WO2025220284A1 - Procédé de récupération de lithium et procédé de récupération de métaux - Google Patents

Procédé de récupération de lithium et procédé de récupération de métaux

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Publication number
WO2025220284A1
WO2025220284A1 PCT/JP2025/000393 JP2025000393W WO2025220284A1 WO 2025220284 A1 WO2025220284 A1 WO 2025220284A1 JP 2025000393 W JP2025000393 W JP 2025000393W WO 2025220284 A1 WO2025220284 A1 WO 2025220284A1
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WIPO (PCT)
Prior art keywords
lithium
solution
metal
extraction
containing solution
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Pending
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PCT/JP2025/000393
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English (en)
Japanese (ja)
Inventor
淳一 荒川
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Jx Metals Circular Solutions Co Ltd
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Jx Metals Circular Solutions Co Ltd
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Publication of WO2025220284A1 publication Critical patent/WO2025220284A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B23/00—Obtaining nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • 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
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • This specification describes a lithium recovery method and a metal recovery method.
  • the battery powder obtained through heat treatment or other processes is brought into contact with an acidic leachate such as sulfuric acid, and the metals in the battery powder are leached into the acidic leachate.
  • an acidic leachate such as sulfuric acid
  • the metals in the battery powder are leached into the acidic leachate.
  • the metals are separated from the metal-containing solution. Specifically, as described in Patent Documents 1 to 3, for example, aluminum ions, iron ions, and manganese ions are separated sequentially or simultaneously from the metal ions in the metal-containing solution by neutralization or solvent extraction. Thereafter, cobalt ions and nickel ions are separated by solvent extraction and then concentrated and extracted.
  • the post-extraction liquid after nickel extraction becomes a lithium-containing solution containing primarily lithium ions.
  • This lithium-containing solution may be subjected to processes such as carbonation, hydroxide ionization using electrodialysis, or other treatments to recover the lithium contained therein in the form of a specified solution or solid compound (see, for example, Patent Documents 4 to 6).
  • JP 2010-180439 A US Patent Application Publication No. 2011/0135547 JP 2014-162982 A Japanese Patent Application Laid-Open No. 2019-011518 JP 2009-270188 A JP 2011-31232 A
  • the lithium-containing solution obtained after extracting nickel ions from the metal-containing solution will also have a low lithium ion concentration. If an attempt is made to recover lithium from a lithium-containing solution with a low lithium ion concentration, the time and effort required for lithium recovery will increase, reducing the lithium recovery efficiency and raising concerns about increased costs.
  • This specification provides a lithium recovery method and a metal recovery method that can suppress the generation of precipitates during nickel ion extraction while increasing the efficiency of subsequent lithium recovery.
  • the lithium recovery method described in this specification is a method for recovering lithium from a metal-containing solution containing lithium ions and nickel ions, and includes a nickel extraction step, which involves extracting and separating nickel ions from the metal-containing solution into a solvent; a lithium concentration step, which involves concentrating the lithium-containing solution obtained after the extraction in the nickel extraction step to obtain a lithium concentrated solution having a higher lithium ion concentration than the metal-containing solution obtained during the extraction in the nickel extraction step; and a lithium recovery step, which recovers lithium from the lithium concentrated solution.
  • the metal recovery method described in this specification involves leaching metals from battery powder in lithium-ion battery waste, and then separating and recovering the metals from the resulting metal-containing solution, and includes the lithium recovery method described above.
  • the lithium recovery method described above can suppress the generation of precipitates during nickel ion extraction while increasing the subsequent lithium recovery efficiency.
  • FIG. 1 is a flow chart showing an example of a metal recovery method including a lithium recovery method according to one embodiment.
  • FIG. 2 is a flow chart showing an example of a pretreatment process for obtaining the battery powder of FIG. 1 from lithium ion battery waste.
  • FIG. 2 is a cross-sectional view schematically illustrating an example of a bipolar membrane electrodialysis device that can be used when performing hydroxide oxidation by electrodialysis in the lithium recovery step included in the metal recovery method of FIG. 1 is a graph showing the change over time in the lithium ion concentration of each solution during nickel ion extraction in Test Example 1 of the embodiment.
  • 1 is a graph showing the change over time in the lithium ion concentration and the sodium ion concentration of the metal-containing solution in Test Example 2 of the embodiment. 1 is a graph showing the relationship between the lithium ion concentration and current efficiency of a lithium-containing solution obtained in the electrodialysis test of Test Example 4.
  • a lithium recovery method in one embodiment is a method for recovering lithium from a metal-containing solution containing lithium ions and nickel ions, and includes a nickel extraction step, a lithium concentration step, and a lithium recovery step in this order.
  • the nickel extraction process involves extracting and separating nickel ions from the metal-containing solution into a solvent.
