[go: up one dir, main page]

WO2012026061A1 - Procédé de récupération de métal et dispositif de récupération de métal - Google Patents

Procédé de récupération de métal et dispositif de récupération de métal Download PDF

Info

Publication number
WO2012026061A1
WO2012026061A1 PCT/JP2011/003849 JP2011003849W WO2012026061A1 WO 2012026061 A1 WO2012026061 A1 WO 2012026061A1 JP 2011003849 W JP2011003849 W JP 2011003849W WO 2012026061 A1 WO2012026061 A1 WO 2012026061A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
solution
metal
ions
recovery
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.)
Ceased
Application number
PCT/JP2011/003849
Other languages
English (en)
Japanese (ja)
Inventor
泰子 小島
山口　欣秀
岡本　正英
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.)
Hitachi Ltd
Original Assignee
Hitachi Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hitachi Ltd filed Critical Hitachi Ltd
Publication of WO2012026061A1 publication Critical patent/WO2012026061A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

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
    • 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
    • C22B7/006—Wet processes
    • C22B7/007—Wet processes by acid 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
    • 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
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/52—Reclaiming serviceable parts of waste cells or batteries, e.g. recycling
    • 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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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 a metal recovery technique for easily recovering metal from a battery.
  • Non-Patent Document 1 features a recycling technology of a lithium ion battery, and systematically describes a method for recovering valuable metals constituting the lithium ion battery.
  • a used lithium ion battery dissolves valuable metals by acid leaching after mechanical processing such as opening, dismantling, and grinding, Using the difference in solubility characteristics for each desired component, the components are separated and collected for each desired component by a process such as separation for each component to form a precipitate, or solvent extraction of the desired component preferentially.
  • Patent Document 1 discloses a technique for recovering Cu and Co using a diaphragm electrolysis method in which a solution obtained by dissolving a valuable metal obtained by acid leaching is used as a catholyte and a cation exchange membrane is used as a diaphragm. .
  • Non-Patent Document 1 aims at improving both the recovery rate of valuable materials and increasing the purity of recovered materials by various devices, but the process is complicated and it is enormous for processing a large amount of waste batteries. There is much room for improvement in terms of capital investment.
  • Patent Document 1 specifically uses the anion selectivity of the anion-selective membrane and the equipment (diaphragm electrolytic cell shown in FIG. 2 of Patent Document 1) using the ion-selective characteristics of the cation exchange membrane. Use the diffusion dialysis equipment (not shown). More specifically, Cu electrodeposition recovery by diaphragm electrolysis ⁇ pH adjustment ⁇ Co electrodeposition recovery by diaphragm electrolysis ⁇ pH adjustment ⁇ precipitation recovery of Fe (OH) 3 and Al (OH) 3 ⁇ by adding carbonate Major valuable metals can be recovered by a series of treatments of Li 2 CO 3 recovery.
  • Fe (OH) 3 and Al (OH) 3 Since there is a tendency to gelled in an aqueous solution of a weakly acidic to neutral, based on the technique of Patent Document 1 Fe (OH) 3 and Al (OH ) The operation of the step of collecting 3 by filtration is not easy. On the other hand, when the liquid is diluted to facilitate the filtration operation, the recovery rate of Li decreases. In addition, since the surface of the gel-like precipitate of Fe (OH) 3 or Al (OH) 3 also has a property of adsorbing Li ions, it is difficult to significantly improve the Li recovery rate from this viewpoint.
  • the present invention provides a metal recovery method for recovering a metal from a positive electrode material of a lithium ion battery containing lithium and a transition metal element, wherein the positive electrode material is dissolved in an acidic solution and transitions between lithium ions and An acid leaching step for leaching metal ions into the acidic solution, and passing an acidic solution containing the lithium ions and transition metal ions through a basic anion exchange resin, and a solution eluted from the ion exchange resin as a first solution. And a metal separation step of collecting the solution eluted from the ion exchange resin into a second container and then collecting the solution into a second container.
  • the waste lithium ion battery subjected to the discharge treatment is disassembled and pulverized (step 101).
  • the pulverized product is subjected to a sieving process to be separated into a casing, a packing / safety valve, circuit elements, a separator, a current collector, and the like (step 102).
  • the active material of the lithium ion battery positive electrode material, negative electrode material, electrolyte
  • the acid solution is used.
  • one kind of mineral acid such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or a plurality of them may be mixed.
  • lithium ions are recovered from the obtained acid exudate (step 104).
  • this acid exudate is sufficiently separated into a liquid A containing a lot of Li, a liquid B containing a lot of Co, and a liquid C containing a lot of acid by performing a retardation treatment with a retardation device (FIG. 4).
  • the acid and Li are separated from the recovered liquid using a so-called acid retardation method, that is, utilizing the Donnan membrane effect of the anion exchange resin column.
  • the acid retardation method is described in Non-Patent Document 2.
  • the charge remaining in the battery is discharged by immersing the battery in a conductive liquid containing an electrolyte.
