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WO2025192009A1 - Procédé de récupération de solution aqueuse - Google Patents

Procédé de récupération de solution aqueuse

Info

Publication number
WO2025192009A1
WO2025192009A1 PCT/JP2025/000808 JP2025000808W WO2025192009A1 WO 2025192009 A1 WO2025192009 A1 WO 2025192009A1 JP 2025000808 W JP2025000808 W JP 2025000808W WO 2025192009 A1 WO2025192009 A1 WO 2025192009A1
Authority
WO
WIPO (PCT)
Prior art keywords
lithium
aqueous solution
chlorine
composite oxide
recovering
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/000808
Other languages
English (en)
Japanese (ja)
Inventor
風彦 永田
陽太郎 井上
雄太 日野
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.)
JFE Steel Corp
Original Assignee
JFE Steel Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JFE Steel Corp filed Critical JFE Steel Corp
Publication of WO2025192009A1 publication Critical patent/WO2025192009A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/04—Halides
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C22B1/08—Chloridising roasting
    • 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
    • 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

  • the present invention relates to an aqueous solution recovery method for recovering lithium contained in a composite oxide obtained by dissolving lithium-ion batteries as an aqueous solution containing lithium.
  • lithium-ion batteries Batteries that use lithium (hereinafter referred to as “lithium-ion batteries”) are used in a wide range of devices, from relatively small devices such as personal computers and smartphones to large devices such as electric vehicles and solar power storage facilities.
  • Lithium-ion batteries are constructed using exterior materials made from metals such as iron or aluminum. Inside the exterior material are positive electrode materials, which consist of aluminum foil with a positive electrode active material such as lithium nickel oxide or lithium cobalt oxide adhered to it, and negative electrode materials, which consist of copper foil with a negative electrode active material such as graphite adhered to its surface. A separator made of a porous resin film such as polypropylene is placed between the positive and negative electrode materials, and the interior of the exterior material is filled with an electrolyte such as lithium hexafluorophosphate and sealed inside.
  • positive electrode materials consist of aluminum foil with a positive electrode active material such as lithium nickel oxide or lithium cobalt oxide adhered to it
  • negative electrode materials which consist of copper foil with a negative electrode active material such as graphite adhered to its surface.
  • a separator made of a porous resin film such as polypropylene is placed between the positive and negative electrode materials, and the interior of the exterior material is filled with an electrolyte such as lithium hex
  • Patent Document 1 discloses a method for producing slag with a high lithium content, by specifying the ranges of Al/Li and Si/Li values and the Al and Si contents for Li-containing slag obtained by melting raw materials such as waste lithium-ion batteries.
  • Patent Document 2 discloses a method for recovering lithium chloride produced in molten metal obtained by melting waste lithium-ion batteries using a pyrometallurgical process, by adding a chloride source to the molten metal, as metal fumes.
  • the present invention was made in consideration of the above circumstances, and its purpose is to provide an aqueous solution recovery method that can recover lithium contained in a composite oxide as an aqueous solution containing lithium.
  • a method for recovering lithium contained in a composite oxide as an aqueous solution containing lithium comprising: a contacting step of contacting the composite oxide with chlorine or a chlorine compound, the chlorine or chlorine compound being adjusted so that the substance amount ratio of chlorine to lithium contained in the composite oxide is 1.0 or more and 5.5 or less, at a temperature of 500°C or more and 1350°C or less; and an aqueous solution recovering step of contacting the chlorine or chlorine compound and the composite oxide that have been subjected to the contacting step with an aqueous solution to recover the aqueous solution into which the lithium has permeated.
  • lithium contained in the composite oxide can be recovered as an aqueous solution containing lithium.
  • the aqueous solution recovery method of the present invention is a method for recovering lithium contained in a composite oxide as an aqueous solution containing lithium.
  • slag remaining after metals containing one or two of cobalt and nickel are recovered from molten metal obtained by dissolving lithium-ion batteries using a pyrometallurgical process may be used.
  • the aqueous solution recovery method of the present invention includes a contacting step in which chlorine or a chlorine compound, which has been adjusted so that the mass ratio of chlorine to lithium contained in the composite oxide is 1.0 or more and 5.5 or less, is brought into contact with the composite oxide at a temperature of 500°C or more and 1350°C or less.
  • the ratio of chlorine to lithium contained in the composite oxide by mass is preferably 5.5 or less, and more preferably 5.0 or less.
  • the chlorine or chlorine compound may be adjusted by calculating the mass of lithium contained in the composite oxide before contacting it with the composite oxide, and adjusting the mass ratio of chlorine to lithium based on the calculated mass of lithium so that the mass ratio of chlorine to lithium is 1.0 or more and 5.5 or less. More specifically, the amount of chlorine or chlorine compound to be contacted with the composite oxide may be adjusted so that the mass ratio of chlorine to lithium is 1.0 or more and 5.5 or less.
