EP4161875A1 - Procédé de récupération de lithium à partir de saumure - Google Patents

Procédé de récupération de lithium à partir de saumure

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Publication number
EP4161875A1
EP4161875A1 EP20940367.4A EP20940367A EP4161875A1 EP 4161875 A1 EP4161875 A1 EP 4161875A1 EP 20940367 A EP20940367 A EP 20940367A EP 4161875 A1 EP4161875 A1 EP 4161875A1
Authority
EP
European Patent Office
Prior art keywords
lithium ion
ion sieve
lithium
reactor
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
EP20940367.4A
Other languages
German (de)
English (en)
Inventor
Craig Johnstone Brown
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.)
Standard Lithium Ltd
Original Assignee
Standard Lithium 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 US16/895,783 external-priority patent/US11583830B2/en
Application filed by Standard Lithium Ltd filed Critical Standard Lithium Ltd
Publication of EP4161875A1 publication Critical patent/EP4161875A1/fr
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/16—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to the conditioning of the fluid carrier
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/36—Selective adsorption, e.g. chromatography characterised by the separation mechanism involving ionic interaction
    • B01D15/361—Ion-exchange
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/02—Loose filtering material, e.g. loose fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/16—Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/022—Metals
    • B01D71/0221—Group 4 or 5 metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/02—Processes using inorganic exchangers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/09—Inorganic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/50—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents
    • B01J49/53—Regeneration or reactivation of ion-exchangers; Apparatus therefor characterised by the regeneration reagents for cationic exchangers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/14—Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/14—Purification
    • C01D3/145—Purification by solid ion-exchangers or solid chelating agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D3/00—Halides of sodium, potassium or alkali metals in general
    • C01D3/14—Purification
    • C01D3/16—Purification by precipitation or adsorption
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/12—Addition of chemical agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2311/00—Details relating to membrane separation process operations and control
    • B01D2311/18—Details relating to membrane separation process operations and control pH control
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2315/00—Details relating to the membrane module operation
    • B01D2315/06—Submerged-type; Immersion type
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/51—Particles with a specific particle size distribution
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention generally relates to methods for recovering ions from brine, and more particularly, to methods for recovering lithium ions from brine.
  • Ion exchange is a well-known technology for recovery of low concentrations of metal ions from aqueous solutions.
  • conventional ion exchange resins such as strong acid cation exchange resins with sulfonic acid functional groups and chelating resins with iminodiacetate groups, have a higher preference for multivalent ions, such as calcium and magnesium, which may be present.
  • multivalent ions such as calcium and magnesium, which may be present.
  • selectivity for lithium over other monovalent ions, such as sodium and potassium may be similar, the presence of these competitive monovalent ions, which normally exist in great excess in brines, makes recovery of lithium unfeasible.
  • Inorganic ion exchange media such as ionic sieves, based upon manganese, titanium, or other oxides, have been identified as potentially useful for recovery of lithium from brines where there exists high concentrations of competitive ions, such as calcium, magnesium, sodium, and potassium.
  • These materials can be termed lithium ion sieves (LIS).
  • LIS exhibit a high preference for lithium because the LIS exchange sites are so narrow that Na + (0.102 nm), K + (0.138 nm), and Ca 2+ (0.100 nm), which have ionic radii larger than Li + (0.074 nm), cannot enter the exchange sites.
  • the ionic radius of the Mg 2+ (0.072 nm) ion is similar to the ionic radius of Li + , a high amount of energy is required for the dehydration of magnesium ions to allow it to enter the exchange sites so that selectivity over Mg 2+ is maintained.
  • LIS have a number of disadvantages.
  • Replacing LIS represents a significant cost.
  • removal and replacement of the degraded LIS, when it is installed in a conventional column is difficult and time consuming.
  • LIS are synthesized as fine powders and, therefore, due to high pressure drop, cannot be used in fixed beds, as is done with conventional ion exchange resins.
  • Chitrakar “Lithium Recovery from Salt Lake Brine by H 2 Ti0 3 ,” Dalton Transactions, 43(23), pages 8933-8939, June 21, 2014 (hereinafter referred to as “Chitrakar”), relates to the synthesis, characterization, and laboratory evaluation of lithium selective adsorbents based upon metatitanic acid.
  • Chitrakar does not mention an industrial process and does not discuss issues concerning solid/liquid separation or washing the brine and eluent from the adsorbent on an industrial scale.
  • Chitrakar does not disclose how to use the adsorbent on a continuous industrial scale. Specifically, the laboratory filtration used in the tests would not be applicable on an industrial scale.
  • the present invention provides a process for recovery of lithium ions from a lithium-bearing brine by contacting the lithium-bearing brine with a lithium ion sieve for less than about one hour in a first mixed or stirred reactor to form a lithium ion complex with the lithium ion sieve and decomplexing the lithium ion from the lithium ion sieve in a second mixed or stirred reactor to form the lithium ion sieve and an acidic lithium salt eluate.