  • a mixed solution of sulfuric acid / ⁇ -butyrolactone was used as the conductive liquid containing the electrolyte.
  • the conductivity (reciprocal of the resistance value) can be adjusted by adjusting the sulfuric acid concentration.
  • the electrical resistance of the solution from the right end to the left end of the discharge vessel was measured and found to be 100 k ⁇ . If the resistance value of the solution is too small, the discharge proceeds too rapidly, which is dangerous. On the other hand, if the resistance value is too large, it takes too much time to reduce the practicality.
  • the solution resistance is preferably in the range of about 1 k ⁇ to 1000 k ⁇ , and the electrolyte concentration may be adjusted so as to fall within this resistance value range.
  • waste battery of the present embodiment in addition to the so-called used battery whose charge capacity has been reduced due to reaching the limit of the predetermined number of times of charge and discharge, half of the battery generated due to problems in the battery manufacturing process, etc. Including old-fashioned inventory items that occur when products and product specifications change.
  • step 101 the waste battery after the discharge treatment is disassembled.
  • disassemble the battery components of the waste battery after discharge such as casing, packing / safety valves, circuit elements, spacers, current collectors, separators, and positive electrode and negative electrode active materials. Sort.
  • waste lithium ion batteries are often filled with gas and are in a pressurized state, and needless to say, work safety considerations are necessary.
  • wet pulverization was performed while cooling in the state of being immersed in a conductive liquid containing the above electrolyte. By adopting wet pulverization under cooling, the gas filled in the battery could be safely crushed without being scattered in the atmosphere.
  • composition of the conductive liquid containing the above electrolyte that dissolves the electrolyte in order to promote the peeling of the positive electrode active material and the negative electrode active material coated and molded on the current collector surface from the respective current collector surfaces It is safe to adjust.
  • the conductivity should be noted.
  • the viscosity and the dielectric constant should be noted.
  • the composition of the conductive liquid used for each process may be changed. In that case, it is necessary to prepare two or more kinds of conductive liquids. In this example, the same composition was used from the viewpoint of simplification and reduction of labor and cost.
  • the wet pulverization method that can be used in this embodiment includes, for example, a ball mill method, but is not necessarily limited thereto.
  • constituent members such as housings, packing / safety valves, circuit elements, spacers, current collectors, separators, and electrode active materials
  • positive electrode active material hereinafter referred to as positive electrode active material
  • negative electrode active material negative electrode active material
  • the slurry obtained by the wet pulverization can be separated by filtration using a relatively coarse filter as it is. good.
  • the recovery rate may be improved by introducing a continuous treatment from wet pulverization to filtration.
  • the casing, packing / safety valve, current collector (aluminum foil, copper foil), etc. have a higher spreadability than the positive electrode active material (typically LiCoO 2 ) or the negative electrode active material (typically graphite). Therefore, the breaking strength is also large. Because of this characteristic, the crushed material of the electrode active material has a smaller size than the crushed material obtained from other members, and as a result, it can be easily separated and collected by sieving or filtering.
  • the under sieve obtained by the above treatment is dissolved (acid leaching; step 103).
  • acid leaching solution sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid may be used alone, or methanol, hydrogen peroxide, etc. may be mixed.
  • hydrogen peroxide is most preferable from the viewpoint of leaching efficiency, but sulfuric acid is most preferable from the viewpoint of separation and recovery described later.
  • an equal mixture of hydrogen peroxide and sulfuric acid was used.
  • the positive electrode active material of the waste battery used in this example is a lithium compound mainly composed of LiCoO 2 , but may include a positive electrode active material of another composition such as iron phosphate, nickel, or manganese. Since the treatment liquid containing hydrochloric acid has a risk of generating chlorine gas, it is desirable not to contain hydrochloric acid, but a treatment liquid containing hydrochloric acid may be used. In such a case, when the treatment liquid containing hydrochloric acid is mixed at a stroke instead of slowly dropping, the lithium compound tends to react and dissolve vigorously and easily generate chlorine gas, but a solvent such as ⁇ -butyrolactone.
  • acid leaching treatment there is a tendency that the amount of chlorine gas by-product tends to decrease or the amount of chlorine gas generated as a by-product tends to decrease.
  • the treatment liquid containing nitric acid may explode upon contact with the ion exchange resin, it needs to be handled with care, for example, diluted to a low concentration.
  • Mineral acids that can be used in this example include sulfuric acid (29% to 98%), hydrochloric acid (36%), phosphoric acid, nitric acid, or a mixed acid thereof. Moreover, you may mix a mineral acid with methanol, hydrogen peroxide solution, etc. as a reducing agent. Mineral acids containing alkali metals other than lithium (sodium, potassium, rubidium, cesium) that are difficult to separate from lithium are not used. In consideration of the type and composition of the lithium compound, the treatment amount, the treatment time, the cost, etc., it can be appropriately selected from these. After the acid leaching process is completed, the undissolved negative electrode active material (carbon material) can be removed by filtering the exudate.
