EP4634419A1 - Extraction de lithium - Google Patents

Extraction de lithium

Info

Publication number
EP4634419A1
EP4634419A1 EP23832719.1A EP23832719A EP4634419A1 EP 4634419 A1 EP4634419 A1 EP 4634419A1 EP 23832719 A EP23832719 A EP 23832719A EP 4634419 A1 EP4634419 A1 EP 4634419A1
Authority
EP
European Patent Office
Prior art keywords
lithium
solution
release
ion
acid
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
EP23832719.1A
Other languages
German (de)
English (en)
Inventor
Sebastian James Allender LEAPER
Ahmed ABDELKARIM
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.)
Watercycle Technologies Ltd
Watercycle Technologies Ltd
Original Assignee
Watercycle Technologies Ltd
Watercycle Technologies 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
Application filed by Watercycle Technologies Ltd, Watercycle Technologies Ltd filed Critical Watercycle Technologies Ltd
Publication of EP4634419A1 publication Critical patent/EP4634419A1/fr
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • C22B26/12Obtaining lithium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16Organic material
    • B01J39/17Organic material containing also inorganic materials, e.g. inert material coated with an ion-exchange resin
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01DCOMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00Lithium compounds
    • C01D15/02Oxides; Hydroxides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the present invention relates to a method of processing lithium-containing solutions to extract or recover lithium, in the form of lithium hydroxide, for further use. More particularly, the invention provides a method of extracting lithium through direct lithium extraction.
  • Lithium hydroxide (specifically, lithium hydroxide monohydrate) is one of two main forms of lithium used for the production of lithium-ion batteries.
  • the demand for lithium hydroxide is growing exponentially due to the increased demand for electric vehicles.
  • the production of lithium hydroxide requires energy-intensive electrolytic methods or additional precipitation steps compared to the second main form, lithium carbonate.
  • Direct Lithium Extraction is a process involving the selective extraction of lithium from aqueous sources such as natural brines, seawater or industrial wastewaters. This can be achieved in various ways including adsorption, ion exchange, electrodialysis, nanofiltration or others.
  • ion exchange represents an energy-efficient process that is driven by adjustments in pH rather than applied pressure or electrical current.
  • a lithium-containing feedstock solution such as brine over lithium-selective ion exchange media
  • lithium ions migrate into the selective media (that is, are extracted or leeched from the feedstock), leaving other components in the feedstock, to replace ions already present.
  • the remaining feedstock can be removed.
  • release solution dilute acid solution
  • the lithium-rich release solution that is created from this process can then undergo further concentration and crystallisation stages to produce salts such as lithium hydroxide or lithium carbonate.
  • Such lithium-selective ion exchange media are sometimes referred to as Lithium-Ion Sieves (LISs).
  • the acid used to release the lithium ions from the lithium-selective ion exchange medium is hydrochloric acid.
  • hydrochloric acid is introduced into the column, lithium ions are removed and the enriched release solution that is formed comprises lithium chloride (typically with small amounts of impurities).
  • That lithium chloride still needs to be converted into lithium carbonate or more preferably lithium hydroxide in order to be used in battery production.
  • Lithium carbonate can be produced from the lithium chloride-containing release solution by way of addition of sodium carbonate as per equation (1 ): 2LICI (aq) + Na2CO3 (aq) — » I 2CO3 (s) + 2NaCI (aq) (1 )
  • lithium hydroxide In order to then produce lithium hydroxide, an additional processing step is required, treating the lithium carbonate with calcium hydroxide as per equation (2). This forms a precipitate of calcium carbonate, leaving a lithium hydroxide solution which can then be crystallised through evaporation or antisolvent addition.
  • the present invention has been devised in the light of the above considerations.
  • the present inventors sought to provide an improved and more environmentally friendly process for DLE of lithium from lithium-containing solutions such as geothermal brines.
  • the inventors have found that by replacing hydrochloric acid with an organic acid (such as oxalic acid or citric acid) in the release step, a solution of the lithium salt of the organic acid is produced and hence included in the lithium-enriched release solution.
  • This solution can be reacted with a suitable precipitant, in the form of an alkali (suitably a non-lithium metal hydroxide) to produce lithium hydroxide, without having to first produce lithium carbonate.