  • a process for recovery of lithium ions from a lithium-bearing brine comprises contacting the lithium-bearing brine with a lithium ion sieve for less than about one hour in a first mixed or stirred reactor to form a lithium ion complex with the lithium ion sieve. Then, the process includes a step of decomplexing lithium ions from the lithium ion sieve in a second mixed or stirred reactor to form an acidic lithium salt eluate solution separated from the lithium ion sieve.
  • the lithium ion sieve may comprise an oxide of titanium or niobium (e.g., metatitanic acid or lithium niobate).
  • the decomplexing may be performed by elution using an acid.
  • a concentration of the acid may be maintained at a constant value through additions of said acid.
  • the concentration of the acid should be less than 0.1 M and preferably at a pH of greater than 1 and less than 3 and most preferably at pH of about 2.
  • An average contact time of the lithium ion complex with the lithium ion sieve and the acid may be less than 1 hour.
  • the acid may be hydrochloric acid or sulfuric acid.
  • a pH of the first reactor may be maintained at a constant value through addition of an alkali.
  • the pH may be maintained at the constant value of greater than 4 and less than 9 or greater than 6 and less than 8.
  • the alkali may be sodium hydroxide (NaOH), ammonium hydroxide, potassium hydroxide, sodium carbonate, magnesium hydroxide, calcium hydroxide, or anhydrous ammonia.
  • the alkali may be sodium hydroxide at a concentration of less than 8% w/w.
  • More than 90% of the lithium ion sieves may have an average particle diameter of less than 40 pm and more than 90% of the lithium ion sieves may have an average particle diameter of greater than 0.4 pm. More than 90% by volume of particles of the lithium ion sieve may be less than 100 pm in diameter and greater than 0.5 pm in diameter. More than 90% by volume of particles of the lithium ion sieve may be greater than 0.5 pm in diameter.
  • the process may further comprise the step of removing lithium ion sieves having an average particle diameter of less than 1 pm before contacting the lithium-bearing brine with the lithium ion sieve.
  • the process may further comprise the steps of separating the lithium ion complex with the lithium ion sieve from the brine with a solid/liquid separation device; and contacting the lithium ion complex with the lithium ion sieve with water before decomplexing in the second reactor.
  • the process may also further comprise the steps of separating the lithium ion sieve from the acidic lithium salt eluate solution with a solid/liquid separation device; contacting the lithium ion sieve with water after decomplexing in the second reactor to obtain a regenerated lithium ion sieve and a dilute acid water wash; and adding the regenerated lithium ion sieve to the first reactor.
  • This process may further comprise the step of dewatering the lithium ion complex with the lithium ion sieve to a moisture content of less than 90% by weight before decomplexing the lithium ion from the lithium ion sieve in the second reactor.
  • This process may also further comprise the step of dewatering the regenerated lithium ion sieve before being added to the first reactor.
  • the step of contacting the lithium ion sieve with water may comprise contacting the lithium ion sieve with sufficient water such that more than 50% of the lithium ion that has been decomplexed from the lithium ion sieve is washed from the lithium ion sieve prior to adding the regenerated lithium ion sieve to the first reactor.
  • the step of contacting the lithium ion sieve with water may also comprise contacting the lithium ion sieve with water in more than one counter-current stage such that more than 50% of the lithium ion that has been decomplexed from the lithium ion sieve is washed from the lithium ion sieve prior to adding the regenerated lithium ion sieve to the first reactor.
  • the process may also further comprise the step of adding the dilute acid water wash and additional concentrated acid to the second reactor.
  • the first reactor may comprise ultrafiltration or microfiltration membranes. Air or other gas may be used to agitate contents of the first reactor. A flux rate through the ultrafiltration membrane or the microfiltration membrane may be greater than 30 LMH at transmembrane pressures of less than 30 kPa.
  • a concentration of the lithium ion sieve may be greater than 50 g/L or greater than 100 g/L.
  • FIG. 1 is a diagrammatic view of an exemplary lithium extraction system for the present process.
  • FIG. 2 is a graph showing the amount of metal ion uptake as a function of pH.
  • FIG. 3 is a graph showing the amount of lithium and titanium extracted as a function of hydrochloric acid concentration.
  • FIG. 4 is a graph showing an exemplary LIS particle size distribution of a sample of metatitanic acid lithium ion sieve taken after a few hours of air agitation in a slurry.
  • FIG. 5 is a diagrammatic view of an alternative lithium extraction system for the present process.
  • FIG. 6 is a graph of lithium concentration as a function of time for an exemplary extraction trial.
  • FIG. 7 is a graph showing the amount of lithium and titanium extracted as a function of pH.
  • FIG. 8 is a graph showing the effect of contact time on lithium capacity and calcium separation.
  • the average particle diameter of conventional ion exchange resins is typically about 400-1250 micrometers.
  • the RECOFLO® short bed ion exchange process utilizes what is normally considered the finest particles used in large-scale industrial applications. These particles typically have an average particle diameter of 100-200 micrometers.
  • the lithium ion sieves utilized in the present invention are preferably in powder form.