  • the method for calculating the mass of lithium is not limited, as long as it is a method that can calculate the mass of lithium contained in the composite oxide. For example, a portion of the composite oxide may be dissolved in acid, and measurement and calculation may be performed using inductively coupled plasma atomic emission spectroscopy (ICP-AES). Alternatively, in the process of producing the composite oxide, the mass concentration of lithium may be calculated based on the mass concentration of lithium contained in each raw material and the weight ratio of each raw material to the total raw materials.
  • ICP-AES inductively coupled plasma atomic emission spectroscopy
  • Chlorine or chlorine compounds are contacted with the composite oxide at a temperature of 500°C or higher and 1350°C or lower. This is because contact at temperatures below 500°C does not promote the chlorination reaction between the lithium contained in the composite oxide and chlorine or chlorine compounds. The higher the temperature, the more promoted the chlorination reaction between lithium and chlorine or chlorine compounds. Therefore, contact at 600°C or higher is preferred, and contact at 800°C or higher is even more preferred. Furthermore, at temperatures above 1350°C, although the chlorination reaction between lithium and chlorine or chlorine compounds is promoted to produce lithium chloride, volatilization of the lithium chloride occurs, preventing its subsequent penetration into an aqueous solution and reducing the lithium recovery rate.
  • chlorine gas may be used as the chlorine.
  • a metal chloride may be used as the chlorine compound.
  • the chlorine compound may include at least one of an alkali metal chloride and an alkaline earth metal chloride.
  • alkaline earth metals also include beryllium and magnesium.
  • the temperature at the time of contact between chlorine or a chlorine compound and the composite oxide may be controlled as the temperature of the composite oxide.
  • it may be controlled as the temperature of the atmosphere inside the reaction vessel into which the chlorine or a chlorine compound and the composite oxide are charged.
  • the aqueous solution recovery method of the present invention includes an aqueous solution recovery step in which an aqueous solution is contacted with chlorine or a chlorine compound that has undergone a contact step and a composite oxide, thereby recovering an aqueous solution into which lithium has permeated.
  • the time for contacting the composite oxide with chlorine or a chlorine compound is preferably 20 minutes or more and 180 minutes or less.
  • the chlorination reaction between lithium and chlorine or a chlorine compound is further promoted, and the lithium contained in the composite oxide can be more reliably recovered as lithium that permeates into the aqueous solution. Note that if the contact time exceeds 180 minutes, no improvement in lithium recovery efficiency will be observed even if the time is extended.
  • the aqueous solution that is brought into contact with the chlorine or chlorine compound and the composite oxide preferably has a pH value of 5.0 or higher and 10.0 or lower.
  • a pH value of 5.0 or higher and 10.0 or lower By setting the pH value of the aqueous solution within this range, the dissolution of heavy metals (nickel, cobalt, manganese, etc.) into the aqueous solution is suppressed, and the penetration of lithium, which contains few coexisting elements, into the aqueous solution is promoted. Pure water, etc. may be used as the aqueous solution.
  • the lithium-containing composite oxide preferably has a lithium content of 0.5% by mass or more, and more preferably 1.0% by mass or more, calculated as elemental lithium.
  • the results of implementing the aqueous solution recovery method of the present invention will be described.
  • one of four types of oxides (A to D) was used as the lithium-containing composite oxide, which differed in the substance ratio of calcium oxide to silicon dioxide (CaO/SiO 2 ) and the mass (mass %) of lithium contained.
  • the component information of the oxides (A to D) used in the examples is shown in Table 1.
  • a chlorine compound was contacted with the oxides (A to D) shown in Table 1 so that the mass ratio of chlorine to lithium contained in each oxide was a predetermined value, and the mixture was maintained at a predetermined temperature for 60 minutes.
  • An aqueous solution with a weight ratio of 30 times the chlorine compound and oxide was then prepared, and the chlorine compound and oxide were immersed in the aqueous solution while stirring for 120 minutes and filtered to obtain an aqueous solution containing lithium.
  • Calcium chloride (CaCl 2 ) was used as the chlorine compound. Pure water with a pH value of 5.0 to 10.0 was used as the aqueous solution.
  • the aqueous solution recovery method of the present invention can recover lithium contained in a composite oxide as an aqueous solution containing lithium. Furthermore, it was confirmed that the aqueous solution recovery method of the present invention can be applied to composite oxides containing lithium and having various compositions, and can recover an aqueous solution containing lithium without causing volatilization of chlorine or chlorine compounds.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Mechanical Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Secondary Cells (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

