WO2022168805A1 - Valuable metal recovery method and recovery device - Google Patents

Valuable metal recovery method and recovery device Download PDF

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Publication number
WO2022168805A1
WO2022168805A1 PCT/JP2022/003697 JP2022003697W WO2022168805A1 WO 2022168805 A1 WO2022168805 A1 WO 2022168805A1 JP 2022003697 W JP2022003697 W JP 2022003697W WO 2022168805 A1 WO2022168805 A1 WO 2022168805A1
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Prior art keywords
battery
contained
electrode active
active material
sulfuric acid
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PCT/JP2022/003697
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French (fr)
Japanese (ja)
Inventor
弘樹 村岡
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三菱マテリアル株式会社
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Priority to DE112022000943.8T priority Critical patent/DE112022000943T5/en
Priority to KR1020237021873A priority patent/KR20230138446A/en
Publication of WO2022168805A1 publication Critical patent/WO2022168805A1/en

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    • 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
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • 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
    • 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
    • C22B21/00—Obtaining aluminium
    • C22B21/0007—Preliminary treatment of ores or scrap or any other metal source
    • 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
    • C22B23/04—Obtaining nickel or cobalt by wet processes
    • C22B23/0407—Leaching processes
    • C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
    • C22B23/043—Sulfurated acids or salts thereof
    • 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
    • C22B3/44—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
    • 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
    • C22B7/001—Dry 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
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation
    • 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 a recovery method and recovery apparatus for valuable metals.
  • This application claims priority based on Japanese Patent Application No. 2021-015218 filed in Japan on February 2, 2021, the contents of which are incorporated herein.
  • Patent Literature 1 describes a technique for adding sulfuric acid to battery slag collected from battery waste, thereby leaching and recovering valuable metals contained in the battery slag with sulfuric acid.
  • An object of the present invention is to efficiently leach out one or both of Ni and Co contained in battery slag into sulfuric acid and recover them.
  • a method for recovering a valuable metal according to one embodiment of the present invention includes a positive electrode active material containing one or both of Ni and Co, and a negative electrode active material containing graphite.
  • one or both of Ni and Co contained in the positive electrode active material in the battery slag is brought into contact with the graphite contained in the negative electrode active material, and the graphite contained in the Carbon dioxide gas can be generated by transferring the electrons from Ni and Co to one or both of Ni and Co. Therefore, one or both of Ni and Co contained in the positive electrode active material in the battery slag can be reduced to divalent and efficiently exuded into sulfuric acid.
  • the residual powder can be obtained by reducing the volume of the battery slag. Then, since sulfuric acid is added to the battery residue (residual powder) whose volume is reduced, Ni and Co contained in the positive electrode active material in the residual powder are leached out into sulfuric acid only by adding a smaller amount of sulfuric acid. can be made
  • hydrogen peroxide may be added to the residual powder together with the sulfuric acid in the acid leaching step.
  • Ni and Co which were not reduced to divalent during the generation of carbon dioxide gas in the heating step, can be reduced to divalent with hydrogen peroxide in the acid leaching step and efficiently leached into sulfuric acid.
  • the valuable metal recovery method of the present invention may further include a recovery step of recovering one or both of Ni and Co contained in the leachate.
  • the recovery step includes an addition step of adding a sulfiding agent to the leachate to generate a treatment liquid, and filtering the treatment liquid to remove the treatment liquid from the filtrate, which is a liquid component, and the leachate. a residue, which is a solid component containing one or both of Ni and Co that has been filtered;
  • Ni and Co contained in the leachate can be efficiently recovered as residue from the filtration process.
  • the method for recovering valuable metals of the present invention may further include a crushing step of crushing battery waste to produce crushed materials, and a removal step of removing aluminum pieces from the crushed materials and removing the battery slag. good. Moreover, in the heating step, the removed battery slag may be heated.
  • the aluminum pieces are removed from the crushed material and the battery slag taken out is heated in the heating step, whereby one or both of Ni and Co can be efficiently produced by melting the aluminum pieces in the heating step. It is possible to prevent inhibition of the reduction. Therefore, one or both of Ni and Co contained in the residual powder can be efficiently leached into sulfuric acid in the acid leaching step. Also, the aluminum pieces removed in the extraction process can be recovered and effectively used.
  • the battery slag may be heated to 700°C or higher in the heating step.
  • Ni and Co contained in the positive electrode active material in the battery slag can be efficiently reduced to divalent in the heating step. Therefore, in the acid leaching step, one or both of Ni and Co contained in the residual powder can be efficiently leached into sulfuric acid.
  • the leaching solution in the acid leaching step, after adding 2 mol/l or more of the sulfuric acid to the residual powder, the leaching solution is heated to 60° C. or more and stirred for 4 hours or more. good too.
  • Ni and Co contained in the residual powder can be efficiently leached into sulfuric acid in the acid leaching step.
  • a valuable metal recovery device (hereinafter referred to as "a valuable metal recovery device of the present invention”) comprises a positive electrode active material containing one or both of Ni and Co, and a negative electrode active material containing graphite.
  • the apparatus for recovering valuable metals of the present invention may further include a recovery apparatus for recovering one or both of Ni and Co contained in the leachate.
  • the same effect as the method for recovering valuable metals of the present invention can be produced.
  • Ni and Co contained in battery slag can be efficiently leached into sulfuric acid and recovered.
  • FIG. 1 is an explanatory diagram for explaining the procedure of a valuable metal recovery method according to an embodiment of the present invention.
  • FIG. 2 is an explanatory diagram for explaining a recovering apparatus for valuable metals according to one embodiment of the present invention.
  • FIG. 1 shows the procedure of a valuable metal recovery method according to one embodiment of the present invention.
  • FIG. 2 schematically shows a valuable metal recovery apparatus 100 for carrying out the recovery method shown in FIG.
  • this recovery method includes a crushing step S1, a removal step S2, a heating step S3, a first acid leaching step S4, a first addition step S5, a first filtration step S6, a neutralization step S7, and a second Filtration step S8, second addition step S9, third filtration step S10, washing step S11, fourth filtration step S12, second acid leaching step S13, fifth filtration step S14, solvent extraction step S15, and carbonation step S16.
  • Steps S5 to S15 correspond to recovery steps of Ni and Co using a recovery apparatus for Ni and Co.
  • the crushing step S1 is a step of crushing the battery waste W1 with the crushing device 1 (Fig. 2) to produce the crushed material C.
  • the crushing device 1 for example, a twin-screw crusher and a hammer crusher can be used.
  • the battery waste W1 contains metals such as Li, Ni, Co, Mn, Al and Cu. Therefore, the crushed material C also contains these metals.
  • the removal step S2 is a step of removing the impurities I from the crushed material C by the removal device 2 (FIG. 2) and removing the battery slag M1.
  • a sieve such as a vibrating sieve can be used for the take-out device 2 .
  • the sieving fraction is the battery slag M1 and the sieve residue is the impurity I.
  • the battery residue M1 is a mixed powder containing the positive electrode active material and the negative electrode active material contained in the battery waste W1.
  • the impurity I contains aluminum pieces contained in the battery waste W1.
  • the heating step S3 is a step of heating the battery residue M1 with the heating device 3 (FIG. 2) to oxidize the graphite contained in the negative electrode active material in the battery residue M1 to generate carbon dioxide G. Electrons contained in graphite move to metal ions (for example, trivalent or tetravalent Ni ions and Co ions) contained in the positive electrode active material in the battery residue M1 as the carbon dioxide gas G is produced in the heating step S3. As a result, these metal ions are reduced to divalent ions. In the heating step S3, the carbon dioxide gas G is released from the battery slag M1 to produce residual powder M2.
  • metal ions for example, trivalent or tetravalent Ni ions and Co ions
  • the temperature for heating the battery residue M1 in the heating step S3 is preferably 700° C. or higher, more preferably 800° C. or higher and 900° C. or lower.
  • the interior of this heating device is preferably an atmospheric atmosphere, but is not limited to this and may be an atmosphere capable of providing oxygen for oxidizing graphite.
  • the heating time in the heating step S3 may be 0.5 hours to 10 hours, 0.5 hours to 5 hours, or 1 hour to 3 hours.
  • first acid leaching step S4 sulfuric acid and hydrogen peroxide A1 are added to the residual powder M2 in the first acid leaching device 4 (FIG. 2) to Ni ions and Co ions contained in the positive electrode active material) are leached into sulfuric acid.
  • a leaching solution E1 is produced which is a mixed solution of the residual powder M2, sulfuric acid and hydrogen peroxide A1.
  • the leachate E1 in order to efficiently leach the metal ions (especially Ni ions and Co ions) contained in the residual powder M2 into sulfuric acid, It is preferable to stir the leachate E1 at 60° C. or higher for 4 hours or longer after adding 2 mol/l or more of sulfuric acid.
  • the first addition step S5 is a step of adding a sulfiding agent A2 to the leachate E1 in the first addition device 5 (Fig. 2) to generate a sulfide of Cu contained in the leachate E1.
  • a treatment liquid P1 which is a mixed liquid of the leachate E1 and the sulfiding agent A2, is produced.
  • the pH of the treatment liquid P1 is less than 1 and the ORP (oxidation-reduction potential) is less than 0 mV (vs. Sulphidating agent A2 is added to Ag/AgCl).
  • a sulfur content such as sodium hydrogen sulfide can be used as the sulfiding agent A2.
  • the first filtering device 6 filters the treatment liquid P1 composed of the liquid component and the solid component to separate the filtrate F1, which is the liquid component, and the residue R1, which is the solid component. It is a process to do.
  • the filtrate F1 contains Li, Ni, Co, Mn and Al.
  • Residue R1 contains Cu sulfide.