  • the average particle size of the powder does not necessarily have to be limited. However, the average particle size is preferably less than about 100 pm, more preferably 10 to 100 pm, even more preferably 20 to 100 pm, and yet even more preferably 20 to 95 pm. Further, the average particle size may be 0.4 to 40 pm. For instance, more than 90% (by volume) of the lithium ion sieve particles may be less than 100 pm in diameter and greater than 0.5 pm in diameter. In the same or different embodiments, more than 90% (by volume) of the lithium ion sieve particles may be greater than 0.5 pm in diameter. Since these materials are synthesized as powders, the cost of agglomeration is avoided. Moreover, the higher surface area afforded by such a powder significantly improves the kinetics of the ion exchange process. In other words, the lithium ion sieves are not a composite bound together with a polymer or other binding agent.
  • Exemplary LIS include, but are not limited to, oxides of manganese and titanium.
  • an exemplary LIS may include an oxide of titanium, preferably metatitanic acid (MTA).
  • MTA metatitanic acid
  • the present invention is equally applicable to other types of lithium ion sieve media such as manganese oxide and lithium niobate (i.e., niobic acid).
  • the lithium ion sieve may also comprise doping agents in addition to an oxide of titanium, niobium, or manganese.
  • the content of the lithium ion sieve would be predominately an oxide of titanium, niobium, or manganese.
  • the powdered lithium ion sieve media may be contacted with a lithium-containing brine in a stirred tank reactor (STR or reactor).
  • the reactor may be a tank containing the liquid to be treated along with the lithium ion sieve.
  • the lithium ion sieve may be maintained in suspension by a mixer or by fluidization by upward liquid or gas bubble flow, which provides intimate contact between the lithium ion sieve and the brine.
  • the pH of the brine in the reactor may be maintained at a constant level through additions of an alkali, such as sodium hydroxide (NaOH), ammonium hydroxide, potassium hydroxide, sodium carbonate, magnesium hydroxide, and calcium hydroxide.
  • the pH of the brine in the reactor may be maintained at greater than 5 and less than 9.
  • magnesium hydroxide does not normally precipitate below a pH of about 8, when the alkali is added, localized high pH conditions at the point where the alkali contacts the brine results in precipitation of magnesium hydroxide. Despite the fact that the pH of the bulk brine is below the theoretical precipitation pH, the precipitate does not quickly dissolve.
  • the presence of magnesium hydroxide causes a number of problems. For example, it can adhere to the surface of the LIS, inhibiting uptake of lithium.
  • the magnesium hydroxide precipitation problem is particularly acute and more pronounced at higher NaOH concentrations.
  • 50% w/w NaOH 50% w/w NaOH is utilized, large quantities of Mg(OH)2 are produced that do not re-dissolve. If a more dilute NaOH solution is utilized, the quantity of Mg(OH)2 produced is less and the Mg(OH)2 re-dissolves more quickly. If 4% w/w NaOH is utilized, only very small quantities of Mg(OH)2 are produced, which re-dissolve in just a few seconds. As such, if sodium hydroxide is used, the sodium hydroxide is preferably at a concentration of less than 8% w/w.
  • ammonia for neutralization.
  • the ammonia can be in the form of anhydrous ammonia gas or liquid ammonium hydroxide so that the amount of brine over- volume is negligible. Only small quantities of Mg(OH)2 precipitate out at the injection point, even if anhydrous ammonia gas or 30% ammonium hydroxide are used, and this precipitate re-dissolves quickly, having no negative impacts on the process.
  • the lithium-depleted (i.e., barren) brine may be separated from the lithium ion sieve and removed from the reactor by various means.
  • the brine/lithium ion sieve slurry i.e., loaded lithium ion sieve
  • the brine/lithium ion sieve slurry may be contacted with water in an additional stirred reactor to remove residual brine before proceeding to the next step.
  • particle size of the lithium ion sieve is greater than about 10 microns, gravity sedimentation can be used.
  • filtration devices such as a rotary drum vacuum or belt filters can be used.
  • the particles size is less than 1 micron, membrane filtration may be used. Combinations of these solid/liquid separation devices can be advantageously used.
  • One example of a possible solid/liquid separation device may be a centrifuge.
  • the lithium ion sieve contained in the reactor may be contacted with an eluent.
  • This eluent may be, among other things, an acid, such as hydrochloric acid (HC1) or sulfuric acid (H2SO4).
  • the acid may be added in a concentration in the order of less than 0.1 M, preferably at a pH of greater than 1 and less than 3 and most preferably at a pH of about 2.
  • HC1 hydrochloric acid
  • H2SO4 sulfuric acid
  • the acid may be added in a concentration in the order of less than 0.1 M, preferably at a pH of greater than 1 and less than 3 and most preferably at a pH of about 2.
  • a “complex” is a combination of individual atom groups, ions, or molecules that combine to create one large ion or molecule.
  • “decomplexing” is the act of separating individual atom groups, ions, or molecules from such a large ion or molecule. Because of the selectivity of the lithium ion sieve for lithium over other metals, the ratio of lithium to other metals may be appreciably higher in the product solution than the feed brine.
  • the lithium ion sieve After the lithium ion sieve has been regenerated, the lithium ion sieve can be reused to treat more brine and extract more lithium.