  • carbon material carbon material
  • Acid retardation is a phenomenon in which when an acid and its salt are passed through a container filled with an anion exchange resin, the acid salt is eluted in this order. If this is utilized, an acid and its salt can be separated and recovered.
  • the acidic solution containing a plurality of salts as an acid salt is passed through the anion exchange resin, the present inventor firstly elutes transition metal ions, then elutes lithium ions, and then The acid was found to elute. The cause is considered to be the influence of ionic radius difference and electrostatic interaction (intermolecular force), but the details are unknown.
  • Co can be recovered by removing Co contained in the recovery solution by utilizing the fact that Co elutes before Li.
  • Li can be recovered without adding Na or K, which is difficult to separate from Li.
  • an ion exchange resin is filled into a hollow container such as a tube or cylinder, and an acid exudate is injected. The acid is separated by the difference in elution time, and the liquid separated in the order of Co, Li, and acid is removed. to recover.
  • FIG. 2 shows the acid retardation device 7.
  • the acid metal separation tank 1 is connected to the acid exudation liquid tank 2 by solution paths 3a and 3b. Furthermore, a solution path 3c for introducing pure water is connected to the acid metal separation tank 1, and the first recovery container 5 and the second recovery container are connected via the solution paths 3d to f and the valve 4. 6 is connected.
  • the solution paths 3a to 3f are constituted by pipes, tubes, etc., and the tanks and collection containers are connected through the solution.
  • the valve 4 switches the solution path from the solution path 3d to the solution path 3e and the solution path 3f.
  • the path is switched by a valve, but instead, the solution path 3 to the recovery containers 5 and 6 may be connected to the acid metal separation tank 1 separately.
  • the acid metal separation tank 1 is filled with an ion exchange resin.
  • a strongly basic anion exchange resin Diaion MA03SS (manufactured by Nippon Nensui, “Diaion” is a registered trademark) was used as the ion exchange resin, but the basic anion exchange is not limited thereto.
  • strong basic type I (trimethylammonium) anion exchange resin, strong basic type II (dimethylethanolammonium) anion exchange resin, or the like can be used. If it is a strongly basic anion exchange resin, the effect of ion adsorption is high.
  • Type I in terms of maintenance, Type I is difficult to regenerate and requires a large amount of regenerant, while Type II is easy to regenerate and requires a small amount of regenerant.
  • Type II is used when a large volume is processed or a high concentration of metal ions is processed and the frequency of regeneration is high.
  • Type I has the advantages of less leakage and better chemical (temperature) stability than Type II.
  • Use type I when you want to purify with high purity.
  • an I-type gel type is used, but a porous type may also be used. The purity of the recovered Li ions is adjusted by the ion exchange capacity, crosslinking density, resin particle size, and the like.
  • a chelate resin is used as an ion adsorption means, Li ions can be eluted first, and Co ions can be eluted later. This is because the chelate resin selectively captures divalent metal ions and does not capture monovalent metal ions. In this case, the order of metal recovery is the reverse of the above.
  • a strongly basic type II anion exchange resin since it has an ethanol-derived hydroxyl group, it can be used as a chelate functional group if a carboxyl group or the like is added thereto.
  • a pressure gauge and a flow meter are respectively provided at the inlet and outlet of each solution path 3.
  • sensors such as a conductivity meter, pH meter, ion concentration meter, etc.
  • a rectifying mechanism for rectifying the flow of the liquid a pressurizing mechanism for supplying the treatment liquid under pressure, and a control for controlling the whole Equipment and equipment necessary to realize functions such as mechanisms are provided without excess or deficiency.
  • FIG. 4 shows a schematic diagram of a chart of the metal ion concentration flowing out from the acid metal separation tank 1 with respect to the time during the separation operation at this time.
  • the acid exudate is passed through the solution path 3b. Then, the entire amount of the acid exudate to be processed at one time is supplied to the metal separation tank 1.
  • the amount of the acid exudate to be treated in a single treatment is an amount that can be sufficiently adsorbed by the ion exchange resin and exert the effect of acid retardation treatment. Then, the acid exudate is passed through the ion exchange resin (actually, the acid exudate does not pass through the ion exchange resin particles but flows through the surface of the particles, but passes through the aggregated ion exchange resin particles.
  • the effluent from the acid metal separation tank 1 has a high Co ion concentration as in period D shown in FIG.
  • This effluent is recovered in the first recovery container 5 via the solution path 3d, the valve 4 and the solution path 3c.
  • the recovery may be started during the supply of the acid exudate, or may be started after the end of the supply.
  • the container 5 collects a solution containing Co at a high concentration (low concentration ratio of Li ions to Co ions).
  • the container 6 collects a solution containing a high concentration of Li ions (a high concentration ratio of Li ions to Co ions) and a low concentration of Co ions and acids.