  • the subsequent lithium concentration process concentrates the lithium-containing solution obtained after extraction in the nickel extraction process.
  • the lithium-containing solution is concentrated to obtain a lithium-concentrated solution with a higher lithium ion concentration than the metal-containing solution obtained during extraction in the nickel extraction process.
  • the lithium recovery method of this embodiment may be incorporated into a metal recovery method having the steps shown in Figure 1, for example.
  • battery powder from lithium-ion battery waste is subjected to an acid leaching step, a neutralization step, a manganese and/or aluminum extraction step, a cobalt extraction step, a nickel extraction step, a lithium concentration step, and a lithium recovery step, in this order.
  • battery powder can be obtained by subjecting lithium-ion battery waste to a pretreatment step.
  • Figures 1 and 2 are merely examples and the method is not limited to such specific flows.
  • the target lithium-ion battery waste is lithium-ion secondary batteries that can be used in mobile phones and various other electronic devices, etc., that have been discarded due to the end of the battery product's life, manufacturing defects, or other reasons. Recovering valuable metals from such lithium-ion battery waste is preferable from the perspective of effective resource utilization.
  • Lithium-ion battery waste has a casing containing aluminum, and may contain a positive electrode active material made of a single metal oxide containing lithium and one or more selected from the group consisting of nickel, cobalt, and manganese, or a composite metal oxide containing two or more selected metals, or an aluminum foil (positive electrode substrate) to which the positive electrode active material is coated and fixed with, for example, polyvinylidene fluoride (PVDF) or other organic binders.
  • PVDF polyvinylidene fluoride
  • Lithium-ion battery waste may also contain copper, iron, etc.
  • the casing may contain an electrolyte solution prepared by dissolving an electrolyte such as lithium hexafluorophosphate in an organic solvent such as ethylene carbonate or diethyl carbonate.
  • Pretreatment process Lithium-ion battery waste is often subjected to a pretreatment process.
  • the pretreatment process may include at least one of roasting, crushing, and sieving. Lithium-ion battery waste is converted into battery powder through the pretreatment process.
  • the roasting, crushing, and sieving pretreatment processes may be performed individually as needed, or may be performed in any order.
  • Battery powder refers to a powder obtained by separating and concentrating positive electrode material components from lithium-ion battery waste through some kind of pretreatment. Battery powder may also be obtained by crushing and sieving lithium-ion battery waste with or without heat treatment, resulting in a powder with concentrated positive electrode material components.
  • the lithium-ion battery waste is heated. Roasting decomposes and removes the electrolyte and organic binder, and metals such as lithium and cobalt contained in the lithium-ion battery waste may be converted into forms that are more soluble in the acid leaching solution during the acid leaching process.
  • the composition of the positive electrode active material changes during roasting, the term "positive electrode active material" is used here even if the material has undergone roasting.
  • the lithium-ion battery waste is preferably heated and maintained at a temperature in the range of 600°C to 800°C for 0.5 to 6 hours. Roasting can be performed in air or in an inert atmosphere such as nitrogen. Roasting under these atmospheres may be performed in this order or the reverse order.
  • the roasting furnace may be, for example, a batch-type stationary furnace, a continuous rotary kiln furnace, or any other type of furnace.
  • the waste lithium-ion batteries can be crushed.
  • crushing the casings of the waste lithium-ion batteries are broken and the positive electrode active material is selectively separated from the aluminum foil to which it is applied.
  • Various known devices or equipment can be used for crushing, but it is particularly preferable to use an impact crusher, which can crush the waste lithium-ion batteries by applying impact while cutting them. Examples of such impact crushers include a sample mill, hammer mill, pin mill, wing mill, tornado mill, and hammer crusher.
  • the lithium-ion battery waste is crushed, it is sieved using a sieve with appropriate mesh sizes. This leaves aluminum and copper on the sieve, while leaving battery powder with some of the aluminum and copper removed.
  • the battery powder contains nickel, the nickel content is, for example, 1% to 30% by mass, typically 5% to 20% by mass.
  • the battery powder contains cobalt, the cobalt content in the battery powder is, for example, 1% to 30% by mass, typically 5% to 20% by mass.
  • the battery powder may also contain, for example, 2% to 8% by mass of lithium, 1% to 30% by mass of manganese, 1% to 10% by mass of aluminum, 1% to 5% by mass of iron, and 1% to 10% by mass of copper.
  • the battery powder may be brought into contact with water before the acid leaching process described below, allowing the lithium in the battery powder to leach into the water.
  • the acid leaching process is carried out on the battery powder that remains after the water leaching.
  • the battery powder may also be subjected to the acid leaching process without water leaching. If water leaching is not carried out, it becomes easier to maintain a high lithium ion concentration in the solution during the wet processing that follows the acid leaching process.