L'invention concerne un procédé de récupération de solution aqueuse qui permet de récupérer du lithium contenu dans un oxyde composite sous forme de solution aqueuse contenant du lithium.　Ce procédé de récupération d'une solution aqueuse qui permet de récupérer du lithium contenu dans un oxyde composite sous forme de solution aqueuse contenant du lithium comprend : une étape de mise en contact consistant à mettre en contact du chlore ou un composé chloré ajusté de telle sorte que le rapport de la quantité de chlore à celle de lithium contenue dans l'oxyde composite est compris entre 1,0 et 5,5 avec l'oxyde composite à une température comprise entre 500 et 1 350 °C ; et une étape de récupération en solution aqueuse consistant à mettre la solution aqueuse en contact avec l'oxyde composite et le chlore ou le composé chloré ayant subi l'étape de mise en contact, ce qui permet de récupérer la solution aqueuse imprégnée de lithium.
PCT/JP2025/000808 2024-03-14 2025-01-14 Procédé de récupération de solution aqueuse Pending WO2025192009A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2024039683 2024-03-14
JP2024-039683 2024-03-14

Publications (1)

Publication Number Publication Date
WO2025192009A1 true WO2025192009A1 (fr) 2025-09-18

Family

ID=97063156

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2025/000808 Pending WO2025192009A1 (fr) 2024-03-14 2025-01-14 Procédé de récupération de solution aqueuse

Country Status (1)

Country Link
WO (1) WO2025192009A1 (fr)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003031229A (ja) * 2001-07-12 2003-01-31 Tmc Kk 有価金属の回収方法
JP2005042189A (ja) * 2003-07-25 2005-02-17 Ise Chemicals Corp コバルトの回収方法
WO2023002048A1 (fr) * 2021-07-23 2023-01-26 Basf Se Procédé de recyclage de matériaux de batterie au lithium-ion
WO2023048196A1 (fr) * 2021-09-22 2023-03-30 株式会社アサカ理研 Procédé de traitement de chlore gazeux
JP2023529256A (ja) * 2021-05-07 2023-07-10 ヨン・ブン・コーポレーション 乾式溶融方法を利用した廃リチウム二次電池からリチウムを回収する方法
JP2023103937A (ja) * 2022-01-14 2023-07-27 株式会社アサカ理研 廃リチウムイオン電池からリチウムを回収する方法
WO2024024589A1 (fr) * 2022-07-28 2024-02-01 Ｊｆｅスチール株式会社 Procédé de récupération d'élément de valeur et procédé de production de métal

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003031229A (ja) * 2001-07-12 2003-01-31 Tmc Kk 有価金属の回収方法
JP2005042189A (ja) * 2003-07-25 2005-02-17 Ise Chemicals Corp コバルトの回収方法
JP2023529256A (ja) * 2021-05-07 2023-07-10 ヨン・ブン・コーポレーション 乾式溶融方法を利用した廃リチウム二次電池からリチウムを回収する方法
WO2023002048A1 (fr) * 2021-07-23 2023-01-26 Basf Se Procédé de recyclage de matériaux de batterie au lithium-ion
WO2023048196A1 (fr) * 2021-09-22 2023-03-30 株式会社アサカ理研 Procédé de traitement de chlore gazeux
JP2023103937A (ja) * 2022-01-14 2023-07-27 株式会社アサカ理研 廃リチウムイオン電池からリチウムを回収する方法
WO2024024589A1 (fr) * 2022-07-28 2024-02-01 Ｊｆｅスチール株式会社 Procédé de récupération d'élément de valeur et procédé de production de métal

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