  • the non-lithium metal hydroxide can be added directly to the solution of the lithium salt of the organic acid (i.e. the lithium enriched release solution).
  • a non-lithium metal hydroxide such as calcium hydroxide
  • the non-lithium metal hydroxide can be added directly to the solution of the lithium salt of the organic acid (i.e. the lithium enriched release solution).
  • calcium hydroxide may be added to a solution of lithium oxalate as per equation (3) for lithium oxalate.
  • organic acids and non-lithium metal hydroxides may be used for which the non-lithium metal cation of the hydroxide and the organic conjugate base anion of the organic acid yields a product that is insoluble or has low solubility in water.
  • the invention provides a method of direct lithium extraction from a lithium- containing feedstock, the method comprising:
  • a release step in which a release solution comprising a protic acid is contacted with the lithium-ion-exchange material, whereby lithium ions are released from the lithium-ion-exchange material into the release solution;
  • a precipitation step in which a precipitant is mixed with the lithium-enriched release solution; wherein the protic acid is an organic acid; and the precipitant is a non-lithium containing alkali.
  • the lithium ions enter the release solution to form the lithium salt of the organic acid, to be replaced in the lithium-ion-exchange material by protons. Then, in the precipitation step, by a further ion exchange lithium hydroxide is formed along with the non-lithium metal salt of the organic acid. That non-lithium metal salt of the organic acid precipitates out of the solution, leaving a solution of lithium hydroxide.
  • non-lithium containing alkali means an alkali which does not contain lithium.
  • Alkali as used herein means any base that is soluble in water and forms hydroxide ions, or the solution of a base in water.
  • the alkali therefore is necessarily a source of hydroxide ions, as is necessary for the desired ion exchange to form lithium hydroxide, and the consequent precipitation.
  • a non-lithium metal hydroxide is used.
  • the organic acid is suitably chosen to release lithium ions in the release step; it is therefore a protic acid.
  • the non-lithium metal hydroxide is chosen such that the salt of its metal with the organic acid is not soluble in water to an appreciable degree ( ⁇ 1 mg/mL, suitably ⁇ 0.5 mg/mL, more suitably ⁇ 0.1 mg/mL), so that it precipitates in the precipitation step.
  • the organic acid may suitably be, for example, citric acid or oxalic acid. Of these oxalic acid may be preferred.
  • the precipitant may preferably be, for example, calcium hydroxide, magnesium hydroxide or barium hydroxide. Of these calcium hydroxide may be preferred.
  • a lithium-containing feedstock has lithium ions ‘removed’ from it by the lithium-ion- exchange material. Those are replaced by, generally, protons.
  • This extraction step is therefore characterised as a first ion exchange.
  • a release solution is used to perform the equivalent ion exchange, in reverse. That is, protons from the release solution exchange with lithium ions and release the lithium ions into the release solution.
  • the depleted feedstock is suitably removed after the extraction step. It may then be, for example, subject to further processing; or recycled back into the feed to act as a ‘new’ feedstock for lithium ion extraction.
  • a single aliquot of feedstock may be subject to the above extraction and release steps multiple times (cycles), gradually reducing the lithium content each time.
  • the first washing step in which the lithium-ion-exchange material is washed with water (suitably deionised water).
  • the first washing step may be conducted for, for example, about 10-120 minutes.
  • the desired ion exchange lithium in the feedstock switching with protons in the lithium-ion-exchange material
  • the feedstock used in the extraction step may suitably have a pH of greater than 7, for example greater than 8 or greater than 9. This may be achieved in a step, before the extraction step, of increasing the pH of the feedstock by addition of an alkaline solution or basic compound, for example NaOH, in the amount required to raise the pH to the desired level.
  • the extraction step may suitably be conducted at a temperature above room temperature, for example around 25-70°C, suitably 50-70°C.
  • a temperature above room temperature for example around 25-70°C, suitably 50-70°C.
  • geothermal brines are used as the feedstock, they are often naturally of elevated temperature (for example about 40-70°C) and hence the extraction step necessarily proceeds at above room temperature where such a feedstock is used directly from the ground source.
