WO2012164976A1 - 有価金属回収方法 - Google Patents
有価金属回収方法 Download PDFInfo
- Publication number
- WO2012164976A1 WO2012164976A1 PCT/JP2012/053475 JP2012053475W WO2012164976A1 WO 2012164976 A1 WO2012164976 A1 WO 2012164976A1 JP 2012053475 W JP2012053475 W JP 2012053475W WO 2012164976 A1 WO2012164976 A1 WO 2012164976A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxidation
- roasting
- battery
- waste battery
- melting
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 128
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 54
- 239000002184 metal Substances 0.000 title claims abstract description 53
- 150000002739 metals Chemical class 0.000 title claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 158
- 230000003647 oxidation Effects 0.000 claims abstract description 157
- 239000010926 waste battery Substances 0.000 claims abstract description 69
- 239000002893 slag Substances 0.000 claims abstract description 24
- 229920003023 plastic Polymers 0.000 claims abstract description 20
- 239000004033 plastic Substances 0.000 claims abstract description 20
- 238000002844 melting Methods 0.000 claims description 36
- 230000008018 melting Effects 0.000 claims description 36
- 238000011084 recovery Methods 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 229910001092 metal group alloy Inorganic materials 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 37
- 229910052799 carbon Inorganic materials 0.000 abstract description 36
- 229910045601 alloy Inorganic materials 0.000 abstract description 32
- 239000000956 alloy Substances 0.000 abstract description 32
- 238000000926 separation method Methods 0.000 abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 38
- 102100029860 Suppressor of tumorigenicity 20 protein Human genes 0.000 description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000010941 cobalt Substances 0.000 description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 229910017052 cobalt Inorganic materials 0.000 description 17
- 229910052742 iron Inorganic materials 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 238000010309 melting process Methods 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- 101000585359 Homo sapiens Suppressor of tumorigenicity 20 protein Proteins 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 238000010923 batch production Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229940038504 oxygen 100 % Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- 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
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting processes
- C22B1/04—Blast roasting
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/02—Obtaining nickel or cobalt by 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
- C22B7/001—Dry processes
-
- 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
-
- 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 method for recovering valuable metals contained in used batteries, for example, waste batteries such as lithium ion batteries.
- waste batteries such as lithium ion batteries
- recover valuable metals contained in them are roughly divided into dry methods and wet methods. is there.
- crushed waste batteries are melted, and valuable metals to be recovered and other metals with low added value are separated and recovered using the difference in oxygen affinity between them. . That is, an element with low added value such as iron is oxidized as much as possible to obtain slag, and valuable materials such as cobalt are collected as an alloy while suppressing oxidation as much as possible.
- Patent Document 1 discloses a method capable of recovering about 80% of valuable metals such as nickel and cobalt by using a high-temperature heating furnace, adding flux to a waste battery, and repeatedly treating slag. Yes.
- the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a valuable metal recovery method capable of stably increasing the recovery rate in recovering valuable metals from waste batteries by a dry method. There is to do.
- the present inventors Prior to the process of recovering valuable metals, the present inventors have provided a pretreatment step for pre-baking the waste battery at a relatively low temperature within a predetermined range, so that the plastic of the battery pack is prior to the oxidation step. It is possible to recover valuable metals more efficiently than before by removing organic carbon that hinders the stability of the oxidation process, such as plastic components derived from the case, and reducing the carbon content in the melt.
- the headline and the present invention were completed. More specifically, the present invention provides the following.
- a method for recovering valuable metals from a waste battery wherein the waste battery is roasted at a temperature of 300 ° C. or higher and lower than 600 ° C., and the waste battery roasted by the roasting step is 1100 ° C. or higher.
- a valuable process comprising: an oxidation process in which baking is performed at 1200 ° C. or less to perform an oxidation process; and a waste process after the oxidation process is melted to separate and recover a slag and an alloy of valuable metals Metal recovery method.