  • the metals in the battery powder are leached by contacting them with an acidic leaching solution containing a mineral or inorganic acid such as sulfuric acid, hydrochloric acid, or nitric acid. This dissolves the metals in the battery powder, resulting in a leached solution containing the metals as metal ions.
  • the solution containing the metals in the battery powder as metal ions is referred to as the metal-containing solution.
  • the metal-containing solution includes the leached solution obtained in the acid leaching process and sent to the subsequent neutralization process, as well as solutions in the middle of the neutralization process or various metal extraction processes.
  • the pH of the acidic leachate during leaching is preferably between -0.5 and 3.0, and may be between 0.5 and 2.0 for the post-leaching solution after leaching is complete.
  • the pH of the solution can be measured using a multi-purpose water quality meter such as the MX-43X and composite electrode GST-5841C manufactured by DKK-TOA Corporation.
  • the acidic leachate may be stirred at 100 to 400 rpm using a stirrer as needed, and the liquid temperature may be raised to 50 to 80°C, or even 65 to 70°C.
  • the post-leaching solution obtained in the acid leaching process may have, for example, a cobalt ion concentration of 10 g/L to 50 g/L, a nickel ion concentration of 10 g/L to 50 g/L, a manganese ion concentration of 0 g/L to 50 g/L, a lithium ion concentration of 1.0 g/L to 30.0 g/L, an aluminum ion concentration of 1.0 g/L to 20 g/L, an iron ion concentration of 0.1 g/L to 5.0 g/L, and a copper ion concentration of 0.005 g/L to 0.2 g/L.
  • the metal ion concentrations in the solution can be confirmed by analysis using an ICP optical emission spectrometer (such as the SPS3300 manufactured by SII NanoTechnology Inc.).
  • the neutralization step In the neutralization step, the pH of the metal-containing solution (the post-leaching solution) is increased, and the neutralization residue is separated to obtain a post-neutralization solution.
  • the neutralization step may include, for example, a dealumination step in which the pH is increased to that of the metal-containing solution to precipitate and remove at least a portion of the aluminum ions, followed by a de-ironization step in which an oxidizing agent is added to oxidize the iron ions, and if necessary, the pH is further increased to precipitate and remove the iron ions.
  • the de-ironization step may be omitted.
  • the pH may be set within the range of 3.0 to 4.5.
  • the oxidation-reduction potential (based on silver/silver chloride potential, ORP) during oxidation may be set between 300 mV and 900 mV.
  • the oxidation-reduction potential of the solution can be measured using a multi-water quality meter MX-43X and composite electrode PST-5721C manufactured by DKK-TOA Corporation.
  • the neutralization residue as precipitate can be removed by solid-liquid separation such as filtration using known devices and methods such as a filter press or thickener.
  • alkaline pH adjusters such as lithium hydroxide, sodium hydroxide, sodium carbonate, and ammonia can be used.
  • the lithium hydroxide solution obtained by electrodialysis in the lithium recovery process described below can be used; in this case, lithium ions circulate within the series of wet treatment processes.
  • the oxidizing agent used in the iron removal stage as long as it is capable of oxidizing iron, but manganese dioxide, positive electrode active material, and/or manganese-containing leaching residue obtained by leaching the positive electrode active material are preferred.
  • the metal-containing solution as the post-neutralization solution can be subjected to solvent extraction to extract and separate manganese ions and/or the remaining aluminum ions that were not completely removed in the neutralization step. In this case, the remaining manganese ions and aluminum ions are extracted, thereby obtaining a post-manganese-extracted solution from which they have been removed.
  • a phosphate ester extractant such as di-2-ethylhexyl phosphoric acid (abbreviation: D2EHPA or product name: DP-8R)
  • a mixture of a phosphate ester extractant and an aldoxime or oxime extractant containing aldoxime as the main component such as 2-hydroxy-5-nonylacetophenone oxime (product name: LIX84), 5-dodecylsalicyldoxime (product name: LIX860), a mixture of LIX84 and LIX860 (product name: LIX984), or 5-nonylsalicylaldoxime (product name: ACORGAM5640)
  • D2EHPA di-2-ethylhexyl phosphoric acid
  • DP-8R aldoxime or oxime extractant containing aldoxime as the main component
  • an aldoxime or oxime extractant containing aldoxime as the main component such as 2-hydroxy-5-nonylacetophenone oxi
  • the equilibrium pH is preferably adjusted to 2.3 to 3.5, more preferably 2.5 to 3.0.
  • the alkaline pH adjuster used here is preferably lithium hydroxide solution obtained by electrodialysis in the lithium recovery process described below, but separately prepared sodium hydroxide or the like can also be used.
  • Countercurrent multi-stage extraction in which the aqueous phase and solvent used in each extraction flow in opposite directions. This prevents other metal ions, such as cobalt ions, nickel ions, and lithium ions, from being extracted, and increases the extraction rate of manganese ions.