  • the desired ion exchange lithium in the lithium-ion- exchange material switching with protons in the release solution
  • a release solution of reduced pH i.e. a proton-rich environment
  • the release solution may suitably have a pH of less than 7, for example less than 6 or less than 5.
  • a suitable choice of release solution is an acidic solution such as citric acid, for example a 0.2 M citric acid solution.
  • a lithium citrate solution is obtained. This can be processed to extract lithium citrate (for example by crystallisation, precipitation etc.). Lithium citrate can then be processed to form, for example, lithium hydroxide as described above.
  • the release step may suitably be conducted at a temperature above room temperature, for example around 25-70°C, suitably 50-70°C.
  • the lithium-ion-exchange material may suitably comprise a lithium-ion selective material (lithium-ion sieve) and a matrix material.
  • the lithium-ion-exchange material may suitably be provided in the form of beads or hollow fibers, with hollow fibers being preferred.
  • the hollow fibers themselves comprise (that is, preferably are in the form of) membranes, comprising a matrix material and an ion selective material.
  • the matrix material comprises or consists of PES.
  • lithium metal oxides and their hydrogen precursors are particularly suitable for use as a lithium selective material held in the matrix material.
  • Lithium manganese oxide (LMO) and its corresponding hydrogen manganese oxide (HMO) derived from, and lithium titanium oxide (LTO) and its corresponding hydrogen titanium oxide (HTO) derived from LTO are suitable.
  • the ion selective material comprises LTO or HTO derived from LTO. That is particularly the case where the matrix material is PES.
  • the selective material Before the extraction step, the selective material may be subjected to a priming step, wherein it (especially, LTO or LMO contained within it) is contacted with a priming solution (which may have the same properties as the release solution discussed herein, especially it may be a protic acid).
  • a priming solution which may have the same properties as the release solution discussed herein, especially it may be a protic acid.
  • HTO derived from LTO
  • HMO derived from LMO
  • the HTO (derived from HTO) or HMO (derived from LMO) selectively ion exchanges its protons for lithium ions from the feedstock.
  • HTO derived from LTO or HMO derived from LMO can act as a selective sieve or adsorbent for lithium ions.
  • the process comprises one fewer steps than the conventional method; (b) the process reduces impurities in the lithium enriched solution produced in the second step; and (c) the overall yield may be increased due to the lower solubility of the precipitated organic acid salts when compared to lithium carbonate.
  • the precipitate from the (iii) precipitation step comprises a salt of the organic acid with few impurities. This allows for further processing or re-sale of the precipitate, making the process more environmentally friendly.
  • the claimed processes are advantageous when compared to the known methods of the prior art which comprise multiple solid-liquid separations and non-zero solubility of by-products results in expensive and contaminated lithium hydroxide. This can detrimentally affect the economics of the process and produces more waste.
  • the invention includes the combination of the aspects and preferred features described except where such a combination is clearly impermissible or expressly avoided. Detailed Description of the Invention
  • Direct lithium extraction is a process where lithium is selectively extracted from impure solutions containing large amounts of multiple ionic species, wherein the majority of other components are left in solution.
  • DLE techniques including electrodialysis, nanofiltration, adsorption and ion-exchange. The latter two approaches hold the most promise in terms of lithium selectivity, energy consumption and cost.
  • DLE represents an alternative to conventional lithium brine extraction processes which utilise successive crystallisation stages (often with the use of evaporation ponds) which remove impurity compounds such as sodium chloride and leave the lithium in solution.
  • the selective material may be provided as beads in a column, with the feedstock poured into/through the column; or it may be provided in the form of hollow fibers, with the feedstock fed through or over the fibers. This facilitates the uptake of the lithium and replaces protons in the material.
  • This initial contact, removing the lithium from the feedstock and ‘storing’ it in the selective material, can be termed an ‘extraction step’ of the DLE process.
  • rate must also be balanced against other factors such as acid/base safety and toxicity, additional cost and so on.
  • a lithium selective material (Lithium-Ion Sieve, LIS) is needed for the desired ion exchanges to occur in the extraction and release steps.
  • Lithium metal oxides and their hydrogen precursors are particularly suitable for use as a lithium selective material held in the matrix material.