- the roasting step and the oxidation step are performed in the single heating furnace by dividing the inside of the single heating furnace into a plurality of zones and heating to different temperatures in each zone ( The valuable metal recovery method according to 1) or (2).
- FIG. 1 is a flowchart showing an example of a valuable metal recovery method from a waste battery.
- the waste battery is a lithium ion battery pack accompanied by a plastic case
- the present invention is not limited to this.
- this valuable metal recovery method includes a roasting process ST10, an oxidation process ST20, a dry process S20, and a wet process S30.
- the valuable metal recovery method in the present embodiment is a total process in which an alloy is obtained in the dry process S20, and then the valuable metal element is separated and recovered in the wet process S30.
- the waste battery in the present invention means not only a used battery but also a defective product in the process.
- what is necessary is just to include a waste battery in the process target, and adding other metals, resin, etc. other than a waste battery suitably is not excluded. In that case, it is a waste battery of the present invention including other metals and resins.
- roasting step ST10 is a pretreatment step performed prior to each of the other steps in the valuable metal recovery method, and is included in a plastic case or the like by roasting the waste battery at a temperature of 300 ° C. to 600 ° C. This process reduces organic carbon. For this reason, from the viewpoint that carbides are not easily left, roasting is preferably oxidative roasting using a gas containing air or oxygen, but does not exclude roasting in a reducing atmosphere such as a nitrogen atmosphere. .
- roasting time is not specifically limited, It is preferable to adjust so that carbon derived from organic matter after roasting step ST10 may be 10% by mass or less with respect to carbon derived from organic matter before roasting step ST10. Thereby, the variation in the oxidation degree in the subsequent oxidation step can be suppressed.
- the carbon derived from an organic substance as used herein refers to a plastic component derived from a plastic case of a battery pack, a resin such as a polyolefin derived from a diaphragm, and an organic derived from an electrolyte among all organic carbon contained in a waste battery.
- organic electrolytic solution in which a lithium salt is dissolved in a solvent is included, but carbon that is a negative electrode active material of the battery is not included.
- carbon derived from an organic substance refers to the carbon described above.
- the roasting temperature in the roasting step ST10 is less than 300 ° C., it does not reach the thermal decomposition temperature of a normal olefin resin, vinyl chloride resin, etc., so the plastic component having a melting point of about 250 ° C. is still melted and oxidized. It is brought into process ST20.
- the variation in the components and weight of each product of the battery pack is greater than the variation in the battery body, and the carbon content in the battery pack is brought into the oxidation process.
- the oxidation conditions required in the oxidation process are greatly changed, and it becomes difficult to control the degree of oxidation.
- the baking temperature in baking process ST10 is 300 degreeC or more required for the thermal decomposition of a plastic component.
- the reaction temperature rapidly rises due to the combustion heat of plastic or the like.
- an aluminum foil which is a battery constituent material and has a melting point of about 660 ° C. is melted into a massive metal. Since it deforms, the reaction efficiency in the subsequent oxidation step is adversely affected, making appropriate oxidation control difficult. Further, there is an increased risk that the battery ruptures due to rapid gasification of the liquid organic substance inside the battery, such as the organic electrolyte solution constituting the electrolyte, and the contents are ejected and cannot be recovered. For this reason, it is preferable that the baking temperature in baking process ST10 is 600 degrees C or less.
- the roasting step ST10 is performed at a limited low temperature range, that is, a roasting temperature in the range of 300 ° C. to 600 ° C., thereby heating other components in the waste battery at a high temperature.
- Organic carbon derived from an outer plastic case or the like can be efficiently removed while avoiding various risks caused by the risk.
- the carbon contained in the waste battery it is as described above that the removal of the plastic derived from the battery pack is particularly effective in strictly controlling the degree of oxidation, but the carbon removed by the roasting process is It is not necessarily limited to this. It is possible to remove the polymer membrane, which is a component of the battery, in the roasting step of the present invention, and the method for recovering valuable metals including the roasting step for the purpose of performing such treatment is also included in the present invention. Range.