  • countercurrent multi-stage extraction it is effective to set the equilibrium pH during the first extraction stage to a value within the above-mentioned range, and then increase the equilibrium pH during each subsequent extraction stage.
  • Countercurrent multi-stage extraction is also suitable for the cobalt extraction process and nickel extraction process described below.
  • Cobalt extraction process In the cobalt extraction step, cobalt ions are separated by solvent extraction from a metal-containing solution as a post-manganese extraction solution obtained after the manganese extraction step. At this time, magnesium ions that may be contained in the metal-containing solution are also extracted, and there is a possibility that these can be removed.
  • a solvent containing a phosphonate ester extractant such as 2-ethylhexyl 2-ethylhexylphosphonate (trade names: PC-88A, Ionquest 801).
  • the equilibrium pH can be adjusted to preferably 5.0 to 6.0, more preferably 5.0 to 5.5.
  • a lithium hydroxide solution obtained by electrodialysis in the lithium recovery process described below as the pH adjuster, but separately prepared sodium hydroxide or the like can also be used.
  • the solvent from which the cobalt ions have been extracted can be scrubbed if necessary, and then back-extracted using a back-extraction solution containing sulfuric acid, hydrochloric acid, or nitric acid, for example, at a pH of 2.0 to 4.0.
  • the back-extracted solution can then be heated and concentrated, allowing the cobalt ions to crystallize as cobalt salts.
  • the metal-containing solution as the post-cobalt extraction solution after the cobalt ions have been extracted in the cobalt extraction step mainly contains nickel ions and lithium ions.
  • nickel ions are extracted and separated from this metal-containing solution.
  • a mixer-settler may be used for extraction, not just in the nickel extraction process.
  • a pH adjuster is first added to the solvent to adjust the equilibrium pH during extraction.
  • the metal-containing solution (aqueous phase) and solvent (organic phase) are mixed in a mixer to form a mixed liquid, and the mixed liquid is stirred.
  • the metal ions to be extracted in the metal-containing solution (nickel ions in the case of extraction in the nickel extraction process) migrate to the solvent.
  • the mixed liquid is then left to stand in a settler, and the aqueous and organic phases are separated based on the difference in their specific gravities. This results in a post-extraction liquid from which the solvent has been separated.
  • the metal-containing solution subjected to the neutralization process described above has a high aluminum content, or if the amount of components to be extracted in each extraction process is large, a large amount of pH adjuster will be required to adjust the pH.
  • the metal-containing solution subjected to the extraction described above may have a relatively high lithium ion concentration.
  • the post-extraction solution from the nickel extraction process lithium sulfate solution, etc.
  • the lithium ion concentration of the metal-containing solution subjected to the extraction described above may be relatively high.
  • the lithium ion concentration of the metal-containing solution used in the nickel extraction step is high, a lithium-containing precipitate may occur in the mixer settler during nickel ion extraction. In this case, the precipitate may clog the piping, making it difficult to carry out the extraction operation smoothly.
  • This precipitate may contain lithium , specifically, a mixture of Li2SO4 ( H2O ) and the solvent oil.
  • the metal-containing solution used in the nickel extraction step has a low lithium ion concentration. Specifically, the lithium ion concentration of the metal-containing solution during nickel ion extraction in the nickel extraction step is set lower than the lithium ion concentration of the lithium concentrated solution obtained in the lithium concentration step described below. This effectively suppresses the generation of precipitates during nickel ion extraction.
  • Metal-containing solutions often contain inorganic acid anions such as sulfate ions.
  • a saturated lithium salt solution is a solution of lithium salts formed from the inorganic acid anions and lithium ions contained in the metal-containing solution
  • the lithium ion concentration of the metal-containing solution during nickel ion extraction be equal to or lower than the lithium ion concentration of the saturated lithium salt solution.
  • saturated lithium salt solution refers to a saturated solution of lithium salts formed from the main inorganic acid anions (sulfate ions, nitrate ions, chloride ions, etc.) contained in the metal-containing solution and lithium ions. If the metal-containing solution contains sulfate ions in the greatest amount among the inorganic acid anions contained therein, the lithium salt is lithium sulfate.
  • a pH adjuster containing lithium ions may be used to adjust the equilibrium pH during nickel ion extraction.
  • the lithium ion concentration of the metal-containing solution during nickel ion extraction refers to the lithium ion concentration of the mixture of the metal-containing solution and the pH adjuster before use (before mixing) of the pH adjuster, and it is preferable that the lithium ion concentration of this mixture be equal to or lower than the lithium ion concentration of the saturated lithium salt solution.
  • the lithium ion-containing pH adjuster examples include lithium hydroxide.
  • Lithium hydroxide may be in the form of a solid, such as a powder, or a solution.
  • the lithium hydroxide solution may be the lithium hydroxide solution obtained in the lithium recovery process described below.