  • Lithium manganese oxide (LMO) and its corresponding hydrogen manganese oxide (HMO) derived from LMO, and lithium titanium oxide (LTO) and its corresponding hydrogen titanium oxide (HTO) derived from LTO are suitable.
  • the lithium selective material is not used in the pure form, but it is rather contained within or embedded in a matrix.
  • the matrix used here is not particularly limited given that it has good chemical and thermal stability.
  • Suitable matrix materials include ceramics and polymers. Suitable ceramics include oxides such as alumina, zirconia and titania.
  • Suitable polymers include both thermoplastics and thermosetting plastics.
  • the matrix material comprises one or more selected from: polysulfone (PSU), polyethersulfone (PES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyimide. In some embodiments it consists of one of those. PES is particularly preferred. Therefore preferably the matrix material comprises or consists of PES.
  • the matrix is suitably porous; this increases the flow of the feedstock to the selective material (which may not necessarily be present on the outer surface of the matrix material) and facilitates transfer of lithium ions.
  • the pores effectively increase the active surface area of the material. Accordingly larger pores, for example of an average pore size 0.1-2 pm, for example 0.5-1 pm, are preferable.
  • a porosity of > 60% may be suitable, in particular > 80%.
  • the pores may have a size (Dso) of 2 pm, for example ⁇ 1 pm.
  • the selective material may suitably be provided in the form of particles.
  • the particle size of the selective material is ⁇ 50 pm, suitably ⁇ 25 pm, or ⁇ 10 pm. Most suitable is a particle size of ⁇ 5 pm, or ⁇ 3 pm.
  • the particles may suitably have a size of > 200 nm, for example > 400 nm, > 1 pm, or > 2 pm.
  • the present lithium-ion-exchange material includes a selective material and a matrix material. It may be provided in various morphologies; for example, it may be formed into beads (for example, substantially spherical beads of average diameter 0.01-10 mm) or, more suitably, into a membrane form.
  • Such a membrane might be a simple flat (e.g. cast) membrane, or have a more complex structure such as that of a hollow fiber.
  • Hollow fiber membranes have been found by the inventors to have several advantages in DLE processes; in particular, a high useful surface area especially where the feedstock is flown in contact with the lithium-ion-exchange material.
  • Such hollow fibers are known in the art of water treatment; they are elongate, generally extruded members with a bore (hollow part) inside the substantially circular cross-section fiber.
  • a hollow fiber morphology of the material may be preferable as a feedstock brought into contact with the fiber has surface contact with a large active area.
  • Hollow fibers can also be packed into a housing to form a membrane module; flow of feedstock through the module again allows high surface contact and hence efficient lithium extraction and release.
  • Suitable hollow fiber dimensions will be apparent to those skilled in the art. For example, a hollow fiber length of 0.2-2 m, an outer diameter of 0.4-5 mm, and a wall thickness of 10-200 pm may be used.
  • the hollow fibers themselves may have, for example, a length of about 1 m, an outer diameter of about 1 mm, and an inner (bore) diameter of about 0.9 mm.
  • the lithium-ion-exchange material is contacted to a lithium-containing solution (feedstock).
  • a lithium-containing solution feedstock
  • this can be done batch-wise or using a continual flow of the lithium-containing solution.
  • Lithium-containing brines are a typical feedstock for DLE, typically containing from 50 to 4000 ppm lithium content.
  • the brines typically also contain multiple other ionic species including Na + , K + , Ca 2+ , Mg 2+ , F’, Cl", Br, SO ', PO -, NO 3 -, CO 3 2 -, and HCO 3 ‘.
  • lithium-containing solutions suitable as a feedstock include the product of leeching lithium from solid materials such as lithium-rich ores, lithium-rich recycled material, lithium-containing anodes and the like. This is often done using sulfuric acid, resulting in acidic lithium-containing solutions.
  • the feedstock is preferably adjusted to a pH of >7, optionally the pH may be raised yet higher, for example >8, >9, >10 or >11 .
  • Suitable bases used to adjust the pH of the feedstock solution are not particularly limited as the lithium- ion sieve is highly selective for lithium ions.