  • the neutralization step S7 is a step of adding a neutralizing agent A3 to the filtrate F1 in the neutralization device 7 (Fig. 2) to generate hydroxides of Mn and Al contained in the filtrate F1.
  • a neutralized liquid N is produced which is a mixed liquid of the filtrate F1 and the neutralizing agent A3.
  • the pH of the neutralization liquid N is adjusted to 3.0 or more and 4.0 or less.
  • Admixture A3 For example, an aqueous sodium hydroxide solution can be used as the neutralizing agent A3.
  • the neutralized liquid N composed of the liquid component and the solid component is filtered in the second filtering device 8 (Fig. 2) to separate the filtrate F2, which is the liquid component, and the residue R2, which is the solid component.
  • the filtrate F2 contains Li, Ni and Co.
  • the residue R2 contains hydroxides of Mn and Al.
  • the second addition step S9 is a step of adding a sulfiding agent A4 to the filtrate F2 in the second addition device 9 (Fig. 2) to generate sulfides of Ni and Co contained in the filtrate F2.
  • a treated liquid P2 is produced which is a mixed liquid of the filtrate F2 and the sulfiding agent A4.
  • the pH of the treatment liquid P2 is 2.0 or more and 3.0 or less and ORP (oxidation A sulfiding agent A4 is added so that the reduction potential) is less than -400 mV (vs Ag/AgCl).
  • a sulfur content such as sodium hydrogen sulfide can be used as the sulfiding agent A4.
  • the treatment liquid P2 composed of the liquid component and the solid component is filtered in the third filtering device 10 (FIG. 2) to separate the filtrate F3, which is the liquid component, and the residue R3, which is the solid component. It is a process to do.
  • the filtrate F3 contains Li.
  • Residue R3 contains sulfides of Ni and Co.
  • the cleaning step S11 is a step in which the residue R3 is washed with the cleaning water W2 in the cleaning device 11 (FIG. 2) so that the Li remaining in the residue R3 is exuded into the cleaning water W2.
  • a slurry S is produced which is a mixture of the residue R3 and the cleaning water W2.
  • the slurry S composed of the liquid component and the solid component is filtered in the fourth filtering device 12 (Fig. 2) to separate the filtrate F4, which is the liquid component, and the residue R4, which is the solid component. It is a process.
  • the filtrate F4 contains Li remaining in the residue R3 without transferring to the filtrate F3.
  • Residue R4 contains sulfides of Ni and Co.
  • the second acid leaching step S13 "sulfuric acid, hydrogen peroxide and sodium hypochlorite A5" (the entirety of which is denoted by A5) is added to the residue R4 in the second acid leaching device 13 (Fig. 2).
  • a leaching solution E2 is produced which is a mixed solution of the residue R4, sulfuric acid, hydrogen peroxide and sodium hypochlorite A5.
  • the residue R4 contains a trace amount of Mn, but this Mn exists as manganese dioxide in the leachate E2 due to the addition of sulfuric acid, hydrogen peroxide and sodium hypochlorite A5.
  • the sulfides of Ni and Co contained in the residue R4 react with sulfuric acid and hydrogen peroxide to produce sulfur (elementary substance).
  • the exudate E2 consisting of the liquid component and the solid component is filtered in the fifth filtering device 14 (Fig. 2) to separate the filtrate F5 which is the liquid component and the residue R5 which is the solid component. It is a process.
  • Filtrate F5 contains Ni and Co.
  • Residue R5 contains manganese dioxide and sulfur (elementary).
  • the solvent extraction step S15 is a step of adding an organic solvent (extraction solvent) and sulfuric acid (reverse extraction solvent) to the filtrate F5 in the solvent extraction device 15 (Fig. 2) such as a mixer settler.
  • an organic solvent extraction solvent
  • sulfuric acid reverse extraction solvent
  • the carbonation step S16 is a step of adding a carbonate A6 to the filtrate F3 of the third filtration step S10 and the filtrate F4 of the fourth filtration step S12 in the carbonation device 16 (FIG. 2) to generate lithium carbonate V2.
  • a carbonate A6 for example, sodium carbonate or sodium carbonate hydrate can be used.
  • the mixture of the filtrate F3, the filtrate F4 and the carbonate A6 may be filtered to separate the filtrate and the residue. Lithium carbonate V2 can be recovered as this residue.
  • Ni and/or Co one or both of Ni and Co contained in the positive electrode active material in the battery residue M1 and graphite contained in the negative electrode active material are powdered. They are in contact, and electrons contained in graphite move to Ni and/or Co in the process of generating carbon dioxide G. Therefore, Ni and/or Co contained in the positive electrode active material in the battery residue M1 can be reduced to divalent. Therefore, these Ni and/or Co can be efficiently leached into sulfuric acid in the first acid leaching step S4.
  • the first acid leaching step S4 sulfuric acid is added to the volume-reduced battery slag M1 (residual powder M2 remaining after carbon dioxide gas G is generated from the battery slag M1). Therefore, Ni and Co contained in the positive electrode active material in the residual powder M2 can be leached into the sulfuric acid only by adding a small amount of sulfuric acid.
  • Ni and Co which were not reduced to divalent at the time of carbon dioxide gas generation in the heating step S3, are reduced to divalent with hydrogen peroxide in the first acid leaching step S4, and sulfuric acid is efficiently produced. can be leached into
  • the battery slag M1 taken out after removing the aluminum pieces (impurities I) from the crushed material C is heated in the heating step S3. and inhibiting the reduction of Co. Therefore, Ni and Co contained in the residual powder M2 can be efficiently leached into sulfuric acid in the first acid leaching step S4. Also, the aluminum pieces removed in the removal step S2 can be recovered and effectively used.
  • the crushing step S1, the extraction step S2 and the carbonation step S16 can be omitted. Further, if a step of recovering Ni and/or Co contained in the leachate E1 is provided, part of steps S5 to S15 can be omitted or changed.
  • Neutralization process An aqueous NaOH solution (25% concentration) was added to the filtrate of the first filtration step to produce a neutralized solution. The NaOH aqueous solution was added until the pH of the neutralization liquid reached 3.5.
  • Table 1 shows the type of battery used in each example and each comparative example, the baking temperature of the battery slag in the heating process, the concentration of sulfuric acid used in the first acid leaching process, and the leaching temperature in the first acid leaching process (the temperature of the leachate). heating temperature), leaching time (stirring time of the leaching solution), and recovery rates of Co and Ni in the solvent extraction step are shown for each example and comparative example.
  • NCM is an NCM-based battery (that is, a battery using a composite oxide of Ni, Co, and Mn as a positive electrode active material).
  • NCA is an NCA-based battery (that is, a battery using a composite oxide of Ni, Co and Al as a positive electrode active material).
  • the recovery rate of Co means "(the mass of Co contained in the sulfate recovered in the solvent extraction step) ⁇ 100/(the mass of Co contained in the battery slag)".
  • the recovery rate of Ni means "(the mass of Ni contained in the sulfate recovered in the solvent extraction step) ⁇ 100 ⁇ (the mass of Ni contained in the battery slag)”.
  • the masses of Co and Ni contained in the sulfate were measured using ICP-AES.
  • the masses of Co and Ni contained in the battery slag were measured by XRF quantitative analysis.
  • Example 3 Comparing Example 3 and Comparative Example 1, the conditions other than the presence or absence of firing are the same, but the difference is whether or not firing is performed. In Example 3 (fired), the Co recovery rate and Ni recovery rate are significantly higher than those of Comparative Example 1 (no firing). When Example 14 and Comparative Example 2 are compared, the conditions other than the presence or absence of firing are the same, but the difference is whether or not firing is performed. In Example 14 (fired), the Co recovery rate and Ni recovery rate are significantly higher than those of Comparative Example 2 (no firing).
  • the sintering temperature is 700°C
  • the Co recovery rate and the Ni recovery rate are significantly higher than those in the example where the sintering temperature is 600°C.
  • the sintering temperature was 800°C and 900°C
  • the Co recovery rate and the Ni recovery rate were significantly higher than those in the example in which the sintering temperature was 700°C.
  • the battery slag M1 is heated to 700° C. or higher (more preferably 800° C. or higher and 900° C. or lower), the concentration of sulfuric acid used in the first acid leaching step S4 is set to 2 mol/l or higher, and the residual powder M2 is By setting the leaching temperature of 60° C. or higher and setting the leaching time of the residual powder M2 to 4 hours or longer, Ni and Co contained in the residual powder M2 can be efficiently leached into sulfuric acid in the first acid leaching step S4. , Ni and Co can be efficiently recovered in the solvent extraction step S15.
  • Ni and Co contained in the battery slag can be efficiently leached into sulfuric acid and recovered.

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Abstract

The present invention has: a heating step (S3) for heating a battery slag (M1) having a positive-electrode active material that includes one or both of Ni and Co and a negative-electrode active material that includes graphite, and thereby oxidizing the graphite included in the negative-electrode active material in the battery slag (M1) to generate carbon dioxide gas (G); and an acid leaching step (S4) for adding sulfuric acid to a residual powder (M2) that remains after generation of carbon dioxide gas (G) from the battery slag (M1), and thereby leaching one or both of the Ni and Co included in the positive-electrode active material in the residual powder (M2) into the sulfuric acid to generate a leachate (E1).

Description

有価金属の回収方法及び回収装置Valuable metal recovery method and recovery device
　本発明は、有価金属の回収方法及び回収装置に関するものである。
　本願は、２０２１年２月２日に、日本に出願された特願２０２１－０１５２１８号に基づき優先権を主張し、その内容をここに援用する。 TECHNICAL FIELD The present invention relates to a recovery method and recovery apparatus for valuable metals.
This application claims priority based on Japanese Patent Application No. 2021-015218 filed in Japan on February 2, 2021, the contents of which are incorporated herein.