  • the solution operation is performed as shown in FIG. Since the recovery to the second recovery container 6 is performed in a state where the liquid supply to the ion exchange resin is stopped, the amount of the solution in the acid metal separation tank 1 is small at the start of the period F.
  • pure water regenerated water
  • pure water liquid having a weaker acid than the acid exudate
  • the acid adsorbed by the ion exchange resin is released due to the increase in pH. Further, in the eluate at this time, as shown in the period F in FIG.
  • the Co ions and Li ions have already been eluted, so the concentration is low.
  • the eluate containing the liberated acid is collected from the solution path 3 a and stored in the acid exudate tank 5.
  • the acid collected in the acid leaching solution tank 5 can be repeatedly used for the acid leaching process in step 103.
  • a positive electrode active material is newly dissolved in the collected acid to form an acid exudate, and an acid retardation treatment is performed. Even if Li ions and Co ions are mixed in the recovery solution, they are contained in the acid extraction solution after the next acid leaching treatment, so that the acid metal can be separated again and recovered in the recovery containers 5 and 6.
  • the ion exchange resin from which the acid has been released has returned to the state before the acid retardation treatment, it can be used for the next acid retardation without treatment.
  • the switching timing of the periods D to F may be performed according to time. Moreover, the inside of the acid metal separation tank 1 may be measured by a measuring instrument, and switching may be performed based on the measurement result. Used when measuring ion conductivity meter (measures the conductivity of the solution), pH meter (measures the pH of the solution), absorbance meter (ion exchange resin that develops color when supplemented with ions) Possible).
  • switching between the periods D and E switching of the solution flow
  • switching between the periods E and F is sufficient when the Li ion concentration is sufficiently high.
  • the present invention is not limited to this, and the period D may be switched to E when the Li ion concentration is sufficiently increased.
  • the Co ion concentration in the container 6 for recovering Li ions becomes high, but this can be solved by further performing ion separation treatment as in the examples described later.
  • the periods D to F are switched instantaneously, but each period may be overlapped, or a pause period during which the outflow of the solution is suspended may be provided between the periods D to F.
  • the positive electrode active material of the lithium ion battery was leached into an acidic solution, and acid retardation treatment of the acid leaching solution was performed.
  • the positive electrode active material of the treated lithium ion battery is a composite oxide containing lithium and a transition metal such as lithium cobaltate, lithium manganate, and lithium nickelate.
  • Manganese and nickel are also transition metals like cobalt, and are common to easily become divalent ions. Also, the ionic radius is close, and the same effect as cobalt can be expected.
  • FIG. 5 shows the analysis result of the eluate after the acid retardation treatment.
  • the acid exudate before treatment is colored pink by Co ions, and its Li / Co concentration ratio is 0.2.
  • the solution eluted from the ion exchange resin at the initial stage of the acid retardation treatment has a darker pink color than the acid exudate before the treatment. This indicates that Co ions are contained at a high concentration.
  • the eluate was sampled at point G in FIG. 5 and its Li / Co concentration ratio was measured. As a result, the value was 4.2. This indicates that the elution of Li has already started at point G. Further, when the eluate at the H point was sampled, the Li / Co concentration ratio was 289. This indicates that the elution of Co ions is almost completed and Li ions are mainly eluted. It can be seen that high concentration of lithium can be achieved by using the eluate at this point.
  • olivine-based positive electrode materials such as LiNiO 2 , LiMnO 2 , Li (Ni 1/3 Co 1/3 Mn 1/3 ) O 2 , LiCoPO 4 , LiFePO 4 , LiCoPO 4 , LiFePO 4, etc.
  • pH adjustment Li and other Co, Ni, Mn, and Fe can be precipitated and recovered as hydroxides.
  • a method such as precipitation recovery or solvent extraction as a hydroxide by adjusting the pH can be used.
  • Li and a transition metal can be isolate
  • Example 2 first, disassembly of the battery, extraction of the positive electrode material, acid leaching of the positive electrode material, and the first acid retardation treatment are performed in the same manner as in Example 1. In this example, after that, the acid retardation treatment is performed again on the recovered liquid, and the acid retardation treatment is performed in multiple stages, thereby increasing the separation ratio of Li, Co, and acid in a substantially power relationship. Can do.
  • both the solution in the first recovery container 5 containing a lot of transition metal ions and the solution in the second recovery container 6 containing a lot of Li ions are targeted.
  • the target solution is poured into the acid leaching solution tank 2 and subjected to acid retardation treatment in the acid metal separation tank 1, and the eluted liquid is first put into the first collection container and then into the second collection container 6.
  • a solution having a lower Li ion concentration ratio to transition metal ions is recovered in the first recovery container 5, or a solution having a higher Li ion concentration ratio to transition metal ions is recovered second. It can be recovered in the container 6. In this way, by repeatedly performing the separation process on the same solution in multiple stages, a solution in which Li ions and transition metal ions are further separated can be recovered.