  • the sum of the lithium ion concentration (g/L) of the metal-containing solution before use (before mixing) of the pH adjuster and the lithium ion concentration (g/L) of the pH adjuster may be set to be equal to or less than the lithium ion concentration (g/L) of the saturated lithium salt solution.
  • the lithium ion concentration (g/L) of the metal-containing solution before use (before mixing) of the pH adjuster is X
  • the lithium ion concentration (g/L) of the pH adjuster is Y
  • the lithium ion concentration (g/L) of the saturated lithium salt solution is Z
  • the main inorganic acid anion contained in the metal-containing solution is sulfate ion
  • the lithium ion concentration of the metal-containing solution before use (before mixing) of the pH adjuster is 10 g/L
  • the lithium ion concentration of the pH adjuster is 20 g/L
  • the lithium ion concentration of the saturated lithium sulfate salt solution at a temperature of 40 °C is 42.5 g/L
  • solubility is often temperature-dependent, and the above solubility refers to the solubility at the temperature at which extraction is performed.
  • the solvent used in the nickel extraction process preferably contains a carboxylic acid extractant.
  • carboxylic acid extractants include neodecanoic acid and naphthenic acid, with neodecanoic acid (such as Versatic Acid 10 (VA-10) manufactured by Shell Chemical Co.) being preferred due to its ability to extract nickel ions.
  • the extractant may be diluted with a hydrocarbon organic solvent such as an aromatic, paraffinic, or naphthenic solvent to a concentration of 10% to 30% by volume, and this may be used as the solvent.
  • the equilibrium pH during extraction is preferably 6.0 to 8.0, more preferably 6.8 to 7.2.
  • the pH adjuster used to adjust the pH at this time is preferably a lithium hydroxide solution; for example, the lithium hydroxide solution obtained by electrodialysis in the lithium recovery step described below can be used.
  • the lithium ion concentration of the metal-containing solution and pH adjuster so that the lithium ion concentration of the lithium-containing solution as the post-extraction liquid separated from the solvent during extraction is less than 15 g/L, for example, 10 g/L to 14 g/L. If the lithium ion concentration of the lithium-containing solution is too low, the load in the lithium concentration step described below will increase, and the lithium recovery rate in the lithium recovery step may decrease.
  • the solvent containing nickel ions may be scrubbed one or more times using a scrubbing solution, if necessary, to remove any lithium ions that may be contained in the solvent.
  • the solvent containing nickel ions can then be stripped using a stripping solution such as sulfuric acid. After this, electrolysis and dissolution can be performed as necessary, followed by heating, allowing the nickel ions to crystallize as nickel salts such as nickel sulfate.
  • At least a portion of the lithium-containing solution after the nickel ions have been extracted can be mixed with the acid leaching solution in the acid leaching process and used. This allows the lithium ions contained in the lithium-containing solution to be circulated throughout the series of wet processing steps from the acid leaching process to the nickel extraction process.
  • lithium enrichment process Since the lithium ion concentration of the metal-containing solution during extraction is adjusted in the nickel extraction step, the lithium ion concentration of the lithium-containing solution obtained after nickel ions are extracted is relatively low. If this solution is subjected to the lithium recovery step as is, it may result in a decrease in the lithium recovery rate and a decrease in the current efficiency when performing electrodialysis. To address this, in this embodiment, a lithium concentration step is performed to concentrate the lithium-containing solution prior to the lithium recovery step.
  • the concentration method is not particularly limited as long as it produces a lithium concentrated solution with a higher lithium ion concentration than the metal-containing solution obtained during extraction in the nickel extraction step.
  • Specific examples include filtration using a filtration membrane and heat concentration. Of these, filtration is preferred because, by selecting an appropriate filtration membrane, it can effectively remove at least a portion of the impurity metal ions, such as manganese ions, cobalt ions, nickel ions, and magnesium ions, that may be contained in the lithium-containing solution in addition to lithium ions.
  • a solution purification process may be performed separately from the heat concentration to remove at least a portion of the impurity metal ions.
  • Filter membranes used in filtration include, for example, microfiltration (MF) membranes, ultrafiltration (UF) membranes, nanofiltration (NF) membranes, and reverse osmosis (RO) membranes.
  • the lithium concentration process can increase the lithium ion concentration of the lithium-containing solution if it involves filtration using a water-permeable filter membrane.
  • a reverse osmosis membrane is a filter membrane that uses the reverse osmosis phenomenon to allow water to pass through while blocking other ions and particles.
  • a nanofiltration membrane is understood to be a pressure-driven filter membrane with performance intermediate between reverse osmosis and ultrafiltration membranes, inhibiting the penetration of ions and particles smaller than 2 nm. Using these membranes in combination makes it possible to effectively concentrate lithium ions through their permeation and remove at least a portion of the above-mentioned impurity metal ions.