　下記特許文献１には、電池廃棄物から回収した電池滓に硫酸を添加することにより、この電池滓に含まれている有価金属を硫酸に浸出させて回収する技術が記載されている。 Patent Literature 1 below describes a technique for adding sulfuric acid to battery slag collected from battery waste, thereby leaching and recovering valuable metals contained in the battery slag with sulfuric acid.
　しかし、本発明者の研究により、下記特許文献１に記載の技術においては、電池滓に含まれる有価金属のうちＮｉ及びＣｏについては効率よく硫酸に浸出させることができないことが判明した。 However, research by the present inventors revealed that Ni and Co, among the valuable metals contained in the battery slag, cannot be efficiently leached into sulfuric acid in the technique described in Patent Document 1 below.
日本国特開２０１９－１６０４２９号公報（Ａ）Japanese Patent Application Laid-Open No. 2019-160429 (A)
　本発明の目的は、電池滓に含まれるＮｉ及びＣｏの一方又は両方を効率よく硫酸に浸出させて回収することである。 An object of the present invention is to efficiently leach out one or both of Ni and Co contained in battery slag into sulfuric acid and recover them.
　本発明の一態様の有価金属の回収方法（以下、「本発明の有価金属の回収方法」と称する）は、Ｎｉ及びＣｏの一方又は両方を含む正極活物質と、グラファイトを含む負極活物質と、を有する電池滓を加熱することにより、前記電池滓中の前記負極活物質に含まれるグラファイトを酸化して炭酸ガスを生成する加熱工程と、前記電池滓から前記炭酸ガスを生成した後に残留する残留粉末に硫酸を添加することにより、前記残留粉末中の前記正極活物質に含まれるＮｉ及びＣｏの一方又は両方を前記硫酸に浸出させて浸出液を生成する酸浸出工程とを有する。 A method for recovering a valuable metal according to one embodiment of the present invention (hereinafter referred to as "a method for recovering a valuable metal of the present invention") includes a positive electrode active material containing one or both of Ni and Co, and a negative electrode active material containing graphite. a heating step of oxidizing the graphite contained in the negative electrode active material in the battery residue to generate carbon dioxide gas by heating the battery residue having a, and remaining after the carbon dioxide gas is generated from the battery residue and an acid leaching step of adding sulfuric acid to the residual powder, thereby leaching one or both of Ni and Co contained in the positive electrode active material in the residual powder into the sulfuric acid to produce a leaching solution.
　前記態様の有価金属の回収方法によれば、加熱工程において電池滓中の正極活物質に含まれるＮｉ及びＣｏの一方又は両方と、負極活物質に含まれるグラファイトと、を接触させ、グラファイトに含まれる電子をＮｉ及びＣｏの一方又は両方に移動させて炭酸ガスを生成することができる。よって、電池滓中の正極活物質に含まれるＮｉ及びＣｏの一方又は両方を２価に還元して効率よく硫酸に浸出させることができる。 According to the valuable metal recovery method of the aspect, in the heating step, one or both of Ni and Co contained in the positive electrode active material in the battery slag is brought into contact with the graphite contained in the negative electrode active material, and the graphite contained in the Carbon dioxide gas can be generated by transferring the electrons from Ni and Co to one or both of Ni and Co. Therefore, one or both of Ni and Co contained in the positive electrode active material in the battery slag can be reduced to divalent and efficiently exuded into sulfuric acid.
　また、前記態様の有価金属の回収方法によれば、電池滓を減容させて残留粉末を得ることができる。そして、電池滓を減容させたもの（残留粉末）に対して硫酸を添加するため、より少ない容量の硫酸を添加するだけで残留粉末中の正極活物質に含まれるＮｉ及びＣｏを硫酸に浸出させることができる。 In addition, according to the recovering method of valuable metals of the aspect, the residual powder can be obtained by reducing the volume of the battery slag. Then, since sulfuric acid is added to the battery residue (residual powder) whose volume is reduced, Ni and Co contained in the positive electrode active material in the residual powder are leached out into sulfuric acid only by adding a smaller amount of sulfuric acid. can be made
　本発明の有価金属の回収方法においては、前記酸浸出工程において前記硫酸と共に過酸化水素を前記残留粉末に添加してもよい。 In the method for recovering valuable metals of the present invention, hydrogen peroxide may be added to the residual powder together with the sulfuric acid in the acid leaching step.
　この特徴を満足することにより、加熱工程の炭酸ガス生成時には２価に還元されなかったＮｉ及びＣｏを、酸浸出工程において過酸化水素により２価に還元して効率よく硫酸に浸出させることができる。 By satisfying this characteristic, Ni and Co, which were not reduced to divalent during the generation of carbon dioxide gas in the heating step, can be reduced to divalent with hydrogen peroxide in the acid leaching step and efficiently leached into sulfuric acid. .
　本発明の有価金属の回収方法は、前記浸出液に含まれる前記Ｎｉ及びＣｏの一方又は両方を回収する回収工程をさらに備えてもよい。
　また、前記回収工程は、前記浸出液に硫化剤を添加して処理液を生成する添加工程と、前記処理液を濾過することにより、前記処理液を、液体成分である濾液と、前記浸出液に含まれていたＮｉ及びＣｏの一方又は両方を含む固体成分である残渣と、に分離する濾過工程とを有してもよい。 The valuable metal recovery method of the present invention may further include a recovery step of recovering one or both of Ni and Co contained in the leachate.
In addition, the recovery step includes an addition step of adding a sulfiding agent to the leachate to generate a treatment liquid, and filtering the treatment liquid to remove the treatment liquid from the filtrate, which is a liquid component, and the leachate. a residue, which is a solid component containing one or both of Ni and Co that has been filtered;
　この特徴を満足することにより、浸出液に含まれるＮｉ及びＣｏの一方又は両方を濾過工程の残渣として効率よく回収することができる。 By satisfying this feature, one or both of Ni and Co contained in the leachate can be efficiently recovered as residue from the filtration process.
　本発明の有価金属の回収方法は、電池廃棄物を破砕して破砕物を製造する破砕工程と、前記破砕物からアルミニウム片を除去して前記電池滓を取り出す取出工程とをさらに有してもよい。また、前記加熱工程においては、取り出された前記電池滓を加熱してもよい。 The method for recovering valuable metals of the present invention may further include a crushing step of crushing battery waste to produce crushed materials, and a removal step of removing aluminum pieces from the crushed materials and removing the battery slag. good. Moreover, in the heating step, the removed battery slag may be heated.
　この特徴を満足することにより、破砕物からアルミニウム片を除去して取り出された電池滓を加熱工程において加熱することにより、加熱工程においてアルミニウム片の溶融によってＮｉ及びＣｏの一方又は両方の効率的な還元が阻害されることを防止することができる。よって、酸浸出工程において残留粉末に含まれるＮｉ及びＣｏの一方又は両方を効率よく硫酸に浸出させることができる。また、取出工程において除去したアルミニウム片を回収して有効に利用することができる。 By satisfying this feature, the aluminum pieces are removed from the crushed material and the battery slag taken out is heated in the heating step, whereby one or both of Ni and Co can be efficiently produced by melting the aluminum pieces in the heating step. It is possible to prevent inhibition of the reduction. Therefore, one or both of Ni and Co contained in the residual powder can be efficiently leached into sulfuric acid in the acid leaching step. Also, the aluminum pieces removed in the extraction process can be recovered and effectively used.
　本発明の有価金属の回収方法においては、前記加熱工程において前記電池滓を７００℃以上に加熱してもよい。 In the method for recovering valuable metals of the present invention, the battery slag may be heated to 700°C or higher in the heating step.
　この特徴を満足することにより、加熱工程において、電池滓中の正極活物質に含まれるＮｉ及びＣｏの一方又は両方を効率よく２価に還元することができる。よって、酸浸出工程において、残留粉末に含まれるＮｉ及びＣｏの一方又は両方を効率よく硫酸に浸出させることができる。 By satisfying this feature, one or both of Ni and Co contained in the positive electrode active material in the battery slag can be efficiently reduced to divalent in the heating step. Therefore, in the acid leaching step, one or both of Ni and Co contained in the residual powder can be efficiently leached into sulfuric acid.
　本発明の有価金属の回収方法においては、前記酸浸出工程において、前記残留粉末に２ｍｏｌ／ｌ以上の前記硫酸を添加してから、前記浸出液を６０℃以上に加熱して４時間以上攪拌してもよい。 In the method for recovering valuable metals of the present invention, in the acid leaching step, after adding 2 mol/l or more of the sulfuric acid to the residual powder, the leaching solution is heated to 60° C. or more and stirred for 4 hours or more. good too.
　この特徴を満足することにより、酸浸出工程において残留粉末に含まれるＮｉ及びＣｏの一方又は両方を効率よく硫酸に浸出させることができる。 By satisfying this characteristic, one or both of Ni and Co contained in the residual powder can be efficiently leached into sulfuric acid in the acid leaching step.
　本発明の他態様の有価金属の回収装置（以下、「本発明の有価金属の回収装置」と称する）は、Ｎｉ及びＣｏの一方又は両方を含む正極活物質と、グラファイトを含む負極活物質と、を有する電池滓を加熱することにより、前記電池滓中の前記負極活物質に含まれるグラファイトを酸化して炭酸ガスを生成する加熱装置と、前記電池滓から前記炭酸ガスを生成した後に残留する残留粉末に硫酸を添加することにより、前記残留粉末中の前記正極活物質に含まれるＮｉ及びＣｏの一方又は両方を前記硫酸に浸出させて浸出液を生成する酸浸出装置とを備える。
　本発明の有価金属の回収装置は、前記浸出液に含まれる前記Ｎｉ及びＣｏの一方又は両方を回収する回収装置を更に備えてもよい。 A valuable metal recovery device according to another aspect of the present invention (hereinafter referred to as "a valuable metal recovery device of the present invention") comprises a positive electrode active material containing one or both of Ni and Co, and a negative electrode active material containing graphite. a heating device for generating carbon dioxide gas by heating the battery slag having , thereby oxidizing the graphite contained in the negative electrode active material in the battery slag, and remaining after the carbon dioxide gas is generated from the battery slag and an acid leaching device for adding sulfuric acid to the residual powder, thereby leaching one or both of Ni and Co contained in the positive electrode active material in the residual powder into the sulfuric acid to produce a leaching solution.