  • the process may be conducted continuously. Two reactor stages may be needed in such a continuous process. Brine may be fed continuously to a loading stage wherein lithium ion sieve is contacted with the brine as a continuously mixed slurry. Lithium ions may then be removed from the brine via uptake by the lithium ion sieve, resulting in the barren brine and a lithium-loaded LIS. The barren brine may then be separated from the lithium-loaded lithium ion sieve and removed from the reactor. The lithium-loaded lithium ion sieve, now separated from the brine, may be passed on to an elution stage.
  • the lithium capacity decreased from 15.5 mg/g at 1 hour to 12.5 mg/g at 2 hours and further decreased to 12 mg/g after 71 hours.
  • the contact time between the LIS and the brine should be less than about 1 hour.
  • Eluent may be fed continuously to the elution stage, and the lithium-loaded lithium ion sieve removed from the loading stage may be contacted with the eluent as a continuously mixed slurry.
  • the lithium ion sieve and liquid are separated, and this separated liquid (i.e., the eluate) is the lithium salt product solution.
  • the lithium content of the lithium ion sieve leaving the elution stage is appreciably reduced and, the lithium ion sieve may be recycled back to the loading stage for reuse. In this manner, the lithium ion sieve may be reused multiple times, and the process may be operated continuously.
  • additional stages may be utilized as shown in FIG. 1.
  • a feed brine flows through a line 2 into a first stirred reactor 4, which contains lithium ion sieve, as part of a loading stage.
  • the lithium ion sieve is maintained in suspension by a mixer 6.
  • the brine/lithium ion sieve slurry is maintained at a constant pH through the addition of NaOH via line 8.
  • the lithium ion sieve loaded with brine flows through line 10 into an additional stirred reactor 12 as part of a washing stage.
  • the barren brine is separated from the loaded lithium ion sieve and flows through line 14.
  • the lithium ion sieve loaded with brine is maintained in suspension by a mixer 16.
  • the loaded lithium ion sieve is contacted with water via line 18 to wash the brine from the lithium ion sieve, which is believed to reduce crosscontamination of the lithium salt product with contaminant ions present in the feed brine.
  • the washed and loaded lithium ion sieve flows through line 20 into a second stirred reactor 22 as part of an elution stage.
  • the wash water is separated from the washed and loaded lithium ion sieve and flows through line 24 to return to the first stirred reactor 4.
  • the washed and loaded lithium ion sieve is maintained in suspension by a mixer 26.
  • the washed and loaded lithium ion sieve is contacted with HC1 via line 28 to elute the lithium ions from the lithium ion sieve.
  • the concentration of acid in the second stirred reactor 22 is maintained at a constant value through the addition of HC1 via line 28.
  • the regenerated lithium ion sieve flows through line 30 into another stirred reactor 32 as part of an acid wash stage.
  • the lithium ions, as LiCl product, are separated from the regenerated lithium ion sieve and flow through line 34.
  • the regenerated lithium ion sieve is maintained in suspension by a mixer 36.
  • the brine may be initially processed in a first loading stage.
  • the treated brine from the first loading stage still containing some residual lithium, may be passed to a second loading stage wherein contact with lithium ion sieve further reduces the lithium content of the brine.
  • the lithium ion sieve from the second loading stage containing some lithium but still having further lithium capacity available, may be passed to the first loading stage.
  • the loaded lithium ion sieve from the first loading stage may then be passed to an elution stage. By this means, the lithium content of the barren brine can be further reduced.
  • additional loading stages may be utilized in this manner.
  • the loaded lithium ion sieve can similarly be processed in several elution stages whereby the lithium ion sieve passes counter-currently to the eluate flow.
  • the lithium content of the lithium ion sieve can be further reduced, and the lithium concentration in the eluate (i.e., the lithium product) can be increased.
  • the active component of the lithium ion sieve may be, for example, an oxide of titanium, such as metatitanic acid (MTA).
  • MTA is a weak acid and, therefore, has a high affinity for hydrogen ions. As a result, at a low pH, where hydrogen ions are available, MTA may not easily exchange hydrogen ions for lithium.
  • the lithium ion sieve may also further comprise small amounts of doping agents.
  • FIG. 2 shows the amount of metal ion uptake as a function of pH. It can be seen that lithium uptake is reduced significantly below a pH of about 6.5 and little lithium will be taken up below a pH of about 4. As the lithium loading proceeds, the pH of the brine drops. When the pH drops to a pH of about 4, no further uptake of lithium can occur.
  • the pH may be adjusted prior to contacting the brine with the LIS by dosing the brine with NaOH or another base, such as sodium carbonate or ammonium hydroxide, prior to treatment.
  • NaOH or another base such as sodium carbonate or ammonium hydroxide
  • Such a pre-treatment will raise the initial pH so that the final pH will not be so low as to prevent lithium uptake.
  • the disadvantage of this approach is that, as shown in FIG. 2, at increased pH levels the amount of sodium ions taken up by the lithium ion sieve increases.
  • magnesium hydroxide may precipitate out of solution.
  • the brine/lithium ion sieve slurry in the loading reactor may be neutralized with an alkali, such as NaOH, in order to maintain the pH so as to maximize the uptake of lithium while minimizing the uptake of sodium.