  • the device used may be the same device as in the first embodiment. Since the ions in the acid-metal separation tank 1 are swept away by the acid recovery with pure water and returned to the state before use, the same acid retardation device can be used repeatedly without special washing. Note that, by repeatedly performing the treatment, the concentrations of Li, Co, and acid all tend to be diluted. Therefore, a solution diluted to a certain concentration can recover high-purity Li, Co, and acid, respectively, through a concentration step.
  • disassembly of the battery, removal of the positive electrode material, acid leaching of the positive electrode material, and acid retardation treatment are performed in the same manner as in Example 1.
  • dialysis treatment is performed using a dialysis apparatus (FIG. 6) in which an ion exchange membrane is installed. This is the difference from the first embodiment.
  • Li selectively recovers with high purity by allowing Li to selectively permeate through the ion exchange membrane.
  • Li and the transition metal are separated by the Donnan film effect. By these two actions, Li can be recovered with high purity.
  • FIG. 6 shows a schematic structure of the dialysis tank 8 used in the valuable metal recovery apparatus in this example.
  • the dialysis tank 8 shown in FIG. 6 is provided with an acid exudate inlet 9 for supplying an acid exudate after filtration and an acid exudate outlet 10 through which the acid exudate subjected to dialysis flows out.
  • a recovery liquid tank 14 having an outflow of recovery liquid outlet 12 is provided. Further, the dialysis pressure tank 13 and the recovery liquid tank 14 are connected via a dialysis membrane 15.
  • a Selemion DSV (“Selemion” is a registered trademark) manufactured by Asahi Glass, which is an anion exchange membrane for diffusion dialysis, is processed, and between the dialysis pressure tank 13 and the recovery liquid tank 14. Used by fitting.
  • Selemion DSV Selemion DSV
  • Asahi Glass which is an anion exchange membrane for diffusion dialysis
  • other anion exchange membranes can be used, but in that case, it is desirable to select them in consideration of ion transport number and oxidation resistance.
  • the acid leachate containing Li ions and transition metal ions from the acid exudate tank 1 flows into the pressurized tank 13 from the acid exudate inlet 9.
  • a recovery liquid (pure water) is supplied from the recovery liquid inlet 11.
  • the transport number of Li ions in the dialysis membrane 15 is significantly larger than the transport number of Co ions.
  • the Li / Co concentration ratio dissolved in the acid exudate before dialysis of the dialysis membrane 15 was about 0.1, but Li / Co dissolved in the recovered liquid recovered by the first stage of dialysis. The concentration ratio was about 0.7, indicating that lithium was concentrated and recovered.
  • the transport number of lithium ion in the dialysis membrane (Asahi Glass Selemion DSV) used in this example is about seven times the transport number of cobalt ion.
  • the acid exudate whose Li ion concentration has been reduced by dialysis is collected from the acid exudate outlet 10.
  • the recovered liquid may be further subjected to an acid retardation treatment in the acid metal separation tank 1 (FIG. 2) to separate it into Li and transition metal.
  • the recovered liquid in which the high concentration Li ions and the low concentration transition metal ions are dissolved is introduced into the acid metal separation tank 1 (FIG. 2) through the recovered liquid outlet 12 from which the recovered liquid flows out, and is subjected to acid retardation treatment.
  • Li ions and transition metal ions are separated.
  • pressure dialysis is used.
  • other methods such as electrodialysis can be used regardless of the driving force (driving source) regardless of the pressure.
  • Li, Co, and acid can be separated and recovered from the positive electrode material by using the dialysis treatment and the acid retardation treatment in combination.
  • disassembly of the battery, removal of the positive electrode material, and acid leaching of the positive electrode material were performed in the same manner as in Example 1.
  • Li, Co, and acid are separated using the acid retardation principle after selectively or non-selectively leaching Li from the positive electrode active material using a mixed solution of sulfuric acid and hydrogen peroxide. .
  • Acid retardation separates Li and the transition metal by the Donnan film effect.
  • dialysis treatment was performed using a dialysis apparatus (FIG. 6) in which an ion exchange membrane was installed.
  • Dialysis recovers Li with high purity by allowing Li to selectively permeate through the ion exchange membrane. Li can be recovered with high purity by the two actions of dialysis and acid retardation.
  • FIG. 6 shows a schematic structure of the dialysis tank 8 used in the valuable metal recovery apparatus in this example.
  • the dialysis tank is the same as in Example 3. From the acid exudate inlet 9, the recovered liquid subjected to acid retardation treatment is allowed to flow. As the target recovery liquid, even if the recovery liquid in the first recovery container 5 containing a large amount of transition metal or the recovery liquid in the second recovery container 6 containing a large amount of Li contains Li and transition metal, either will do.
  • the acid exudate in which the Li ion concentration is reduced by dialysis (concentration ratio of transition metal ions is increased) is recovered from the acid exudate outlet 10.
  • the recovered liquid in which Li ions are dissolved is recovered from the recovered liquid outlet 12. This recovered liquid has a higher concentration ratio of Li ions to transition metal ions than the recovered liquid immediately after the acid retardation treatment, and Li is easily recovered.
  • Li, Co, and acid can be separated and recovered with high purity from the positive electrode material by using the dialysis treatment and the acid retardation treatment in combination.
  • SYMBOLS 1 Acid metal separation tank, 2 ... Acid exudate tank, 3a-3f ... Solution path