The apparatus for recovering valuable metals of the present invention may further include a recovery apparatus for recovering one or both of Ni and Co contained in the leachate.
　本発明の有価金属の回収装置によれば、上記本発明の有価金属の回収方法と同様の効果を生じさせることができる。 According to the apparatus for recovering valuable metals of the present invention, the same effect as the method for recovering valuable metals of the present invention can be produced.
　以上のように、本発明によれば、電池滓に含まれるＮｉ及びＣｏの一方又は両方を効率よく硫酸に浸出させて回収することができる。 As described above, according to the present invention, one or both of Ni and Co contained in battery slag can be efficiently leached into sulfuric acid and recovered.
図１は、本発明の一実施形態に係る有価金属の回収方法の手順を説明するための説明図である。FIG. 1 is an explanatory diagram for explaining the procedure of a valuable metal recovery method according to an embodiment of the present invention. 図２は、本発明の一実施形態に係る有価金属の回収装置を説明するための説明図である。FIG. 2 is an explanatory diagram for explaining a recovering apparatus for valuable metals according to one embodiment of the present invention.
　本発明の一実施形態に係る有価金属の回収方法について説明する。この回収方法は、いわゆるリチウムイオン電池の廃棄物の処理に適用されたものである。図１は、本発明の一実施形態に係る有価金属の回収方法の手順を示している。図２は、図１に示す回収方法を行うための有価金属の回収装置１００を模式的に示している。 A method for recovering valuable metals according to one embodiment of the present invention will be described. This recovery method is applied to the disposal of so-called lithium ion battery waste. FIG. 1 shows the procedure of a valuable metal recovery method according to one embodiment of the present invention. FIG. 2 schematically shows a valuable metal recovery apparatus 100 for carrying out the recovery method shown in FIG.
　図１に示すように、この回収方法は、破砕工程Ｓ１、取出工程Ｓ２、加熱工程Ｓ３、第１酸浸出工程Ｓ４、第１添加工程Ｓ５、第１濾過工程Ｓ６、中和工程Ｓ７、第２濾過工程Ｓ８、第２添加工程Ｓ９、第３濾過工程Ｓ１０、洗浄工程Ｓ１１、第４濾過工程Ｓ１２、第２酸浸出工程Ｓ１３、第５濾過工程Ｓ１４、溶媒抽出工程Ｓ１５、及び炭酸化工程Ｓ１６を有する。工程Ｓ５～Ｓ１５は、Ｎｉ及びＣｏの回収装置を用いたＮｉ及びＣｏの回収工程に相当する。 As shown in FIG. 1, this recovery method includes a crushing step S1, a removal step S2, a heating step S3, a first acid leaching step S4, a first addition step S5, a first filtration step S6, a neutralization step S7, and a second Filtration step S8, second addition step S9, third filtration step S10, washing step S11, fourth filtration step S12, second acid leaching step S13, fifth filtration step S14, solvent extraction step S15, and carbonation step S16. have. Steps S5 to S15 correspond to recovery steps of Ni and Co using a recovery apparatus for Ni and Co.
　破砕工程Ｓ１は、電池廃棄物Ｗ１を破砕装置１（図２）により破砕して破砕物Ｃを製造する工程である。破砕装置１には、例えば、二軸破砕機及びハンマークラッシャーを使用することができる。電池廃棄物Ｗ１には、Ｌｉ、Ｎｉ、Ｃｏ、Ｍｎ、Ａｌ及びＣｕなどの金属が含まれている。したがって、破砕物Ｃにも、これらの金属が含まれている。 The crushing step S1 is a step of crushing the battery waste W1 with the crushing device 1 (Fig. 2) to produce the crushed material C. For the crushing device 1, for example, a twin-screw crusher and a hammer crusher can be used. The battery waste W1 contains metals such as Li, Ni, Co, Mn, Al and Cu. Therefore, the crushed material C also contains these metals.
　取出工程Ｓ２は、取出装置２（図２）により破砕物Ｃから不純物Ｉを除去して電池滓Ｍ１を取り出す工程である。取出装置２には、振動篩等の篩を使用することができる。篩を使用する場合、篩通過分が電池滓Ｍ１であって篩残分が不純物Ｉである。電池滓Ｍ１は、電池廃棄物Ｗ１に含まれていた正極活物質及び負極活物質を有する混合粉末である。不純物Ｉは、電池廃棄物Ｗ１に含まれていたアルミニウム片を含んでいる。 The removal step S2 is a step of removing the impurities I from the crushed material C by the removal device 2 (FIG. 2) and removing the battery slag M1. A sieve such as a vibrating sieve can be used for the take-out device 2 . When a sieve is used, the sieving fraction is the battery slag M1 and the sieve residue is the impurity I. The battery residue M1 is a mixed powder containing the positive electrode active material and the negative electrode active material contained in the battery waste W1. The impurity I contains aluminum pieces contained in the battery waste W1.
　加熱工程Ｓ３は、電池滓Ｍ１を加熱装置３（図２）によって加熱することにより、電池滓Ｍ１中の負極活物質に含まれるグラファイトを酸化して炭酸ガスＧを生成する工程である。グラファイトに含まれる電子は、加熱工程Ｓ３において炭酸ガスＧの生成に伴って電池滓Ｍ１中の正極活物質に含まれる金属イオン（例えば３価または４価のＮｉイオン及びＣｏイオン）に移動する。これにより、これら金属イオンは２価に還元される。加熱工程Ｓ３においては、電池滓Ｍ１から炭酸ガスＧが抜けて残留粉末Ｍ２が生じる。 The heating step S3 is a step of heating the battery residue M1 with the heating device 3 (FIG. 2) to oxidize the graphite contained in the negative electrode active material in the battery residue M1 to generate carbon dioxide G. Electrons contained in graphite move to metal ions (for example, trivalent or tetravalent Ni ions and Co ions) contained in the positive electrode active material in the battery residue M1 as the carbon dioxide gas G is produced in the heating step S3. As a result, these metal ions are reduced to divalent ions. In the heating step S3, the carbon dioxide gas G is released from the battery slag M1 to produce residual powder M2.
　なお、加熱工程Ｓ３において電池滓Ｍ１を加熱する温度についてであるが、電池滓Ｍ１に含まれる有価金属（特に従来技術では第１酸浸出工程Ｓ４において硫酸に浸出させにくい３価または４価のＮｉイオン及びＣｏイオン）を効率よく２価に還元するために、７００℃以上であることが好ましく、８００℃以上９００℃以下であることがより好ましい。また、この加熱装置の内部は大気雰囲気であると好ましいが、これに限定されずにグラファイトを酸化するための酸素を提供することができる雰囲気であればよい。
　加熱工程Ｓ３の加熱時間は０．５時間から１０時間、０．５時間から５時間又は１時間から３時間であってもよい。 Regarding the temperature for heating the battery residue M1 in the heating step S3, the valuable metal contained in the battery residue M1 (particularly, in the prior art, trivalent or tetravalent Ni, which is difficult to leach out with sulfuric acid in the first acid leaching step S4, ions and Co ions) to be divalent, the temperature is preferably 700° C. or higher, more preferably 800° C. or higher and 900° C. or lower. The interior of this heating device is preferably an atmospheric atmosphere, but is not limited to this and may be an atmosphere capable of providing oxygen for oxidizing graphite.
The heating time in the heating step S3 may be 0.5 hours to 10 hours, 0.5 hours to 5 hours, or 1 hour to 3 hours.
　第１酸浸出工程Ｓ４は、第１酸浸出装置４（図２）において残留粉末Ｍ２に硫酸及び過酸化水素Ａ１を添加することにより、残留粉末Ｍ２に含まれる金属イオン（特に、残留粉末Ｍ２中の正極活物質に含まれるＮｉイオン及びＣｏイオン）を硫酸に浸出させる工程である。第１酸浸出工程Ｓ４においては、残留粉末Ｍ２と硫酸及び過酸化水素Ａ１との混合液である浸出液Ｅ１が生成される。なお、残留粉末Ｍ２に含まれる金属を硫酸に浸出させる条件についてであるが、残留粉末Ｍ２に含まれる金属イオン（特にＮｉイオン及びＣｏイオン）を効率よく硫酸に浸出させるために、残留粉末Ｍ２に２ｍｏｌ／ｌ以上の硫酸を添加してから浸出液Ｅ１を６０℃以上で４時間以上攪拌することが好ましい。 In the first acid leaching step S4, sulfuric acid and hydrogen peroxide A1 are added to the residual powder M2 in the first acid leaching device 4 (FIG. 2) to Ni ions and Co ions contained in the positive electrode active material) are leached into sulfuric acid. In the first acid leaching step S4, a leaching solution E1 is produced which is a mixed solution of the residual powder M2, sulfuric acid and hydrogen peroxide A1. Regarding the conditions for leaching the metals contained in the residual powder M2 into sulfuric acid, in order to efficiently leach the metal ions (especially Ni ions and Co ions) contained in the residual powder M2 into sulfuric acid, It is preferable to stir the leachate E1 at 60° C. or higher for 4 hours or longer after adding 2 mol/l or more of sulfuric acid.