  • the pH may generally be greater than about 5 and less than about 9, preferably greater than 6 and less than 8.
  • the pH is preferably between 6 and 7.
  • Lithium is typically eluted from the LIS with an acid, such as hydrochloric acid, to concurrently regenerate the lithium ion sieve and produce a lithium product, as shown by equation (2).
  • the lithium ion sieve effectively neutralizes the acid by this reaction.
  • the amount of lithium eluted from the lithium ion sieve increases as the concentration of HC1 increases.
  • the acid concentration may be maintained at a concentration of less than 0.1 M (defined as mol dm 3 in FIG. 3).
  • the acid concentration may correspond to a pH of less than 3 and greater than 1 and preferably at a pH of approximately 2.
  • One method to minimize such degradation of the lithium ion sieve is to minimize the contact time between the LIS and the acid. Because in one embodiment the lithium ion sieve is in powdered form, the kinetics of the ion exchange process are quite rapid and the exchange reaction of equation (2), above, is mostly completed in less than one hour. In an embodiment, the contact time between the LIS and the elution acid is less than one hour. Therefore, lithium is essentially completely removed from the lithium ion sieve while minimizing the degradation of the lithium ion sieve.
  • FIG. 4 shows a typical particle size distribution of a sample of metatitanic acid lithium ion sieve taken after a few hours of air agitation in a slurry.
  • the effective particle size (dio) is about 0.5 pm and 90% (by volume) of the material is in the range of 0.4-40 pm.
  • the effective size is the diameter of the particle for which 10 percent of the total grains are smaller, and 90 percent of the total grains are larger, on a weight or volume basis.
  • the effective size of this material is about 0.5 pm.
  • the coarser material may settle from a water slurry by gravity in less than one hour, the finer particles do not easily settle even after a day.
  • larger lithium ion sieve particles are agglomerates of fine particles produced by sintering during the synthesis process.
  • the large particles are susceptible to mechanical attrition during mixing with the process liquids, so that there would be an increasing proportion of fine particles over time. Consequently, separation of the lithium ion sieve from the process liquids by gravity sedimentation is not ideal.
  • Membranes are being increasingly used in bioreactors for wastewater treatment.
  • MLR membrane bioreactor
  • microfiltration or ultrafiltration membranes with pore sizes of less than 0.1 pm are submerged in a suspension of wastewater and bio-solids. Clear filtered/treated wastewater is drawn through the membranes by vacuum.
  • the wastewater/biosolids slurry is typically agitated by air sparging. Air agitation promotes oxygen transfer to the bio-solids and prevents membrane fouling due to build-up of bio-solids on the membrane surface.
  • the suspended solids concentration is typically less than 30 g/L and more typically 10-15 g/L. Higher suspended concentrations are not employed, as oxygen transfer is impeded due to resulting higher and non-Newtonian fluid viscosity. In addition, higher suspended solids concentrations reduce the membrane flux rate and/or increase the trans -membrane pressure. Typical flux rates for submerged membranes in membrane bioreactors are 10-30 liters per hour per square meter (which units are normally abbreviated as “LMH”).
  • the submerged ultrafiltration or microfiltration membrane process may be used in the present invention as a means of separating the lithium ion sieve from the process liquids.
  • the pore size of the membranes at typically less than about 1 pm, is smaller than the smallest lithium ion sieve particles, so nearly 100% solids separation can be achieved.
  • oxygen transfer is not an issue.
  • submerged aeration air agitation
  • Embodiments described here are a significant departure from typical immersed membrane applications such as MBRs.
  • Lithium ion sieve particles allow treatment of much higher suspended solids concentrations while achieving appreciable higher fluxes. Fluxes obtained in conventional MBR applications are typically less than 30 LMH at transmembrane pressures of 10-30 KPa and total suspended solids (TSS) levels of less than 30 g/L. In contrast, with the present invention, fluxes as high as 300 LMH at transmembrane pressures of 20 KPa have been obtained with lithium ion sieves, at TSS levels of more than 100 g/L.
  • the suspended solids concentration may be greater than about 50 g/L and preferably greater than 100 g/L. Without intended to be bound by any particular theory, it is believed that a higher solids concentration in the reactor is advantageous because it reduces the reactor volume required to achieve a given lithium ion sieve-liquid contact time.
  • the acid eluent becomes lower in acid concentration as it passes through the bed and is neutralized by the reaction provided by equation (2) above.
  • the pH of acid entering the bed may then be appreciably less than less than 1. Consequently, if the lithium ion sieve is regenerated in a fixed bed, the lithium ion sieve toward the entry end of the bed will be severely degraded by the more concentrated acid.
  • the lithium ion sieve may be regenerated as a slurry in a reactor vessel where the lithium ion sieve is in contact with acid at a uniform concentration.
  • the acid concentration may be maintained at a concentration of less than 0.1 M, and preferably at an acid concentration corresponding to a pH of less than 3 and greater than 1 and preferably at a pH of approximately 2.
  • the residual feed brine may be removed from the lithium ion sieve after loading and prior to acid elution by mixing the loaded lithium ion sieve with water and then separating out the water.