Landscapes

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

Abstract

L'invention concerne un procédé de récupération de métaux de valeur permettant de récupérer des métaux de batteries lithium-ion sans utiliser d'étapes incommodes et à l'aide d'un appareillage relativement simple. Un matériau d'électrode positive contenant un oxyde composite de lithium/métal de transition est dissous dans une solution acide; la solution acide résultante contenant des ions lithium et des ions de métal de transition est amenée à traverser une résine échangeuse d'anions basique; et les ions métalliques sont séparés par collecte d'une solution éluée de la résine échangeuse d'anions sur une période initiale (D) dans un premier récipient, ladite solution ayant une concentration relative élevée en ions de métal de transition, et par collecte d'une solution éluée sur une période ultérieure (E) dans un deuxième récipient, ladite solution ayant une concentration relative élevée en ions lithium.
PCT/JP2011/003849 2010-08-27 2011-07-06 Procédé de récupération de métal et dispositif de récupération de métal Ceased WO2012026061A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010190252A JP5568414B2 (ja) 2010-08-27 2010-08-27 金属回収方法及び金属回収装置
JP2010-190252 2010-08-27

Publications (1)

Publication Number Publication Date
WO2012026061A1 true WO2012026061A1 (fr) 2012-03-01

Family

ID=45723085

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/003849 Ceased WO2012026061A1 (fr) 2010-08-27 2011-07-06 Procédé de récupération de métal et dispositif de récupération de métal

Country Status (2)

Country Link
JP (1) JP5568414B2 (fr)
WO (1) WO2012026061A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103834809A (zh) * 2012-11-27 2014-06-04 欣兴电子股份有限公司 金属污泥的处理方法
EP2975686A1 (fr) * 2014-07-15 2016-01-20 Lars Walch GmbH & Co. KG Procédé de recyclage
WO2021047352A1 (fr) * 2019-09-14 2021-03-18 湖南金源新材料股份有限公司 Procédés de séparation de manganèse-lithium et de préparation de liquide de pré-extraction lors de la récupération complète de déchets de batterie ternaire, et procédé de récupération complète d'éléments de cobalt-nickel-manganèse-lithium dans des déchets de batterie ternaire
CN115970653A (zh) * 2022-12-05 2023-04-18 西安建筑科技大学 一种锂离子电池浸出液净化除杂树脂的制备及其除杂方法
WO2023074442A1 (fr) * 2021-10-28 2023-05-04 住友金属鉱山株式会社 Procédé de production d'une solution contenant du lithium et procédé de production d'hydroxyde de lithium
US20230304128A1 (en) * 2022-02-23 2023-09-28 Green Li-Ion Pte. Ltd. Processes and systems for purifying and recycling lithium-ion battery waste streams
US11876196B2 (en) 2020-08-24 2024-01-16 Green Li-Ion Pte. Ltd. Process for removing impurities in the recycling of lithium-ion batteries
US12024755B2 (en) 2022-04-18 2024-07-02 Green Li-Ion Pte. Ltd. Process and system for recovering lithium from lithium-ion batteries
US12051788B2 (en) 2022-01-17 2024-07-30 Green Li-Ion Pte. Ltd. Process for recycling lithium iron phosphate batteries
US12322770B2 (en) 2023-08-23 2025-06-03 Green Li-Ion Pte. Ltd. Processes and systems for purifying independent streams of manganese, nickel, and cobalt from lithium-ion battery waste streams