  • Suitable bases include NaOH, KOH, NaCO 3 , KCO 3 , NaHCO 3 , KHCO 3 , NH4OH, ammonium carbonate, ammonium persulfate, ammonia, Ca(OH)2 and Ba(OH)2 (and their associated oxides). In terms of cost, NaOH is preferred.
  • the extraction step may also or instead suitably be conducted at raised temperature (that is, >room temperature; for example >30°C, >40°C, >50°C, >60°C or >70°C).
  • a temperature of 25-70°C, and particularly 50-70°C, may be preferred.
  • the length of time for which there is contact between the feedstock and the selective material depends on several factors, for example how the selective material is provided. If it is provided in fibers, or a column, through which a feedstock is flown, the rate of flow is important. If the selective material is simply placed in contact with a stationary feedstock for some length of time, the time it is left is the relevant feature.
  • the extraction step may be conducted for 10-150 minutes.
  • the de-lithiated feedstock is suitably removed from contact with the selective material, and the selective material may be rinsed with fresh water. This can remove any impurities loosely bound to the lithium-ion-exchange material before the release step is carried out.
  • a protic acidic solution (release solution) is introduced; this replaces the lithium ions with protons.
  • the lithium is released from the selective material, forming a lithium-rich solution which can be removed for further processing. This can be termed a ‘release step’ of the DLE process.
  • Suitable acids include oxalic acid and citric acid.
  • Citric acid is preferable as it is a relatively easily obtainable, low toxicity acid which provides lithium citrate solutions that are readily processed.
  • oxalic acid may be preferred due to the relatively lower solubility of metal oxalates (especially calcium oxalate, 6.1 mg/L at 20°C, where the precipitant is calcium hydroxide) than of metal citrates (especially calcium citrate, 850 mg/L at 18°C, where the precipitant is calcium hydroxide).
  • the pH of the release solution (which is generally aqueous) depends of course on the acid included in it and how much is included; generally, it has a pH ⁇ 7, for example ⁇ 6, ⁇ 5, ⁇ 4, or ⁇ 3.
  • the lithium-ion exchange material is exposed to a solution of an organic acid.
  • a solution of an organic acid can be done batch-wise or using a continual flow of organic acid solution.
  • the organic acid may be one which comprises a carboxylic acid group.
  • the organic acid comprises two or more carboxylic acid groups.
  • the organic acid is not particularly limited, provided the solubility of its lithium salt is greater than that of another metal salt of the organic acid.
  • Suitable organic acids include oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, citric acid, malic acid, and tartaric acid. Of these, citric and especially oxalic acid are preferable as lithium oxalate is soluble in water whereas other oxalate salts are insoluble in water.
  • the release step may suitably be conducted at raised temperature (that is, >room temperature; for example >30°C, >40°C, >50°C, >60°C or >70°C).
  • the release step may suitably be conducted at up to 70°C.
  • a temperature above room temperature, for example around 25-70°C, suitably 50-70°C, may be preferred.
  • a precipitant is added to the lithium-enriched release solution in order to perform a double-displacement reaction to liberate lithium hydroxide and precipitate the organic conjugate base anions as an insoluble salt.
  • the precipitant is an alkali (that is, produces an alkali solution upon addition to water; any base that is soluble in water and forms hydroxide ions, or the solution of a base in water).
  • the precipitant contains metal cations that form insoluble salts with organic acids such as oxalic acid and citric acid
  • Suitable precipitants for use in the precipitation step may include alkaline earth metal hydroxides such as Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2, alkaline earth metal oxides (which hydrate to provide alkaline earth metal hydroxides) such as MgO, CaO, SrO and BaO, or an alkali metal hydroxide such as NaOH or KOH.
  • alkaline earth metal hydroxides such as Mg(OH)2, Ca(OH)2, Sr(OH)2 and Ba(OH)2
  • alkaline earth metal oxides which hydrate to provide alkaline earth metal hydroxides
  • an alkali metal hydroxide such as NaOH or KOH.
  • the precipitant cannot be a lithium hydroxide or oxide.
  • the precipitant is preferably Mg(OH)2 or Ca(OH)2, more preferably Ca(OH)2.