  • the lithium concentration step it is preferable to obtain a lithium concentrated solution having a lithium ion concentration of 15 g/L or more by concentrating the lithium-containing solution as described above. More preferably, the lithium ion concentration of the lithium concentrated solution is 20.0 g/L to 30.0 g/L. This makes it easier to improve the lithium recovery rate in the subsequent lithium recovery step and the current efficiency of electrodialysis. Furthermore, it is preferable that the lithium concentrated solution have a manganese ion concentration of 0.001 g/L or less, a cobalt ion concentration of 0.001 g/L or less, a nickel ion concentration of 0.001 g/L or less, and a magnesium ion concentration of 0.001 g/L or less.
  • lithium recovery process In the lithium recovery step, lithium is recovered in the form of a solution, a solid, etc. from the lithium concentrated solution obtained in the lithium concentration step. Typically, hydroxylation and/or carbonation can be carried out in the lithium recovery step.
  • lithium hydroxide solution may be produced from the above-mentioned lithium concentrated solution, such as lithium sulfate solution.
  • the details are not particularly important as long as lithium hydroxide solution can be produced, but methods that can be used include, for example, a carbonation and chemical conversion method in which calcium hydroxide is used after lithium carbonate is produced, a chemical conversion method using barium hydroxide, and electrodialysis.
  • a lithium carbonate solution is first obtained by adding a carbonate to a lithium-containing solution or by blowing carbon dioxide gas into the solution. Then, calcium hydroxide is added to the lithium carbonate solution to produce a lithium hydroxide solution according to the reaction formula Li2CO3 + Ca(OH) 2 ⁇ 2LiOH + CaCO3 .
  • barium hydroxide is added to the lithium-containing solution to produce a lithium hydroxide solution according to the reaction Li2SO4 + Ba(OH) 2 ⁇ 2LiOH + BaSO4 .
  • Calcium ions and barium ions that may remain in the lithium hydroxide solution obtained by the chemical conversion method can be removed using a cation exchange resin, a chelating resin, or the like. Electrodialysis will be described in detail below.
  • a lithium hydroxide solution can be produced from a lithium concentrate solution by performing electrodialysis using a commercially available bipolar membrane electrodialysis device 1 (hereinafter simply referred to as "electrodialysis device 1") as shown in Figure 3.
  • the illustrated electrodialysis device 1 has an anode 2 and a cathode 3 within a cell, and a bipolar membrane 4, an anion exchange membrane 5, a cation exchange membrane 6, and a bipolar membrane 7 arranged sequentially between the anodes 2 and 3, from the anode 2 side toward the cathode 3 side.
  • the bipolar membranes 4 and 7 are each composed of a cation exchange layer and an anion exchange layer stacked one on top of the other.
  • a lithium concentrate is supplied to the deionization compartment R1
  • pure water is supplied to each of the acid compartment R2 and alkaline compartment R3, and a predetermined voltage is applied between the anode 2 and the cathode 3.
  • lithium ions (Li + ) in the lithium concentrate in the deionization compartment R1 pass through the cation exchange membrane 6 and move to the alkaline compartment R3.
  • water (H 2 O) is decomposed by the bipolar membrane 7, and hydroxide ions (OH ⁇ ) are present, resulting in a lithium hydroxide solution being obtained as the post-dialysis solution.
  • inorganic acid anions in the lithium concentrate in the deionization compartment R1 pass through the anion exchange membrane 5 and move to the acid compartment R2.
  • these anions and hydrogen ions (H + ) generated from water (H 2 O) by the bipolar membrane 4 produce an acid solution such as a sulfuric acid solution.
  • the post-dialysis solution (lithium hydroxide solution) obtained in the alkaline compartment R3 contains almost no inorganic acid anions.
  • the inorganic acid anions are sulfate ions (SO 4 2 ⁇ ), but they may be nitrate ions (NO 3 ⁇ ) or chloride ions (Cl ⁇ ) depending on the type of acid used in the acid leaching process.
  • lithium salts are separated from the lithium concentrate as described above, leaving the desalination solution.
  • concentration of inorganic acid anions tends to be higher in the acid solution than in the post-dialysis solution (lithium hydroxide solution), and also tends to be higher in the desalination solution than in the post-dialysis solution (lithium hydroxide solution).
  • the lithium hydroxide solution obtained by hydroxylation can be effectively used as a pH adjuster in the neutralization process and in the extraction process for various metals.
  • the lithium ion concentration of the lithium hydroxide solution can be increased by heating and concentrating it, and then this can be used as a pH adjuster.
  • solid lithium hydroxide can be precipitated from the lithium hydroxide solution by crystallization procedures such as heating and concentrating it or distilling it under reduced pressure.