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103496801B (zh) * 2013-09-11 2017-10-03 洛阳鼎力环保科技有限公司 一种电解锰含铬废水处理及回收六价铬的方法
JP6652454B2 (ja) * 2016-06-24 2020-02-26 株式会社東芝 金属の回収方法および金属の回収装置
WO2019028174A2 (fr) 2017-08-02 2019-02-07 Lilac Solutions, Inc. Système d'échange d'ions pour extraction de lithium
KR102667270B1 (ko) * 2018-02-17 2024-05-17 리락 솔루션즈, 인크. 리튬 추출 및 전환을 위한 통합 시스템
KR102716644B1 (ko) * 2018-10-15 2024-10-14 주식회사 엘지에너지솔루션 양극재 분석 방법
EP3987069A4 (fr) * 2019-06-21 2023-07-12 Xerion Advanced Battery Corp. Procédés d'extraction de lithium à partir de spodumène
KR20220119166A (ko) * 2020-01-09 2022-08-26 리락 솔루션즈, 인크. 바람직하지 않은 금속의 분리 방법
JP7498991B2 (ja) * 2021-09-22 2024-06-13 株式会社アサカ理研 塩素ガスの処理方法
EP4499260A1 (fr) 2022-03-28 2025-02-05 Lilac Solutions, Inc. Dispositifs pour une utilisation efficace de sorbant dans l'extraction de lithium
CN114717414A (zh) * 2022-05-20 2022-07-08 宁波互邦新材料有限公司 一种用于电池的硫酸锰的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1154159A (ja) * 1997-06-04 1999-02-26 Japan Energy Corp 電池正極廃材からコバルト、ニッケルもしくはマンガンおよびリチウムを回収および再生する方法ならびに電池正極材原料
JP2002167628A (ja) * 2000-11-28 2002-06-11 National Institute Of Advanced Industrial & Technology リチウム回収装置および方法
JP2007122885A (ja) * 2005-10-25 2007-05-17 Sumitomo Metal Mining Co Ltd リチウムイオン電池からの有価金属回収方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IL83251A0 (en) * 1986-08-13 1987-12-31 Advanced Separation Tech Process for the separation of acids and their corresponding metal salts
US5547579A (en) * 1995-01-20 1996-08-20 Eco-Tec Limited Process and apparatus for purification of contaminated acids

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1154159A (ja) * 1997-06-04 1999-02-26 Japan Energy Corp 電池正極廃材からコバルト、ニッケルもしくはマンガンおよびリチウムを回収および再生する方法ならびに電池正極材原料
JP2002167628A (ja) * 2000-11-28 2002-06-11 National Institute Of Advanced Industrial & Technology リチウム回収装置および方法
JP2007122885A (ja) * 2005-10-25 2007-05-17 Sumitomo Metal Mining Co Ltd リチウムイオン電池からの有価金属回収方法