  • the residual feed brine may be removed by directly filtering the loaded lithium ion sieve through a suitable filter.
  • the preferred particle size of the lithium ion sieve is in the range of 0.4-40 pm.
  • Solids particles in this range can be filtered and de-watered using conventional solid/liquid separation devices, employing filter media, such as woven filter cloths with openings of greater than 10 pm in lieu of membranes with pore sizes of less than 1 pm.
  • filter media such as woven filter cloths with openings of greater than 10 pm in lieu of membranes with pore sizes of less than 1 pm.
  • the dewatered lithium ion sieve may then be washed directly on the filter to remove the residual brine from the lithium ion sieve without the necessity of re-slurrying the lithium ion sieve in water.
  • Exemplary types of filters include, but are not limited to, horizontal belt vacuum and pressure filters, rotary drum vacuum and rotary disk vacuum and pressure filters, pressure filter presses, and centrifuges.
  • the lithium ion sieve is preferably separated from the acidic lithium salt eluate solution to minimize the return of the recovered lithium with the regenerated lithium ion sieve back to the loading reactor.
  • a similar approach may be utilized as is used for separating feed brine from the loaded lithium ion sieve.
  • the regenerated lithium ion sieve may be mixed with water and then separating out the water.
  • the lithium ion sieve may be filtered through a suitable filter, preferably one with water washing capabilities.
  • the working capacity of a metatitanic acid lithium ion sieve may be about 0.01 g lithium per gram of lithium ion sieve.
  • the flow of lithium ion sieve on a dry basis would then be 100 g lithium ion sieve/g Li recovered.
  • the slurry in the loading reactor contains a suspended solids concentration of 100 g/L (i.e..
  • the regenerated lithium ion sieve slurry could be mixed with water in a washing reactor to recover the lithium values prior to recycling the lithium ion sieve to the loading reactor.
  • To separate 90% of the lithium from the lithium ion sieve would require 9 liters of water per gram of recovered lithium.
  • the diluted liquid in the washing reactor could then be separated by gravity or a membrane, for example.
  • the concentration of lithium would then be only 0.1 g/1. However, this concentration is too low to be of practical use.
  • the lithium ion sieve should be dewatered to a moisture content appreciably less than 90%.
  • the regenerated lithium ion sieve should be dewatered when it is removed from the regeneration reactor. Otherwise, a large portion of the recovered lithium will be recycled with the lithium ion sieve back to the loading reactor. Even if the regenerated lithium ion sieve is dewatered to a high degree, the lithium lost to the moisture entrained in the lithium ion sieve may be problematic.
  • all of the lithium eluted from the lithium ion sieve would be withdrawn with the lithium ion sieve. If this lithium ion sieve was then recycled back to the loading reactor, no net lithium would be recovered.
  • the lithium from the liquid entrained with the dewatered lithium ion sieve should be recovered.
  • the regenerated lithium ion sieve may be washed with water. The lithium would then be recovered in the wash water. The amount of wash water should be sufficient to recover most of the lithium, but not so much as to excessively dilute the recovered lithium salt solution.
  • One method to achieve this would be to re-slurry the lithium ion sieve in water and then re-filter the lithium ion sieve from the slurry. To wash 90% of the lithium from the lithium ion sieve would require about 9 mL of water per mL of entrained liquid in the lithium ion sieve, allowing recovery of a lithium salt solution containing 1 g/L lithium under these conditions.
  • the amount of wash water can be reduced and the lithium concentration can concomitantly be increased by utilizing two or more counter-current washes. Accordingly, the dewatered lithium ion sieve recovered from the first wash stage is re-slurried in water once again in a second wash stage and then dewatered yet again. The wash water recovered from the second stage dewatering device is utilized in the first wash stage in lieu of fresh water. With two counter-current wash stages, the amount of water required for 90% lithium recovery can be reduced from about 9 mL of water per mL of entrained liquid to about 3 mL of water per mL of entrained liquid, and the concentration of recovered lithium can be increased from 1 g/L to about 3 g/L.
  • the slurry may be dewatered by a device such as a horizontal vacuum belt filter.
  • the dewatered lithium ion sieve cake may then be washed directly on the filter.
  • One or more count-current wash stages can be employed on the filter.
  • a centrifuge may be used. If a centrifuge is used, the solids may be re-slurried in water and then dewatered with the centrifuge. If several washing stages are used, the dewatered solids from a first centrifuge may be re-slurried with water again and then dewatered in a second centrifuge.
  • the centrate from the second centrifuge may be used as the water to slurry the solids feeding the first centrifuge. Additional centrifuges can be utilized in this manner to effectively achieve a multi-stage countercurrent solids wash.
  • the particle size of the lithium ion sieve is too small, such dewatering becomes more difficult. Indeed, even if the majority of the particles are greater than 10 micrometers in diameter, the presence of particles much less than 10 micrometers in diameter makes dewatering difficult. In particular, if the average particle size of the ion sieve is 0.1 pm or less, dewatering becomes virtually impossible.