　第１添加工程Ｓ５は、第１添加装置５（図２）において、浸出液Ｅ１に硫化剤Ａ２を添加することにより浸出液Ｅ１に含まれるＣｕの硫化物を生成する工程である。第１添加工程Ｓ５においては、浸出液Ｅ１と硫化剤Ａ２との混合液である処理液Ｐ１が生じる。ここで、第１添加工程Ｓ５においては、浸出液Ｅ１に含まれるＣｕの硫化物を効率よく生成するために、処理液Ｐ１のｐＨが１未満であってＯＲＰ（酸化還元電位）が０ｍＶ未満（ｖｓ　Ａｇ／ＡｇＣｌ）になるように硫化剤Ａ２を添加する。硫化剤Ａ２には、例えば、硫化水素ナトリウムのような硫黄分を使用することができる。 The first addition step S5 is a step of adding a sulfiding agent A2 to the leachate E1 in the first addition device 5 (Fig. 2) to generate a sulfide of Cu contained in the leachate E1. In the first addition step S5, a treatment liquid P1, which is a mixed liquid of the leachate E1 and the sulfiding agent A2, is produced. Here, in the first addition step S5, in order to efficiently generate Cu sulfide contained in the leachate E1, the pH of the treatment liquid P1 is less than 1 and the ORP (oxidation-reduction potential) is less than 0 mV (vs. Sulphidating agent A2 is added to Ag/AgCl). A sulfur content such as sodium hydrogen sulfide can be used as the sulfiding agent A2.
　第１濾過工程Ｓ６は、第１濾過装置６（図２）において、液体成分と固体成分とからなる処理液Ｐ１を濾過して、液体成分である濾液Ｆ１と固体成分である残渣Ｒ１とに分離する工程である。濾液Ｆ１には、Ｌｉ、Ｎｉ、Ｃｏ、Ｍｎ及びＡｌが含まれている。残渣Ｒ１にはＣｕの硫化物が含まれている。 In the first filtering step S6, the first filtering device 6 (FIG. 2) filters the treatment liquid P1 composed of the liquid component and the solid component to separate the filtrate F1, which is the liquid component, and the residue R1, which is the solid component. It is a process to do. The filtrate F1 contains Li, Ni, Co, Mn and Al. Residue R1 contains Cu sulfide.
　中和工程Ｓ７は、中和装置７（図２）において、濾液Ｆ１に中和剤Ａ３を添加することにより濾液Ｆ１に含まれるＭｎ及びＡｌの水酸化物を生成する工程である。中和工程Ｓ７においては、濾液Ｆ１と中和剤Ａ３との混合液である中和液Ｎが生じる。ここで、中和工程Ｓ７においては、濾液Ｆ１に含まれるＭｎ及びＡｌの水酸化物を効率よく生成するために、中和液ＮのｐＨが３．０以上４．０以下になるように中和剤Ａ３を添加する。中和剤Ａ３には、例えば、水酸化ナトリウム水溶液を使用することができる。 The neutralization step S7 is a step of adding a neutralizing agent A3 to the filtrate F1 in the neutralization device 7 (Fig. 2) to generate hydroxides of Mn and Al contained in the filtrate F1. In the neutralization step S7, a neutralized liquid N is produced which is a mixed liquid of the filtrate F1 and the neutralizing agent A3. Here, in the neutralization step S7, in order to efficiently generate hydroxides of Mn and Al contained in the filtrate F1, the pH of the neutralization liquid N is adjusted to 3.0 or more and 4.0 or less. Add Admixture A3. For example, an aqueous sodium hydroxide solution can be used as the neutralizing agent A3.
　第２濾過工程Ｓ８は、第２濾過装置８（図２）において、液体成分と固体成分とからなる中和液Ｎを濾過して、液体成分である濾液Ｆ２と固体成分である残渣Ｒ２とに分離する工程である。濾液Ｆ２には、Ｌｉ、Ｎｉ及びＣｏが含まれている。残渣Ｒ２には、Ｍｎ及びＡｌの水酸化物が含まれている。 In the second filtering step S8, the neutralized liquid N composed of the liquid component and the solid component is filtered in the second filtering device 8 (Fig. 2) to separate the filtrate F2, which is the liquid component, and the residue R2, which is the solid component. This is the step of separating. The filtrate F2 contains Li, Ni and Co. The residue R2 contains hydroxides of Mn and Al.
　第２添加工程Ｓ９は、第２添加装置９（図２）において、濾液Ｆ２に硫化剤Ａ４を添加することにより濾液Ｆ２に含まれるＮｉ及びＣｏの硫化物を生成する工程である。第２添加工程Ｓ９においては、濾液Ｆ２と硫化剤Ａ４との混合液である処理液Ｐ２が生じる。ここで、第２添加工程Ｓ９においては、濾液Ｆ２に含まれるＮｉ及びＣｏの硫化物を効率よく生成するために、処理液Ｐ２のｐＨが２．０以上３．０以下であってＯＲＰ（酸化還元電位）が－４００ｍＶ未満（ｖｓ　Ａｇ／ＡｇＣｌ）になるように硫化剤Ａ４を添加する。硫化剤Ａ４には、例えば、硫化水素ナトリウムのような硫黄分を使用することができる。 The second addition step S9 is a step of adding a sulfiding agent A4 to the filtrate F2 in the second addition device 9 (Fig. 2) to generate sulfides of Ni and Co contained in the filtrate F2. In the second addition step S9, a treated liquid P2 is produced which is a mixed liquid of the filtrate F2 and the sulfiding agent A4. Here, in the second addition step S9, in order to efficiently generate the sulfides of Ni and Co contained in the filtrate F2, the pH of the treatment liquid P2 is 2.0 or more and 3.0 or less and ORP (oxidation A sulfiding agent A4 is added so that the reduction potential) is less than -400 mV (vs Ag/AgCl). A sulfur content such as sodium hydrogen sulfide can be used as the sulfiding agent A4.
　第３濾過工程Ｓ１０は、第３濾過装置１０（図２）において、液体成分と固体成分とからなる処理液Ｐ２を濾過して、液体成分である濾液Ｆ３と固体成分である残渣Ｒ３とに分離する工程である。濾液Ｆ３には、Ｌｉが含まれている。残渣Ｒ３には、Ｎｉ及びＣｏの硫化物が含まれている。 In the third filtration step S10, the treatment liquid P2 composed of the liquid component and the solid component is filtered in the third filtering device 10 (FIG. 2) to separate the filtrate F3, which is the liquid component, and the residue R3, which is the solid component. It is a process to do. The filtrate F3 contains Li. Residue R3 contains sulfides of Ni and Co.
　洗浄工程Ｓ１１は、洗浄装置１１（図２）において、残渣Ｒ３を洗浄水Ｗ２によって洗浄することにより、残渣Ｒ３に残留しているＬｉを洗浄水Ｗ２に浸出させる工程である。洗浄工程Ｓ１１においては、残渣Ｒ３と洗浄水Ｗ２との混合物であるスラリーＳが生成される。 The cleaning step S11 is a step in which the residue R3 is washed with the cleaning water W2 in the cleaning device 11 (FIG. 2) so that the Li remaining in the residue R3 is exuded into the cleaning water W2. In the cleaning step S11, a slurry S is produced which is a mixture of the residue R3 and the cleaning water W2.
　第４濾過工程Ｓ１２は、第４濾過装置１２（図２）において、液体成分と固体成分とからなるスラリーＳを濾過して、液体成分である濾液Ｆ４と固体成分である残渣Ｒ４とに分離する工程である。濾液Ｆ４には、濾液Ｆ３に移行せずに残渣Ｒ３に残留したＬｉが含まれている。残渣Ｒ４には、Ｎｉ及びＣｏの硫化物が含まれている。 In the fourth filtering step S12, the slurry S composed of the liquid component and the solid component is filtered in the fourth filtering device 12 (Fig. 2) to separate the filtrate F4, which is the liquid component, and the residue R4, which is the solid component. It is a process. The filtrate F4 contains Li remaining in the residue R3 without transferring to the filtrate F3. Residue R4 contains sulfides of Ni and Co.
　第２酸浸出工程Ｓ１３は、第２酸浸出装置１３（図２）において残渣Ｒ４に「硫酸、過酸化水素及び次亜塩素酸ナトリウムＡ５」（これら全体に対して符号Ａ５を付す）を添加することにより、残渣Ｒ４に含まれるＮｉ及びＣｏを硫酸に浸出させる工程である。第２酸浸出工程Ｓ１３においては、残渣Ｒ４と硫酸、過酸化水素及び次亜塩素酸ナトリウムＡ５との混合液である浸出液Ｅ２が生成される。ここで、残渣Ｒ４には微量のＭｎが含まれていることも考えられるが、このＭｎは硫酸、過酸化水素及び次亜塩素酸ナトリウムＡ５の添加により浸出液Ｅ２において二酸化マンガンとして存在する。また、浸出液Ｅ２においては、残渣Ｒ４に含まれていたＮｉ及びＣｏの硫化物と硫酸及び過酸化水素とが反応して硫黄（単体）が生成する。 In the second acid leaching step S13, "sulfuric acid, hydrogen peroxide and sodium hypochlorite A5" (the entirety of which is denoted by A5) is added to the residue R4 in the second acid leaching device 13 (Fig. 2). This is a step of leaching Ni and Co contained in the residue R4 into sulfuric acid. In the second acid leaching step S13, a leaching solution E2 is produced which is a mixed solution of the residue R4, sulfuric acid, hydrogen peroxide and sodium hypochlorite A5. Here, it is conceivable that the residue R4 contains a trace amount of Mn, but this Mn exists as manganese dioxide in the leachate E2 due to the addition of sulfuric acid, hydrogen peroxide and sodium hypochlorite A5. Further, in the leachate E2, the sulfides of Ni and Co contained in the residue R4 react with sulfuric acid and hydrogen peroxide to produce sulfur (elementary substance).