- the roasting temperature in the range of 300 ° C to 600 ° C in the roasting step ST10 enables slow thermal decomposition of the organic electrolyte that constitutes the electrolyte, and prevents the explosion of the waste battery due to the rapid expansion of the liquid. Even if it explodes, it can be stopped at a small burst, and the risk of the contents being ejected and uncollectable can be reduced. This eliminates the need for a separate pretreatment such as drilling prior to the entire process, and increases productivity.
- a heating furnace capable of roasting waste batteries in the above temperature range can be used without any particular limitation, and as an example, a kiln can be used.
- a kiln can be used since the rotary kiln conventionally used for cement manufacture etc. can be used suitably, the details of the embodiment of the present invention are explained below using the rotary kiln as a representative example of the kiln, but the kiln in the present invention is Not limited to this.
- the kiln includes all types of kilns such as a tunnel kiln (Haas Furness) that can roast waste batteries at a predetermined temperature in the roasting step ST10.
- the roasting step ST10 is performed by using the kiln 1 shown in FIG. 2 as a roasting furnace.
- the kiln body 10 is a cylindrical rotary kiln made of carbon steel having a thickness of 15 to 30 mm. The interior is lined with refractory bricks.
- a drive gear 11 is provided outside the kiln body 10 to transmit the rotational force to the kiln body.
- a burner pipe 12 for blowing hot air for heating the inside is provided in the kiln main body.
- the kiln body 10 provided with these is installed so as to have an inclination of 3 to 4% with respect to the horizontal plane in use.
- the temperature inside the kiln main body 10 is heated to 300 ° C. to 600 ° C. with hot air blown from the burner pipe 12.
- the waste battery is carried in from the carry-in port 13 in the A direction. The waste battery moves in the kiln body 10 toward the discharge port 14 while being stirred and roasted along the inclination of the kiln body 10.
- the waste battery that has undergone the above process is discharged from the discharge port 14 in the B direction.
- most of the plastics and the like are vaporized by thermal decomposition, and the remainder becomes carbide.
- most of this carbide is also physically removed from the waste battery and removed along with the rotational vibration in the kiln.
- the roasting step ST10 and the subsequent oxidation step ST20 can be performed continuously in the same furnace.
- the waste battery is removed from the kiln 1 after the end of the roasting step ST10.
- the oxidation step ST20 is continuously performed on the waste battery in the kiln 1.
- the waste battery subjected to the roasting process in the roasting process ST10 is subjected to an oxidation process by supplying oxygen while roasting at a temperature of 1100 ° C. or higher and 1200 ° C. or lower.
- the oxidation treatment is performed in the melting step in the dry process.
- the oxidation step ST20 is provided before the melting step ST21, and the oxidation treatment is performed in advance. It is characterized by doing.
- This oxidation treatment is performed before the melting step ST21 in the dry step S20, and is performed in the oxidation furnace by providing an oxidation furnace separately from the melting furnace for performing the melting step ST21.
- iron accounts for approximately 20%
- cobalt accounts for approximately 20%
- carbon accounts for 25%
- aluminum accounts for approximately 5%.
- Oxidation is performed with the oxidation state corresponding to the obtained state as the optimum oxidation degree.
- the oxidation degree of iron is small, it is not preferable because much iron that should be distributed to the slag side remains in the alloy recovered after melting.
- the oxidation treatment time required for obtaining the optimum degree of oxidation described above is undesirably long. For example, if the oxidation treatment is performed in a pure oxygen atmosphere at a temperature slightly exceeding 1100 ° C., the necessary oxidation treatment is completed in about 1 hour, but if the oxidation treatment is performed in the same atmosphere at 900 ° C., the oxidation treatment time is 4 hours or more. Necessary.
- the roasting temperature in oxidation process ST20 is 1100 degreeC or more and 1200 degrees C or less.