  • the dry lithium ion sieve may be classified by a suitable device such as an air classifier or the wet lithium ion sieve may be classified by elutriation to remove the fine particles with a diameter of less than 1-10 micrometers. By doing so, separation of the lithium ion sieve from the liquid to be treated is facilitated. Removal of the fine particles will significantly improve filtration rates, avoid blinding of filtration media, and produce a filter cake with a lower moisture content. By removing the fine particles in this manner, conventional solid/liquid separation devices, such as horizontal belt vacuum and pressure filters, rotary drum vacuum and rotary disk vacuum and pressure filters, pressure filter presses, centrifuges, and the like may be more effectively employed.
  • a suitable device such as an air classifier
  • the wet lithium ion sieve may be classified by elutriation to remove the fine particles with a diameter of less than 1-10 micrometers.
  • the feed brine should be efficiently separated from the loaded lithium ion sieve.
  • Purity requirements for battery grade lithium carbonate, for instance, are very stringent. Any residual feed brine retained with the loaded lithium ion sieve will contaminate the product with impurities in the feed brine, such as calcium, magnesium, sodium, potassium, etc. As the concentration of these impurities in the brine is much higher than the lithium, even minimal amounts of brine carry-over are problematic. In fact, the impurity contribution from entrained brine on the loaded lithium ion sieve is potentially greater than the quantity of impurities actually exchanged on to the lithium ion sieve in most cases.
  • test unit was constructed to demonstrate the process according to one embodiment of the invention.
  • a schematic drawing of the test unit is shown in FIG. 5.
  • the test unit consisted of six reactors (R1-R6), each one equipped with air agitation diffusers and five of which were equipped with immersed membrane modules.
  • Reactor R4 utilized for acid regeneration of the lithium ion sieve, was not equipped with a membrane.
  • the working volume of each of the reactors was approximately 5 liters with the exception of the reactor R4, which had a working volume of approximately 1.1 liter.
  • Lithium titanate was used as the lithium ion sieve.
  • the LTO was synthesized by reacting lithium hydroxide with titanium dioxide at a molar ratio of approximately 2.2:1 at a temperature of 700°C for 4 hours.
  • FIG. 4 discussed above, provides the particle size distribution of the LTO used in this example.
  • the initial LTO produced from the synthesis was converted to metatitanic acid (HTO) by pickling the LTO in 0.2 N HC1 for 16 hours and then washing the resulting HTO with water.
  • Reactor R1 and reactor R2 were initially charged with 100 g/L aqueous slurries of the LIS, while the remaining reactors were initially charged with 500 g/L slurries of the LIS.
  • the lithium ion sieve was conveyed from reactor to reactor as a slurry by peristaltic pumps.
  • the flow rate of the lithium ion sieve slurries was adjusted so that the solids transfer rate was approximately 100 g/h on a dry weight basis.
  • the membrane modules were lab-scale immersed-type POREFLONTM units, manufactured by Sumitomo Electric Corporation, each having an effective membrane area of 0.1 m 2 . Liquid was drawn through the membranes by vacuum using peristaltic pumps. The vacuum was maintained at less than 40 kPa.
  • the lithium containing brine was made up from brine obtained from the Smackover formation in southern Arkansas and had a composition as shown in Table 1 below. After extraction of lithium from the brine in accordance with the process, the brine was re-fortified with lithium chloride and recycled to the process. As a result, the lithium concentration in the feed brine was somewhat higher than the initial brine as received. The sodium and potassium concentrations were estimated based upon published brine assays.
  • Reactor Rl the loading reactor, was equipped with a pH controller that automatically controlled the addition of 1 N NaOH such that a pH of 7.8 was maintained. Thus, the acid generated by the ion exchange reaction was continually neutralized.
  • Feed brine was introduced to reactor Rl and allowed to contact the HTO.
  • the HTO was fed to reactor Rl from reactor R6 as a 500 g/L slurry.
  • the solids concentration of the lithium ion sieve in reactor Rl was about 100 g/L.
  • the HTO extracted lithium ions from the brine, the HTO was partially converted back to LTO. Lithium-depleted (i.e., barren) brine was drawn through the membranes by a pump.
  • the loaded lithium ion sieve (i.e., LTO) was withdrawn from the reactor Rl as a brine slurry and directed to reactor R2, which was the brine wash reactor. Water was fed to reactor R2 so that the residual brine was washed from the LTO. The wash water was withdrawn from reactor R2 through another immersed membrane module.
  • Loaded/washed LIS was withdrawn from reactor R2 as a water slurry and directed to reactor R3, which was the thickener reactor. Water was withdrawn from reactor R3 through another immersed membrane module, thus increasing the solids concentration in reactor R3 to approximately 500 g/L.
  • the thickened slurry of loaded/washed LIS at a solids concentration of about 500 g/L was withdrawn from reactor R3 and directed to reactor R4, which was the regeneration reactor.
  • the lithium ion sieve in reactor R4 was contacted with hydrochloric acid at a concentration of approximately 0.2 M.
  • the lithium ion sieve solids concentration in reactor R4 was approximately 500 g/L.
  • the acid concentration was monitored and maintained by a conductivity controller at a constant level through the addition of 5 M HC1 to a conductivity set point of 150 mS/cm.