  • the lithium concentrated solution used in the electrodialysis described above has an increased lithium ion concentration. This allows for improved current efficiency during electrodialysis. Details will be explained in the Examples section, but this is based on the finding that the higher the lithium ion concentration of the solution used in electrodialysis, the better the current efficiency of electrodialysis. This is thought to be because, when the lithium ion concentration of the solution used in electrodialysis is high, the difference in lithium ion concentration between that solution and the lithium hydroxide solution obtained by electrodialysis becomes greater, improving current efficiency.
  • the carbonation may be carried out by, for example, adjusting the pH to 10-13, adding a carbonate such as sodium carbonate or ammonium carbonate to the lithium concentrated solution, or by blowing in carbon dioxide gas, to recover the lithium ions in the lithium concentrated solution as solid lithium carbonate. Since the solubility of lithium carbonate is approximately 2 g/L in terms of lithium ion concentration, the higher the lithium ion concentration in the lithium concentrated solution before carbonation, the higher the lithium recovery rate.
  • a carbonate such as sodium carbonate or ammonium carbonate
  • the purity of the lithium carbonate is low, it can be purified as necessary.
  • the crude lithium carbonate is subjected to repulp washing and carbon dioxide gas is blown into it to dissolve the carbonic acid in the liquid. Impurities are then separated from the lithium bicarbonate solution by solid-liquid separation. After that, the solution is deoxidized and concentrated, and then separated into purified lithium carbonate and a filtrate by solid-liquid separation. Further washing can then be carried out.
  • metal ion concentrations were measured using an ICP optical emission spectrometer SPS3300 manufactured by SII Nanotechnology Inc., and pH was measured using a multi-purpose water quality meter MX-43X and composite electrode GST-5841C manufactured by DKK-TOA Corporation.
  • the lithium hydroxide solution prepared by hydroxide oxidation in the lithium recovery process was used as a pH adjuster in each of the neutralization process, manganese and/or aluminum extraction process, cobalt extraction process, and nickel extraction process, and a metal recovery method including these processes was continuously carried out.
  • the lithium ion concentration of the lithium hydroxide solution used as the pH adjuster was 28 g/L.
  • nickel ions were transferred from the metal-containing solution to the solvent in a mixer settler using a solvent containing the carboxylic acid extractant VA-10.
  • the nickel ion concentration in the metal-containing solution before extraction was 8-12 g/L
  • the nickel ion concentration in the post-extraction solution was 0.001-0.01 g/L.
  • the solvent was a mixture of VA-10 and a hydrocarbon organic solvent, containing VA-10 at a concentration of 25% by volume.
  • the equilibrium pH during extraction was adjusted to 6.8-7.2, typically around 7.0, using the pH adjuster described above.
  • the anion of the inorganic acid contained in the pre-extraction solution is sulfate ion, and the lithium ion concentration in a saturated solution of lithium sulfate as a lithium salt (lithium ion concentration of the saturated lithium salt solution) is 42.5 g/L at the temperature during extraction (40°C).
  • the lithium ion concentration of this saturated lithium salt solution can be calculated from the lithium sulfate (Li 2 SO 4 ) concentration of 337 g/L in the saturated lithium sulfate solution at 40°C by the formula: 337 ⁇ 6.94 ⁇ 2/109.945 ⁇ 42.5.
  • the sum of the lithium ion concentration of the pre-extraction solution and the lithium ion concentration of the pH adjuster was 46 to 48 during Period A, which was higher than the lithium ion concentration of the saturated lithium salt solution (42.5 g/L).
  • Period B the sum was 40 to 41, which was lower than the lithium ion concentration of the saturated lithium salt solution (42.5 g/L).
  • period C the total was 43 to 44, which was higher than the lithium ion concentration (42.5 g/L) of the saturated lithium salt solution.
  • the precipitates formed in the mixer settler were analyzed by X-ray diffraction (XRD), and it was confirmed that the precipitates contained Li2SO4 ( H2O ).
  • XRD X-ray diffraction
  • the precipitates were insoluble in water or acid and the nature of the precipitates, it was estimated that the precipitates were a mixture of Li2SO4 ( H2O ) and oil.
  • Test Example 2 The metal recovery method was continuously carried out in the same manner as in Test Example 1, except that the lithium hydroxide solution prepared by hydroxide oxidation was not used, and separately prepared sodium hydroxide was used as a pH adjuster in each of the neutralization step, manganese and/or aluminum extraction step, cobalt extraction step, and nickel extraction step. The lithium ion concentration and sodium ion concentration of the metal-containing solution subjected to the nickel extraction step were measured, and the changes in each concentration over time were confirmed. The results are shown in Figure 5.
  • Figure 5 shows that when sodium hydroxide is used as the pH adjuster, the lithium ion concentration in the metal-containing solution remains sufficiently low. Furthermore, no precipitates formed in the mixer-settler used for extraction in the nickel extraction process. This suggests that the formation of precipitates becomes apparent when lithium hydroxide solution is used as a pH adjuster and lithium is circulated within the wet process, as in Test Example 1. For this reason, the metal recovery method described above is considered to be particularly effective in such cases.