- the oxidation treatment time in the oxidation step is qualitatively higher in oxygen concentration, and the higher the oxidation temperature, the shorter the time required to obtain the optimum degree of oxidation. For example, if the oxidation time is set to about 1 hour, 1100 ° C. or higher is required in an oxygen 100% atmosphere, and approximately 1200 ° C. is required in an air atmosphere. Since the target oxidation time varies depending on the allowable amount of capital investment and the required processing capacity, the oxygen concentration in the atmosphere and the oxidation temperature may be controlled accordingly.
- a heating furnace capable of performing oxidation treatment inside the waste battery by supplying oxygen while roasting the waste battery in the above temperature range can be used without any particular limitation.
- a kiln represented by a rotary kiln can be preferably used.
- the oxidation step ST20 is performed by using the kiln 1 shown in FIG. 2 as an oxidation furnace.
- the temperature inside the kiln main body 10 is heated to 1100 to 1200 ° C. with hot air blown from the burner pipe 12.
- the waste battery is carried in from the carry-in port 13 in the A direction. The waste battery moves in the kiln body 10 toward the discharge port 14 while being stirred and roasted along the inclination of the kiln body 10.
- an oxidant such as air is added to the kiln body 10.
- aluminum foil is used as a positive electrode material for lithium ion batteries.
- Carbon is used as the negative electrode material.
- the outer shell of the battery is made of iron or aluminum. These materials basically act as a reducing agent. For this reason, the total reaction for converting these materials into gas or slag is an oxidation reaction. Therefore, it is necessary to introduce oxygen into the kiln body 10. This is why air is introduced in the oxidation step ST20.
- the oxidizing agent is not particularly limited, but from the viewpoint of easy handling, a gas containing oxygen such as air, pure oxygen, and oxygen-enriched gas is preferably used. These are fed directly into the kiln body 10 in the oxidation step ST20.
- the introduction amount of the oxidizing agent is approximately 1.2 times the chemical equivalent required for the oxidation of each substance to be oxidized.
- the waste battery oxidized through the above process is discharged from the discharge port 14 in the B direction.
- the exhaust gas generated during the oxidation process is discharged in the C direction.
- the main elements constituting the material of the waste battery are generally oxidized in the order of aluminum> lithium> carbon> manganese> phosphorous> iron> cobalt> nickel> copper due to the difference in affinity with oxygen. That is, aluminum is most easily oxidized and copper is most hardly oxidized.
- nickel, and copper which have a relatively low affinity with oxygen, in the oxidation step ST20, while increasing the iron oxidation degree with respect to iron and cobalt that are close to each other in the affinity with oxygen, At the same time, it is required to strictly adjust the degree of oxidation to suppress cobalt oxidation.
- the oxidation process ST20 in the present invention is an oxidation process at a lower temperature than the oxidation process in the melting process ST21, the reaction rate is relatively slow, and the cylindrical kiln main body 10
- the waste battery moving in the kiln main body 10 is oxidized, so that the oxidation can be easily controlled by adjusting the amount of oxygen, the oxidation time, and the temperature. is there.
- the plastic component has been removed to a certain amount in the preceding roasting step ST10, which is different from the case where the oxidation treatment is performed in the melting step in the dry process. Therefore, the oxidation can be easily controlled.
- this oxidation step ST20 the oxidation treatment is performed to such an extent that the remaining carbon is almost entirely oxidized. Thereby, the dispersion
- the roasting step ST10 and the oxidation step ST20 have the above-mentioned effects by sequentially performing them in separate furnaces prepared for the respective steps. Can also be carried out continuously in a single furnace. For example, by providing a temperature zone of 300 ° C. to 600 ° C. and a temperature zone of 1100 ° C. to 1200 ° C. in the same heating furnace such as a kiln (not shown), the roasting process ST10 and the oxidation process ST20 are simply performed. It can carry out continuously in one heating furnace.
- both processes can be performed continuously as a batch process in a single heating furnace.