  • the precipitant is preferably Ca(OH)2 as the solubility of calcium oxalate is the lowest of alkaline earth oxalates.
  • the precipitant is added in the precipitation step as an aqueous solution.
  • the precipitant may be added in the precipitation step as a solid.
  • the precipitant is added in sufficient volume to cause precipitation of the organic conjugate base anions as an insoluble salt.
  • the precipitate may be separated from the supernatant solution by any suitable means, for example, gravity separation, filtration, centrifugation, hydrocyclonic separation and the like.
  • the solution of lithium hydroxide may be subjected to an isolation to produce solid lithium hydroxide.
  • the lithium hydroxide may be isolated as the monohydrate (LiOH-H2O) or the anhydrate (LiOH) through evaporation of the liquid or by crystallisation.
  • Suitable crystallisation techniques include antisolvent crystallisation wherein lithium hydroxide precipitates from solution upon addition of a suitable organic solvent such as acetone. The antisolvent may then be recovered after separation of the solid lithium hydroxide by, for example, distillation.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Electrochemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

L'invention concerne un procédé d'extraction directe de lithium à partir d'une charge d'alimentation contenant du lithium, le procédé comprenant des étapes d'extraction, de libération et de précipitation. Dans l'étape de libération, dans laquelle une solution de libération comprenant un acide protique est mise en contact avec le matériau d'échange d'ions lithium, des ions lithium sont libérés du matériau d'échange d'ions lithium dans la solution de libération, l'acide protique est un acide organique. Dans l'étape de précipitation, dans laquelle un précipitant est mélangé avec la solution de libération enrichie en lithium, le précipitant est un alcali ne contenant pas de lithium.
EP23832719.1A 2022-12-14 2023-12-13 Extraction de lithium Pending EP4634419A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB2218894.0A GB202218894D0 (en) 2022-12-14 2022-12-14 Lithium extraction
PCT/EP2023/085653 WO2024126601A1 (fr) 2022-12-14 2023-12-13 Extraction de lithium

Publications (1)

Publication Number Publication Date
EP4634419A1 true EP4634419A1 (fr) 2025-10-22

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EP (1) EP4634419A1 (fr)
AR (1) AR131364A1 (fr)
GB (1) GB202218894D0 (fr)
WO (1) WO2024126601A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
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EP4717783A1 (fr) * 2024-09-27 2026-04-01 Vito NV Procédés d'élimination de lithium de solutions comprenant du lithium

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4438749A3 (fr) * 2016-11-14 2025-01-08 Lilac Solutions, Inc. Extraction de lithium avec des particules revêtues d'échange d'ions
AR112663A1 (es) * 2017-08-02 2019-11-27 Lilac Solutions Inc Extracción de litio con perlas porosas de intercambio iónico
US10439200B2 (en) * 2017-08-02 2019-10-08 Lilac Solutions, Inc. Ion exchange system for lithium extraction
US10648090B2 (en) * 2018-02-17 2020-05-12 Lilac Solutions, Inc. Integrated system for lithium extraction and conversion
TWI877188B (zh) * 2019-07-26 2025-03-21 德商巴斯夫歐洲公司 自廢鋰離子電池中回收鋰之方法
CA3184777A1 (fr) * 2020-06-08 2021-12-16 Standard Lithium Ltd. Procede de recuperation de lithium a partir de saumure
CA3178825A1 (fr) * 2020-06-09 2021-12-16 David Henry SNYDACKER Extraction de lithium en presence de scalants
WO2022098303A1 (fr) * 2020-11-04 2022-05-12 Nanyang Technological University Procédé de récupération d'ions métalliques à partir de batteries
EP4063527A1 (fr) * 2021-03-10 2022-09-28 EnBW Energie Baden-Württemberg AG Procédés d'extraction du lithium à partir de saumure et de récupération du lithium lors du recyclage des batteries lithium-ion
CN114345291B (zh) * 2021-11-15 2023-07-25 成都开飞高能化学工业有限公司 一种高吸附容量粒状钛基锂离子筛吸附剂的制备方法

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AR131364A1 (es) 2025-03-12
WO2024126601A1 (fr) 2024-06-20
GB202218894D0 (en) 2023-01-25

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