  • the lithium hydroxide solution obtained by hydroxide oxidation was used as the pH adjuster.
  • the lithium ion concentration of this pH adjuster was 12 g/L, and the lithium ion concentration of the pre-extraction solution was 17 g/L or less.
  • the sum of the lithium ion concentration of the pH adjuster and the lithium ion concentration of the metal-containing solution was 29 or less, which is less than the lithium ion concentration of a saturated lithium salt solution (42.5 g/L). Under these conditions, extraction was performed with an equilibrium pH of 6.8 to 7.0, and no precipitate was formed.
  • the lithium ion concentration of the post-extraction solution after separation from the solvent was 18 g/L or less.
  • Test Example 4 A test was conducted in which a number of lithium-containing solutions with different lithium ion concentrations ranging from 10 g/L to 20 g/L were subjected to electrodialysis to prepare lithium hydroxide solutions (post-dialysis solutions).
  • the electrodialysis conditions were a constant voltage of 32 V and a liquid supply rate of 0.13 L/min/ m2 .
  • Figure 6 shows a graph illustrating the relationship between lithium ion concentration (feedstock solution concentration) and current efficiency obtained as a result of the test.
  • Figure 6 shows that the higher the lithium ion concentration of the lithium-containing solution used for electrodialysis, the better the current efficiency during electrodialysis. Therefore, concentrating the lithium-containing solution before electrodialysis to increase the lithium ion concentration is thought to contribute to improving the current efficiency during electrodialysis.
  • Figure 6 also shows the Li loss rate, which is the amount of lithium ions in the post-dialysis solution divided by the amount of lithium ions in the lithium-containing solution; the Li loss rate was approximately the same regardless of the Li concentration of the lithium-containing solution.
  • the lithium recovery method described above may be able to suppress the formation of precipitates during nickel ion extraction while still allowing lithium to be effectively recovered afterwards.
  • this embodiment may contribute to Goal 9 "Build resilient infrastructure, promote inclusive and sustainable industrialization and foster innovation" and Goal 12 "Ensure sustainable consumption and production patterns" of the United Nations-led Sustainable Development Goals (SDGs) by promoting waste reuse and improving resource utilization efficiency.

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Abstract

La présente invention concerne un procédé de récupération de lithium à partir d'une solution contenant des métaux comprenant des ions lithium et des ions nickel, ledit procédé comprenant : une étape d'extraction du nickel consistant à effectuer une extraction qui implique l'extraction et la séparation des ions nickel présents dans la solution contenant des métaux dans un solvant; une étape de concentration du lithium consistant à concentrer la solution contenant du lithium obtenue après l'extraction de l'étape d'extraction du nickel et à obtenir un concentré de lithium présentant une concentration en ions lithium supérieure à celle de la solution contenant des métaux au moment de l'extraction pendant l'étape d'extraction du nickel; et une étape de récupération du lithium consistant à récupérer le lithium à partir du concentré de lithium.
PCT/JP2025/000393 2024-04-15 2025-01-08 Procédé de récupération de lithium et procédé de récupération de métaux Pending WO2025220284A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018181816A1 (fr) * 2017-03-31 2018-10-04 Ｊｘ金属株式会社 Procédé de traitement de déchets de batterie lithium-ion
WO2023054667A1 (fr) * 2021-09-30 2023-04-06 株式会社アサカ理研 Procédé de récupération de lithium à partir de batteries lithium-ion usagées
WO2023058548A1 (fr) * 2021-10-05 2023-04-13 東レ株式会社 Procédé de récupération d'ions métalliques monovalents
JP2023100242A (ja) * 2022-01-05 2023-07-18 Ｊｘ金属株式会社 リチウムイオン電池廃棄物の金属回収方法
WO2024014522A1 (fr) * 2022-07-14 2024-01-18 Jx Metals Corporation Procédé de récupération de métaux

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018181816A1 (fr) * 2017-03-31 2018-10-04 Ｊｘ金属株式会社 Procédé de traitement de déchets de batterie lithium-ion
WO2023054667A1 (fr) * 2021-09-30 2023-04-06 株式会社アサカ理研 Procédé de récupération de lithium à partir de batteries lithium-ion usagées
WO2023058548A1 (fr) * 2021-10-05 2023-04-13 東レ株式会社 Procédé de récupération d'ions métalliques monovalents
JP2023100242A (ja) * 2022-01-05 2023-07-18 Ｊｘ金属株式会社 リチウムイオン電池廃棄物の金属回収方法
WO2024014522A1 (fr) * 2022-07-14 2024-01-18 Jx Metals Corporation Procédé de récupération de métaux

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