  • Reactor R5 was the first of two counter-currently operated acid wash reactors. The majority of the HCl/lithium chloride was washed from the lithium ion sieve in reactor R5, while most of the residual HCl/lithium chloride was washed from the lithium ion sieve in reactor R6.
  • the acid wash- water was withdrawn from reactor R5 through another immersed membrane module.
  • the acid wash-water withdrawn from reactor R5 constituted the recovered lithium chloride product from the process.
  • a slurry of lithium ion sieve at a concentration of about 500 g/L was withdrawn from reactor R5 and directed to reactor R6.
  • Fresh water added to reactor R6 washed most of the remaining HCl/lithium chloride from the lithium ion sieve.
  • the wash-water was withdrawn from reactor R6 through another immersed membrane module and directed to reactor R5.
  • the concentration of lithium chloride in the wash- water in reactor R6 was thereby reduced to less than 10% of the lithium concentration in reactor R4.
  • the lithium ion sieve/wash-water slurry was withdrawn from reactor R6 and directed back to reactor R1 wherein it was reused to extract lithium from the feed brine.
  • the lithium product contained a lithium concentration of 4,300 mg/L. More lithium was removed from the product (2,322 mg/h) than was actually extracted from the brine (957 mg/h). Without intending to be bound to any particular theory, it is believed that the difference (1,365 mg/h) was likely residual lithium on the lithium ion sieve that had not been completely removed from the LTO during the initial pickling in HC1. Based upon the lithium that was actually extracted from the brine, the lithium ion sieve capacity was 9.6 mg/g. The liquid residence time in the strip reactor was 2.2 hours. Based upon the lithium that was loaded and recovered, the lithium concentration factor was about 10 times.
  • the feed brine contained a calcium concentration of 22,000 mg/L while the product contained a calcium concentration of only 1,400 mg/L.
  • the ratio of calcium to lithium in the feed was 90.
  • the feed brine contained an estimated sodium concentration of 43,000 mg/L while the product contained a sodium concentration of only 9,770 mg/L.
  • the ratio of sodium to lithium in the feed was 176.
  • the feed brine contained a magnesium concentration of 2,170 mg/L while the product contained a magnesium concentration of only 76 mg/L.
  • the ratio of magnesium to lithium in the feed was 8.9.
  • the system and method described herein have the ability to selectively recover lithium from brines containing high concentrations of calcium, sodium, and magnesium.
  • references herein to terms such as “vertical,” “horizontal,” etc. are made by way of example, and not by way of limitation, to establish a frame of reference. It is understood that various other frames of reference may be employed for describing the invention without departing from the spirit and scope of the invention. It is also understood that features of the invention are not necessarily shown to scale in the drawings. Furthermore, to the extent that the terms “composed of,” “includes,” “having,” “has,” “with,” or variants thereof are used in either the detailed description or the claims, such terms are intended to be inclusive and open- ended in a manner similar to the term “comprising.”
  • references herein to terms modified by language of approximation, such as “about,” “approximately,” and “substantially,” are not to be limited to the precise value specified.
  • the language of approximation may correspond to the precision of an instrument used to measure the value and, unless otherwise dependent on the precision of the instrument, may indicate +/- 10% of the stated value(s).
  • a feature “connected” or “coupled” to or with another feature may be directly connected or coupled to or with the other feature or, instead, one or more intervening features may be present.
  • a feature may be “directly connected” or “directly coupled” to or with another feature if intervening features are absent.
  • a feature may be “indirectly connected” or “indirectly coupled” to or with another feature if at least one intervening feature is present.
  • a feature “on” or “contacting” another feature may be directly on or in direct contact with the other feature or, instead, one or more intervening features may be present.
  • a feature may be “directly on” or in “direct contact” with another feature if intervening features are absent.
  • a feature may be “indirectly on” or in “indirect contact” with another feature if at least one intervening feature is present.

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Abstract

Un procédé de récupération d'ions lithium à partir d'une saumure contenant du lithium comprend les étapes consistant à mettre en contact de la saumure contenant du lithium avec un tamis d'ion lithium (LIS) (ce LIS comprenant un oxyde de titane ou de niobium) dans un premier réacteur agité pour former un complexe d'ion lithium avec le tamis d'ion lithium, et décomplexer l'ion lithium du tamis d'ion lithium dans un second réacteur agité pour former le tamis d'ion lithium et un éluat de sel de lithium acide.
EP20940367.4A 2020-06-08 2020-06-09 Procédé de récupération de lithium à partir de saumure Pending EP4161875A1 (fr)

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US20230373803A1 (en) * 2022-05-20 2023-11-23 Schlumberger Technology Corporation Lithium recovery from precipitated solids
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EP3538266B1 (fr) * 2016-11-14 2024-08-21 Lilac Solutions, Inc. Extraction de lithium avec des particules revêtues d'échange d'ions
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US11534748B2 (en) 2017-12-27 2022-12-27 Standard Lithium Ltd. Process for recovery of lithium from brine
US10648090B2 (en) * 2018-02-17 2020-05-12 Lilac Solutions, Inc. Integrated system for lithium extraction and conversion
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