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103834809A (zh) * 2012-11-27 2014-06-04 欣兴电子股份有限公司 金属污泥的处理方法
CN103834809B (zh) * 2012-11-27 2016-01-20 欣兴电子股份有限公司 金属污泥的处理方法
EP2975686A1 (fr) * 2014-07-15 2016-01-20 Lars Walch GmbH & Co. KG Procédé de recyclage
WO2021047352A1 (fr) * 2019-09-14 2021-03-18 湖南金源新材料股份有限公司 Procédés de séparation de manganèse-lithium et de préparation de liquide de pré-extraction lors de la récupération complète de déchets de batterie ternaire, et procédé de récupération complète d'éléments de cobalt-nickel-manganèse-lithium dans des déchets de batterie ternaire
US12218322B2 (en) 2019-09-14 2025-02-04 Hunan Jin Yuan New Materials Joint Stock Company Limited Manganese-lithium separation process and pre-extraction solution preparation process in comprehensive recovery of ternary battery wastes, and method for comprehensive recovery of cobalt, nickel, manganese and lithium elements from ternary battery wastes
US11876196B2 (en) 2020-08-24 2024-01-16 Green Li-Ion Pte. Ltd. Process for removing impurities in the recycling of lithium-ion batteries
US12218325B2 (en) 2020-08-24 2025-02-04 Green Li-Ion Pte. Ltd. Process for removing impurities in the recycling of lithium-ion batteries
JP2023066149A (ja) * 2021-10-28 2023-05-15 住友金属鉱山株式会社 リチウム含有溶液の製造方法および水酸化リチウムの製造方法
WO2023074442A1 (fr) * 2021-10-28 2023-05-04 住友金属鉱山株式会社 Procédé de production d'une solution contenant du lithium et procédé de production d'hydroxyde de lithium
JP7698239B2 (ja) 2021-10-28 2025-06-25 住友金属鉱山株式会社 リチウム含有溶液の製造方法および水酸化リチウムの製造方法
US12051788B2 (en) 2022-01-17 2024-07-30 Green Li-Ion Pte. Ltd. Process for recycling lithium iron phosphate batteries
US20230304128A1 (en) * 2022-02-23 2023-09-28 Green Li-Ion Pte. Ltd. Processes and systems for purifying and recycling lithium-ion battery waste streams
US12297520B2 (en) * 2022-02-23 2025-05-13 Green Li-Ion Pte. Ltd. Processes and systems for purifying and recycling lithium-ion battery waste streams
US12024755B2 (en) 2022-04-18 2024-07-02 Green Li-Ion Pte. Ltd. Process and system for recovering lithium from lithium-ion batteries
CN115970653A (zh) * 2022-12-05 2023-04-18 西安建筑科技大学 一种锂离子电池浸出液净化除杂树脂的制备及其除杂方法
US12322770B2 (en) 2023-08-23 2025-06-03 Green Li-Ion Pte. Ltd. Processes and systems for purifying independent streams of manganese, nickel, and cobalt from lithium-ion battery waste streams
US12322771B2 (en) 2023-08-23 2025-06-03 Green Li-Ion Pte. Ltd. Adaptable processes and systems for purifying co-precipitated or independent streams of manganese, nickel, and cobalt from lithium-ion battery waste streams

Also Published As

Publication number Publication date
JP5568414B2 (ja) 2014-08-06
JP2012046794A (ja) 2012-03-08

Similar Documents

Publication Publication Date Title
JP5568414B2 (ja) 金属回収方法及び金属回収装置
JP5501180B2 (ja) リチウム抽出方法及び金属回収方法
JP5422495B2 (ja) 金属回収方法及び透析装置
JP5618913B2 (ja) 滲出液および金属回収方法
JP2013001951A (ja) 透析促進剤および金属回収方法
Xu et al. Lithium extraction from high Mg/Li brine via electrochemical intercalation/de-intercalation system using LiMn2O4 materials
Wang et al. Recovery of lithium, nickel, and cobalt from spent lithium-ion battery powders by selective ammonia leaching and an adsorption separation system
Xiong et al. Olivine-FePO4 preparation for lithium extraction from brines via Electrochemical De-intercalation/Intercalation method
CN110783658B (zh) 一种退役动力三元锂电池回收示范工艺方法
KR101047986B1 (ko) Ｃｃｄ 공정을 이용한 리튬 이온의 흡착/탈착 장치 및 그 방법
CN109256597B (zh) 一种从废旧钴酸锂电池中回收锂和钴的方法及系统
KR20230111606A (ko) 리튬 인산철 배터리 재활용 공정
JP2013095951A (ja) リチウム回収方法
CN109355502B (zh) 一种从酸性体系中萃取锂离子的方法
JP6400014B2 (ja) 使用済みガルバニ電池のリチウムマンガン酸化物含有部分からの、湿式冶金法によるリチウムの回収方法
JP2013001950A (ja) 透析促進剤および金属回収方法
Wang et al. Direct lithium extraction using intercalation materials
WO2020038383A1 (fr) Procédé et dispositif de purification d'une solution électrolytique d'une batterie à flux
CN110643831A (zh) 一种无隔膜电化学提锂系统及其提锂方法
US20180273866A1 (en) Novel process for removal of nitrogen from natural gas
WO2023175157A1 (fr) Procédé de transformation de masse noire en produits chimiques de batterie
KR20240165990A (ko) 리튬 이온 배터리들로부터 금속을 회수하기 위한 개선된 시스템 및 방법
JP6080070B2 (ja) レアメタルの回収方法及び回収装置
Liu et al. Production of LiOH from spent LiFePO4 using selective electrodialysis with bipolar membrane
CN105036089A (zh) 有色金属冶炼烟气硫酸制酸系统的废稀硫酸回收装置及其回收方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11819538

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11819538

Country of ref document: EP

Kind code of ref document: A1