　第５濾過工程Ｓ１４は、第５濾過装置１４（図２）において、液体成分と固体成分とからなる浸出液Ｅ２を濾過して、液体成分である濾液Ｆ５と固体成分である残渣Ｒ５とに分離する工程である。濾液Ｆ５には、Ｎｉ及びＣｏが含まれている。残渣Ｒ５には、二酸化マンガン及び硫黄（単体）が含まれている。 In the fifth filtering step S14, the exudate E2 consisting of the liquid component and the solid component is filtered in the fifth filtering device 14 (Fig. 2) to separate the filtrate F5 which is the liquid component and the residue R5 which is the solid component. It is a process. Filtrate F5 contains Ni and Co. Residue R5 contains manganese dioxide and sulfur (elementary).
　溶媒抽出工程Ｓ１５は、ミキサセトラ等の溶媒抽出装置１５（図２）において濾液Ｆ５に有機溶媒（抽出溶媒）及び硫酸（逆抽出溶媒）を添加する工程である。これにより、濾液Ｆ５に含まれていたＮｉ及びＣｏを硫酸塩Ｖ１として回収し、濾液Ｆ５に含まれていた不純物（リン、フッ素）を溶液Ｌとして排出する。 The solvent extraction step S15 is a step of adding an organic solvent (extraction solvent) and sulfuric acid (reverse extraction solvent) to the filtrate F5 in the solvent extraction device 15 (Fig. 2) such as a mixer settler. As a result, Ni and Co contained in the filtrate F5 are recovered as sulfate V1, and impurities (phosphorus and fluorine) contained in the filtrate F5 are discharged as a solution L.
　炭酸化工程Ｓ１６は、炭酸化装置１６（図２）において、第３濾過工程Ｓ１０の濾液Ｆ３及び第４濾過工程Ｓ１２の濾液Ｆ４に炭酸塩Ａ６を添加して炭酸リチウムＶ２を生成する工程である。この炭酸塩には、例えば、炭酸ナトリウム又は炭酸ナトリウム水和物を使用することができる。さらに、必要であれば、炭酸化工程Ｓ１６において、濾液Ｆ３、濾液Ｆ４及び炭酸塩Ａ６の混合液を濾過して濾液と残渣とに分離してもよい。この残渣として炭酸リチウムＶ２を回収することができる。 The carbonation step S16 is a step of adding a carbonate A6 to the filtrate F3 of the third filtration step S10 and the filtrate F4 of the fourth filtration step S12 in the carbonation device 16 (FIG. 2) to generate lithium carbonate V2. . For this carbonate, for example, sodium carbonate or sodium carbonate hydrate can be used. Furthermore, if necessary, in the carbonation step S16, the mixture of the filtrate F3, the filtrate F4 and the carbonate A6 may be filtered to separate the filtrate and the residue. Lithium carbonate V2 can be recovered as this residue.
　上記実施の形態によれば、加熱工程Ｓ３において電池滓Ｍ１中の正極活物質に含まれるＮｉ又は／及びＣｏ（Ｎｉ及びＣｏの一方又は両方）と負極活物質に含まれるグラファイトとが粉末状態で接触しており、炭酸ガスＧが生成する過程で、グラファイトに含まれる電子がＮｉ又は／及びＣｏに移動する。よって、電池滓Ｍ１中の正極活物質に含まれるＮｉ又は／及びＣｏを２価に還元することができる。このため、これらＮｉ又は／及びＣｏを第１酸浸出工程Ｓ４において効率よく硫酸に浸出させることができる。 According to the above embodiment, in the heating step S3, Ni and/or Co (one or both of Ni and Co) contained in the positive electrode active material in the battery residue M1 and graphite contained in the negative electrode active material are powdered. They are in contact, and electrons contained in graphite move to Ni and/or Co in the process of generating carbon dioxide G. Therefore, Ni and/or Co contained in the positive electrode active material in the battery residue M1 can be reduced to divalent. Therefore, these Ni and/or Co can be efficiently leached into sulfuric acid in the first acid leaching step S4.
　また、上記実施の形態によれば、第１酸浸出工程Ｓ４においては電池滓Ｍ１を減容させたもの（電池滓Ｍ１から炭酸ガスＧを生成した後に残る残留粉末Ｍ２）に対して硫酸を添加するため、少量の硫酸を添加するだけで残留粉末Ｍ２中の正極活物質に含まれるＮｉ及びＣｏを硫酸に浸出させることができる。 Further, according to the above embodiment, in the first acid leaching step S4, sulfuric acid is added to the volume-reduced battery slag M1 (residual powder M2 remaining after carbon dioxide gas G is generated from the battery slag M1). Therefore, Ni and Co contained in the positive electrode active material in the residual powder M2 can be leached into the sulfuric acid only by adding a small amount of sulfuric acid.
　さらに、上記実施の形態によれば、加熱工程Ｓ３の炭酸ガス生成時には２価に還元されなかったＮｉ及びＣｏを、第１酸浸出工程Ｓ４において過酸化水素により２価に還元して効率よく硫酸に浸出させることができる。 Furthermore, according to the above-described embodiment, Ni and Co, which were not reduced to divalent at the time of carbon dioxide gas generation in the heating step S3, are reduced to divalent with hydrogen peroxide in the first acid leaching step S4, and sulfuric acid is efficiently produced. can be leached into
　そして、上記実施の形態によれば、破砕物Ｃからアルミニウム片（不純物Ｉ）を除去して取り出された電池滓Ｍ１を加熱工程Ｓ３において加熱するので、加熱工程Ｓ３においてアルミニウム片が溶融し、Ｎｉ及びＣｏの還元を阻害することを防止できる。よって、第１酸浸出工程Ｓ４において残留粉末Ｍ２に含まれるＮｉ及びＣｏを効率よく硫酸に浸出させることができる。また、取出工程Ｓ２において除去したアルミニウム片を回収して有効に利用することができる。 Then, according to the above embodiment, the battery slag M1 taken out after removing the aluminum pieces (impurities I) from the crushed material C is heated in the heating step S3. and inhibiting the reduction of Co. Therefore, Ni and Co contained in the residual powder M2 can be efficiently leached into sulfuric acid in the first acid leaching step S4. Also, the aluminum pieces removed in the removal step S2 can be recovered and effectively used.
　なお、上記実施の形態において、破砕工程Ｓ１、取出工程Ｓ２及び炭酸化工程Ｓ１６を省略することができる。また、浸出液Ｅ１に含まれるＮｉ又は／及びＣｏを回収する工程が設けられていれば、工程Ｓ５～Ｓ１５の一部を省略又は変更することができる。 In addition, in the above embodiment, the crushing step S1, the extraction step S2 and the carbonation step S16 can be omitted. Further, if a step of recovering Ni and/or Co contained in the leachate E1 is provided, part of steps S5 to S15 can be omitted or changed.
　次に、本発明の一実施形態に係る有価金属の回収方法における実施例（実施例１～２２）及びその比較例（比較例１、２）について説明する。以下、各実施例及び各比較例の工程を上記実施形態と対応させて説明する。なお、各実施例については以下の工程を全て行ったが、各比較例については以下の加熱工程を省略した。また、各実施例及び各比較例においては、上記実施形態の全ての工程を行ったわけではない。 Next, examples (Examples 1 to 22) and comparative examples (Comparative Examples 1 and 2) of the method for recovering valuable metals according to one embodiment of the present invention will be described. The steps of each example and each comparative example will be described below in correspondence with the above embodiment. In addition, although all the following processes were performed about each Example, the following heating processes were abbreviate|omitted about each comparative example. In each example and each comparative example, not all the steps of the above embodiments were performed.
（破砕工程、取出工程）
　まず、リチウムイオン二次電池の廃棄物（電池廃棄物）から取り出した電池滓１４．５ｇをアルミナ製焼成ボートに投入してアルミナ製円筒管内に静置した。 (Crushing process, removal process)
First, 14.5 g of battery slag taken out from lithium ion secondary battery waste (battery waste) was put into an alumina firing boat and allowed to stand in an alumina cylindrical tube.
（加熱工程）
　アルミナ製円筒管を加熱することにより電池滓を大気雰囲気下で２時間焼成した。焼成後の電池滓を室温下まで放冷した。 (Heating process)
By heating an alumina cylindrical tube, the battery slag was calcined in the atmosphere for 2 hours. The fired battery residue was allowed to cool to room temperature.
（第１酸浸出工程）
　放冷終了後の電池滓に硫酸１００ｍｌ及び過酸化水素水（濃度３０％）５ｍｌの混合液を添加して浸出液を作製した。さらに、この浸出液を加熱して攪拌しながら電池滓に含まれるＮｉ及びＣｏを浸出させた。攪拌終了後の浸出液を室温まで放冷した。 (First acid leaching step)
A liquid mixture of 100 ml of sulfuric acid and 5 ml of hydrogen peroxide (concentration: 30%) was added to the battery residue after standing to cool to prepare a leachate. Further, Ni and Co contained in the battery slag were leached out while heating and stirring this leaching solution. After stirring, the leachate was allowed to cool to room temperature.
（第１添加工程）
　第１酸浸出工程において室温になった浸出液に、ＮａＳＨ水溶液（濃度２５０ｇ／ｌ）を添加して処理液を生成した。ＮａＳＨ水溶液の添加は、処理液を撹拌しながら処理液のＯＲＰ（酸化還元電位）が０ｍＶ（ｖｓ　Ａｇ／ＡｇＣｌ）に達するまで行った。 (First addition step)
An aqueous solution of NaSH (concentration: 250 g/l) was added to the leaching solution that had reached room temperature in the first acid leaching step to produce a treatment solution. The NaSH aqueous solution was added while stirring the treatment liquid until the ORP (oxidation-reduction potential) of the treatment liquid reached 0 mV (vs Ag/AgCl).
