of any of Aspects 1 to 8, further comprising: deploying the column into a modular extraction system of extracting lithium from brines.
  • Aspect 10 The method of any of Aspects 1 to 9, wherein the lithium carbonate obtained from the column contains lithium in excess of 99.999% purity.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

Des aspects de la présente invention concernent la préparation de carbonate de lithium et d'hydroxyde de lithium à l'aide d'une résine échangeuse d'ions. Un procédé donné à titre d'exemple peut comprendre l'ajout d'une composition aqueuse comprenant des ions lithium dans une colonne. La colonne peut comprendre des résines échangeuses d'ions saturées de sodium. Le procédé donné à titre d'exemple peut comprendre l'ajout d'eau dans la colonne pour éliminer les sels de sodium résiduels et l'ajout d'une solution d'hydroxyde de sodium à la colonne pour obtenir de l'hydroxyde de lithium.
PCT/US2024/026320 2023-05-02 2024-04-25 Préparation de carbonate de lithium et d'hydroxyde de lithium Pending WO2024228907A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US202363463548P 2023-05-02 2023-05-02
US63/463,548 2023-05-02
US18/644,735 2024-04-24
US18/644,735 US20240367989A1 (en) 2023-05-02 2024-04-24 Preparation of lithium carbonate and lithium hydroxide

Publications (1)

Publication Number Publication Date
WO2024228907A1 true WO2024228907A1 (fr) 2024-11-07

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11229880B2 (en) 2017-10-26 2022-01-25 International Battery Metals, Ltd. Modular extraction apparatus
WO2022109156A1 (fr) * 2020-11-20 2022-05-27 Lilac Solutions, Inc. Production de lithium avec de l'acide volatil
US11377362B2 (en) * 2020-11-20 2022-07-05 Lilac Solutions, Inc. Lithium production with volatile acid
US20230019776A1 (en) * 2020-01-17 2023-01-19 Bl Technologies, Inc. Ion exchange system and method for conversion of aqueous lithium solution

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11229880B2 (en) 2017-10-26 2022-01-25 International Battery Metals, Ltd. Modular extraction apparatus
US20230019776A1 (en) * 2020-01-17 2023-01-19 Bl Technologies, Inc. Ion exchange system and method for conversion of aqueous lithium solution
WO2022109156A1 (fr) * 2020-11-20 2022-05-27 Lilac Solutions, Inc. Production de lithium avec de l'acide volatil
US11377362B2 (en) * 2020-11-20 2022-07-05 Lilac Solutions, Inc. Lithium production with volatile acid

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