（第１濾過工程）
　第１添加工程の処理液を濾過して濾液と残渣とに分離した。 (First filtration step)
The treated liquid in the first addition step was filtered to separate into a filtrate and a residue.
（中和工程）
　第１濾過工程の濾液にＮａＯＨ水溶液（濃度２５％）を添加して中和液を生成した。ＮａＯＨ水溶液の添加は、中和液のｐＨが３．５になるまで行った。 (Neutralization process)
An aqueous NaOH solution (25% concentration) was added to the filtrate of the first filtration step to produce a neutralized solution. The NaOH aqueous solution was added until the pH of the neutralization liquid reached 3.5.
（第２添加工程）
　中和液にＮａＳＨ水溶液（濃度２５０ｇ／ｌ）を添加して処理液を生成した。ＮａＳＨ水溶液の添加は、処理液を撹拌しながら処理液のＯＲＰ（酸化還元電位）が－４００ｍＶ（ｖｓ　Ａｇ／ＡｇＣｌ）に達するまで行った。 (Second addition step)
An aqueous NaSH solution (concentration: 250 g/l) was added to the neutralized liquid to produce a treatment liquid. The NaSH aqueous solution was added while stirring the treatment liquid until the ORP (oxidation-reduction potential) of the treatment liquid reached −400 mV (vs Ag/AgCl).
（第３濾過工程）
　第２添加工程の処理液において黒色の沈殿物が十分生成したことを確認した後、この処理液を濾過して濾液と残渣とに分離した。 (Third filtration step)
After confirming that a sufficient amount of black precipitate was formed in the treated liquid in the second addition step, this treated liquid was filtered to separate the filtrate and the residue.
（第２酸浸出工程）
　第３濾過工程の残渣に硫酸（濃度０．５ｍｏｌ／ｌ）１００ｍｌ及び過酸化水素水（濃度３０％）５ｍｌを添加して浸出液を作製した。この浸出液を６０℃に加熱して４時間撹拌した。その後、この浸出液を室温下まで放冷した。 (Second acid leaching step)
100 ml of sulfuric acid (concentration: 0.5 mol/l) and 5 ml of hydrogen peroxide solution (concentration: 30%) were added to the residue of the third filtration step to prepare a leachate. The leachate was heated to 60° C. and stirred for 4 hours. After that, this leachate was allowed to cool to room temperature.
（第５濾過工程）
　第２酸浸出工程の浸出液を濾過して濾液と残渣とに分離した。 (Fifth filtration step)
The leachate of the second acid leach step was filtered to separate the filtrate and the residue.
（溶媒抽出工程）
　第５濾過工程の濾液３０ｌに対し、ミキサセトラにおいて抽出溶媒（ＰＣ－８８Ａの含有率が２０ｖｏｌ％であって希釈剤ケロシンの含有率が８０ｖｏｌ％であるもの）及び逆抽出溶媒（硫酸）を添加した。これにより、この濾液に含まれるＮｉ及びＣｏを硫酸塩として回収した。なお、ＰＣ－８８Ａとは、大八化学工業株式会社製の金属抽出剤である。 (Solvent extraction step)
To 30 l of the filtrate of the fifth filtration step, an extraction solvent (PC-88A content of 20 vol% and diluent kerosene content of 80 vol%) and reverse extraction solvent (sulfuric acid) were added in a mixer settler. . As a result, Ni and Co contained in this filtrate were recovered as sulfates. PC-88A is a metal extractant manufactured by Daihachi Chemical Industry Co., Ltd.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１は、各実施例及び各比較例において使用した電池の種類、加熱工程における電池滓の焼成温度、第１酸浸出工程において使用した硫酸の濃度、第１酸浸出工程における浸出温度（浸出液の加熱温度）及び浸出時間（浸出液の攪拌時間）、溶媒抽出工程におけるＣｏ及びＮｉの回収率を実施例及び比較例ごとに示している。 Table 1 shows the type of battery used in each example and each comparative example, the baking temperature of the battery slag in the heating process, the concentration of sulfuric acid used in the first acid leaching process, and the leaching temperature in the first acid leaching process (the temperature of the leachate). heating temperature), leaching time (stirring time of the leaching solution), and recovery rates of Co and Ni in the solvent extraction step are shown for each example and comparative example.
　表１において、ＮＣＭとは、ＮＣＭ系電池（すなわち、正極活物質としてＮｉ，Ｃｏ及びＭｎの複合酸化物が使用された電池）である。ＮＣＡとは、ＮＣＡ系電池（すなわち、正極活物質としてＮｉ，Ｃｏ及びＡｌの複合酸化物が使用された電池）である。Ｃｏの回収率とは、「（溶媒抽出工程において回収した硫酸塩に含まれるＣｏの質量）×１００÷（電池滓に含まれるＣｏの質量）」を意味している。Ｎｉの回収率とは、「（溶媒抽出工程において回収した硫酸塩に含まれるＮｉの質量）×１００÷（電池滓に含まれるＮｉの質量）」を意味している。硫酸塩に含まれるＣｏ，Ｎｉの質量は、ＩＣＰ－ＡＥＳを用いて測定した。電池滓に含まれるＣｏ，Ｎｉの質量は、ＸＲＦの定量分析により測定した。 In Table 1, NCM is an NCM-based battery (that is, a battery using a composite oxide of Ni, Co, and Mn as a positive electrode active material). NCA is an NCA-based battery (that is, a battery using a composite oxide of Ni, Co and Al as a positive electrode active material). The recovery rate of Co means "(the mass of Co contained in the sulfate recovered in the solvent extraction step)×100/(the mass of Co contained in the battery slag)". The recovery rate of Ni means "(the mass of Ni contained in the sulfate recovered in the solvent extraction step)×100÷(the mass of Ni contained in the battery slag)". The masses of Co and Ni contained in the sulfate were measured using ICP-AES. The masses of Co and Ni contained in the battery slag were measured by XRF quantitative analysis.
　実施例３及び比較例１を比較すると、焼成の有無以外の条件は同一であるが焼成を行っているか否かが異なっている。そして、実施例３（焼成を行った）においては、比較例１（焼成を行っていない）に比較してＣｏ回収率及びＮｉ回収率が顕著に高くなっている。実施例１４及び比較例２を比較すると、焼成の有無以外の条件は同一であるが焼成を行っているか否かが異なっている。そして、実施例１４（焼成を行った）においては、比較例２（焼成を行っていない）に比較してＣｏ回収率及びＮｉ回収率が顕著に高くなっている。 Comparing Example 3 and Comparative Example 1, the conditions other than the presence or absence of firing are the same, but the difference is whether or not firing is performed. In Example 3 (fired), the Co recovery rate and Ni recovery rate are significantly higher than those of Comparative Example 1 (no firing). When Example 14 and Comparative Example 2 are compared, the conditions other than the presence or absence of firing are the same, but the difference is whether or not firing is performed. In Example 14 (fired), the Co recovery rate and Ni recovery rate are significantly higher than those of Comparative Example 2 (no firing).
　実施例１～４を比較すると、浸出温度以外の条件は同一であるが浸出温度は互いに異なっている。実施例１２～実施例１５を比較すると、浸出温度以外の条件は同一であるが浸出温度は互いに異なっている。そして、浸出温度が６０℃及び８０℃である実施例においては、浸出温度が２５℃及び４０℃である実施例よりもＣｏ回収率及びＮｉ回収率が顕著に高くなっている。 Comparing Examples 1 to 4, the conditions other than the leaching temperature are the same, but the leaching temperatures are different. Comparing Examples 12 to 15, conditions other than the leaching temperature are the same, but the leaching temperatures are different. In the examples in which the leaching temperatures were 60°C and 80°C, the Co recovery rate and the Ni recovery rate were significantly higher than those in the examples in which the leaching temperatures were 25°C and 40°C.
　実施例３、５～７を比較すると、焼成温度以外の条件は同一であるが焼成温度は互いに異なっている。実施例１４、１６～１８を比較すると、焼成温度以外の条件は同一であるが焼成温度は互いに異なっている。そして、焼成温度が７００℃である実施例においては、焼成温度が６００℃である実施例よりもＣｏ回収率及びＮｉ回収率が顕著に高くなっている。さらに、焼成温度が８００℃及び９００℃である実施例においては、焼成温度が７００℃である実施例よりもＣｏ回収率及びＮｉ回収率が顕著に高くなっている。 Comparing Examples 3 and 5 to 7, the conditions other than the firing temperature are the same, but the firing temperatures are different. Comparing Examples 14 and 16 to 18, the conditions other than the firing temperature are the same, but the firing temperatures are different. In the example in which the sintering temperature is 700°C, the Co recovery rate and the Ni recovery rate are significantly higher than those in the example where the sintering temperature is 600°C. Furthermore, in the examples in which the sintering temperature was 800°C and 900°C, the Co recovery rate and the Ni recovery rate were significantly higher than those in the example in which the sintering temperature was 700°C.
　実施例３、８及び９を比較すると、硫酸濃度以外の条件は同一であるが硫酸濃度は互いに異なっている。実施例１４、１９及び２０を比較すると、硫酸濃度以外の条件は同一であるが硫酸濃度は互いに異なっている。そして、硫酸濃度が２ｍｏｌ／ｌ及び２．５ｍｏｌ／ｌである実施例においては、硫酸濃度が１．５ｍｏｌ／ｌである実施例よりもＣｏ回収率及びＮｉ回収率が顕著に高くなっている。 Comparing Examples 3, 8 and 9, the conditions other than the sulfuric acid concentration are the same, but the sulfuric acid concentrations are different. Comparing Examples 14, 19 and 20, the conditions are the same except for the sulfuric acid concentration, but the sulfuric acid concentration is different. In addition, in the examples in which the sulfuric acid concentrations were 2 mol/l and 2.5 mol/l, the Co recovery rate and the Ni recovery rate were significantly higher than those in the example in which the sulfuric acid concentration was 1.5 mol/l.
　実施例３、１０及び１１を比較すると、浸出時間以外の条件は同一であるが浸出時間は互いに異なっている。実施例１４、２１及び２２を比較すると、浸出時間以外の条件は同一であるが浸出時間は互いに異なっている。そして、浸出時間が４時間である実施例においては、浸出時間が２時間及び３時間である実施例よりもＣｏ回収率及びＮｉ回収率が顕著に高くなっている。 Comparing Examples 3, 10 and 11, the conditions other than the leaching time are the same, but the leaching time is different. Comparing Examples 14, 21 and 22, the conditions are the same except for the leaching time, but the leaching time is different from each other. In the example in which the leaching time was 4 hours, the Co recovery rate and the Ni recovery rate were significantly higher than those in the examples in which the leaching time was 2 hours and 3 hours.
　以上の実施例及び比較例により次の結論を導出することができる。上記実施の形態において、電池滓Ｍ１を加熱工程Ｓ３で焼成することにより、第１酸浸出工程Ｓ４において残留粉末Ｍ２に含まれるＮｉ及びＣｏを効率よく硫酸に浸出させることができ、溶媒抽出工程Ｓ１５においてＮｉ及びＣｏを効率よく回収することができる。 The following conclusions can be drawn from the above examples and comparative examples. In the above embodiment, by baking the battery slag M1 in the heating step S3, the Ni and Co contained in the residual powder M2 can be efficiently leached into sulfuric acid in the first acid leaching step S4, and the solvent extracting step S15. Ni and Co can be efficiently recovered in.
　また、加熱工程Ｓ３において電池滓Ｍ１を７００℃以上（より好ましくは８００℃以上９００℃以下）に加熱し、第１酸浸出工程Ｓ４において使用する硫酸の濃度を２ｍｏｌ／ｌ以上とし、残留粉末Ｍ２の浸出温度を６０℃以上とし、残留粉末Ｍ２の浸出時間を４時間以上とすることにより、第１酸浸出工程Ｓ４において残留粉末Ｍ２に含まれるＮｉ及びＣｏを効率よく硫酸に浸出させることができ、溶媒抽出工程Ｓ１５においてＮｉ及びＣｏを効率よく回収することができる。 Further, in the heating step S3, the battery slag M1 is heated to 700° C. or higher (more preferably 800° C. or higher and 900° C. or lower), the concentration of sulfuric acid used in the first acid leaching step S4 is set to 2 mol/l or higher, and the residual powder M2 is By setting the leaching temperature of 60° C. or higher and setting the leaching time of the residual powder M2 to 4 hours or longer, Ni and Co contained in the residual powder M2 can be efficiently leached into sulfuric acid in the first acid leaching step S4. , Ni and Co can be efficiently recovered in the solvent extraction step S15.
　電池滓に含まれるＮｉ及びＣｏの一方又は両方を効率よく硫酸に浸出させて回収することができる。 One or both of Ni and Co contained in the battery slag can be efficiently leached into sulfuric acid and recovered.
　１　　破砕装置
　２　　取出装置
　３　　加熱装置
　４　　第１酸浸出装置
　５　　第１添加装置
　６　　第１濾過装置
　７　　中和槽値
　８　　第２濾過装置
　９　　第２添加装置
　１０　　第３濾過装置
　１１　　洗浄装置
　１２　　第４濾過装置
　１３　　第２酸浸出装置
　１４　　第５濾過装置
　１５　　溶媒抽出装置
　１６　　炭酸化装置 1 crushing device 2 removal device 3 heating device 4 first acid leaching device 5 first addition device 6 first filtration device 7 neutralization tank value 8 second filtration device 9 second addition device 10 third filtration device 11 washing device 12 third 4 Filtration Apparatus 13 2nd Acid Leaching Apparatus 14 5th Filtration Apparatus 15 Solvent Extraction Apparatus 16 Carbonation Apparatus

Claims (9)

  1. 　Ｎｉ及びＣｏの一方又は両方を含む正極活物質と、グラファイトを含む負極活物質と、を有する電池滓を加熱することにより、前記電池滓中の前記負極活物質に含まれるグラファイトを酸化して炭酸ガスを生成する加熱工程と、
    　前記電池滓から前記炭酸ガスを生成した後に残留する残留粉末に硫酸を添加することにより、前記残留粉末中の前記正極活物質に含まれるＮｉ及びＣｏの一方又は両方を前記硫酸に浸出させて浸出液を生成する酸浸出工程とを有することを特徴とする有価金属の回収方法。     By heating a battery residue having a positive electrode active material containing one or both of Ni and Co and a negative electrode active material containing graphite, graphite contained in the negative electrode active material in the battery residue is oxidized to form carbonic acid. a heating step to generate a gas;
    By adding sulfuric acid to the residual powder remaining after the carbon dioxide gas is generated from the battery slag, one or both of Ni and Co contained in the positive electrode active material in the residual powder is leached into the sulfuric acid to form a leachate. A method for recovering valuable metals, comprising: an acid leaching step that produces
  2. 　前記酸浸出工程においては、前記硫酸と共に過酸化水素を前記残留粉末に添加することを特徴とする請求項１に記載の有価金属の回収方法。 The method for recovering valuable metals according to claim 1, wherein in the acid leaching step, hydrogen peroxide is added to the residual powder together with the sulfuric acid.
  3. 　前記浸出液に含まれる前記Ｎｉ又は／及びＣｏの一方を回収する回収工程をさらに備えることを特徴とする請求項１又は２に記載の有価金属の回収方法。 The method for recovering valuable metals according to claim 1 or 2, further comprising a recovery step of recovering one of said Ni and/or Co contained in said leachate.
  4. 　前記回収工程は、
    　前記浸出液に硫化剤を添加して処理液を生成する添加工程と、
    　前記処理液を濾過することにより、前記処理液を、液体成分である濾液と、前記浸出液に含まれていたＮｉ及びＣｏの一方又は両方を含む固体成分である残渣と、に分離する濾過工程とを有することを特徴とする請求項３に記載の有価金属の回収方法。     The recovery step includes
    an adding step of adding a sulfiding agent to the leachate to generate a treatment liquid;
    a filtration step of separating the treatment liquid into a filtrate, which is a liquid component, and a residue, which is a solid component containing one or both of Ni and Co contained in the leachate, by filtering the treatment liquid; The method for recovering valuable metals according to claim 3, characterized by having
  5. 　電池廃棄物を破砕して破砕物を製造する破砕工程と、
    　前記破砕物からアルミニウム片を除去して前記電池滓を取り出す取出工程とをさらに備え、
    　前記加熱工程においては、取り出された前記電池滓を加熱することを特徴とする請求項１～４のいずれか１項に記載の有価金属の回収方法。     a crushing step of crushing battery waste to produce crushed products;
    a removing step of removing the aluminum pieces from the crushed material and removing the battery slag;
    The method for recovering valuable metals according to any one of claims 1 to 4, wherein in the heating step, the removed battery slag is heated.
  6. 　前記加熱工程において、前記電池滓を７００℃以上に加熱することを特徴とする請求項１～５のいずれか１項に記載の有価金属の回収方法。 The method for recovering valuable metals according to any one of claims 1 to 5, wherein in the heating step, the battery slag is heated to 700°C or higher.
  7. 　前記酸浸出工程において、前記残留粉末に２ｍｏｌ／ｌ以上の前記硫酸を添加してから、前記浸出液を６０℃以上に加熱して４時間以上攪拌することを特徴とする請求項１～６のいずれか１項に記載の有価金属の回収方法。 7. The method according to any one of claims 1 to 6, wherein in the acid leaching step, after adding 2 mol/l or more of the sulfuric acid to the residual powder, the leaching solution is heated to 60° C. or more and stirred for 4 hours or more. 1. The method for recovering valuable metals according to 1.
  8. 　Ｎｉ又はＣｏの一方又は両方を含む正極活物質と、グラファイトを含む負極活物質と、を有する電池滓を加熱することにより、前記電池滓中の前記負極活物質に含まれるグラファイトを酸化して炭酸ガスを生成する加熱装置と、
    　前記電池滓から前記炭酸ガスを生成した後に残留する残留粉末に硫酸を添加することにより、前記残留粉末中の前記正極活物質に含まれるＮｉ又はＣｏの一方又は両方を前記硫酸に浸出させて浸出液を生成する酸浸出装置とを備えることを特徴とする有価金属の回収装置。     By heating a battery residue having a positive electrode active material containing one or both of Ni and Co and a negative electrode active material containing graphite, the graphite contained in the negative electrode active material in the battery residue is oxidized to form carbonic acid. a heating device for generating gas;
    By adding sulfuric acid to the residual powder remaining after the carbon dioxide gas is generated from the battery slag, one or both of Ni or Co contained in the positive electrode active material in the residual powder is leached out into the sulfuric acid to form a leachate. An apparatus for recovering valuable metals, comprising: an acid leaching apparatus that produces
  9. 　前記浸出液に含まれる前記Ｎｉ及びＣｏの一方又は両方を回収する回収装置を更に備えることを特徴とする請求項８に記載の有価金属の回収装置。 The apparatus for recovering valuable metals according to claim 8, further comprising a recovery apparatus for recovering one or both of said Ni and Co contained in said leachate.
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