- ⁇ Dry process S20> In the dry process S20, a melting process ST21 is performed in which the waste battery that has been oxidized in the oxidation process ST20 is melted at about 1500 ° C. Melting process ST21 can be performed with a conventionally known electric furnace or the like.
- the oxidation process is performed in advance in the oxidation process ST20, it is not necessary to perform the oxidation process on the waste battery melted in the dry process as in the prior art.
- an additional oxidation step for performing additional oxidation treatment for a very short time can be provided in the melting step ST21.
- This additional oxidation step makes it possible to control the degree of oxidation more finely.
- the additional oxidation process can be performed in a very short time compared to the conventional oxidation process at the time of melting, so there is little adverse effect on work efficiency and less lance consumption, resulting in a problem of cost increase. Hateful.
- SiO 2 silicon dioxide
- CaO limestone
- slag which is an oxide such as iron or aluminum, and alloys of nickel, cobalt, and copper, which are valuable metals, are generated. Since they have different specific gravities, they are recovered by slag separation ST22 and alloy separation ST23, respectively. At this time, if the content of aluminum oxide in the slag is relatively large, a slag having a high melting point and a high viscosity is obtained. However, as described above, SiO 2 and CaO are added to lower the melting point of the slag in the melting step ST21. Therefore, the viscosity can be reduced by lowering the melting point of the slag. For this reason, slag separation ST22 can be performed efficiently. Note that dust, exhaust gas, and the like in the melting step ST21 are detoxified in a conventionally known exhaust gas treatment ST24.
- a dephosphorization step ST25 is further performed on the obtained alloy.
- ethylene carbonate, diethyl carbonate, or the like is used as an organic solvent, and LiPF 6 (lithium hexafluorophosphate) or the like is used as an electrolyte as an electrolyte.
- LiPF 6 lithium hexafluorophosphate
- electrolyte electrolyte
- phosphorus in this LiPF 6 has the property of being relatively easily oxidized, it has a property of relatively high affinity with iron group elements such as iron, cobalt and nickel.
- Phosphorus in the alloy is difficult to remove in the subsequent wet process of recovering each element as a metal from the alloy obtained by the dry process, and accumulates as impurities in the processing system, so that the operation cannot be continued. For this reason, it is removed in this dephosphorization step ST25.
- phosphorus in the alloy can be oxidized and absorbed in CaO by adding lime or the like that generates CaO by reaction and blowing in an oxygen-containing gas such as air.
- the alloy obtained in this way is composed of cobalt, nickel derived from the positive electrode material, lithium derived from the electrolyte, copper derived from the conductive material of the negative electrode, and the like.
- the dry process and the wet process by obtaining an alloy with few impurities by making the dry process a broad pretreatment and also greatly reducing the amount of processing to be put into the wet process.
- the wet process is basically a complicated process that is not suitable for mass processing, it is necessary to perform the processing time of the wet process, in particular, the dissolution process ST31 in a short time in order to combine with the dry process.
- the melting time can be shortened by granulating the alloy.
- the average surface area in terms of the surface area is 300 mm 2 from 1 mm 2, it is preferable from 0.4mg Speaking in average weight in the range of 2.2 g. If it is less than the lower limit of this range, it is not preferable because the particles are too fine and difficult to handle, and further, the reaction is too early and it becomes difficult to dissolve at once due to excessive heat generation. If the upper limit is exceeded, the dissolution rate in the subsequent wet process decreases, which is not preferable.
- a method of granulating the alloy by shot a conventionally known method of quenching by inflow of molten metal into flowing water can be used.
- the wet process can use a conventionally known method and is not particularly limited.
- a conventionally known method for example, in the case of an alloy composed of cobalt, nickel, copper, and iron when the waste battery is a lithium ion battery, after acid dissolution (dissolution step ST31), iron removal, copper separation recovery, nickel / cobalt separation, Valuable metal elements can be recovered through the element separation step ST32 in the procedures of nickel recovery and cobalt recovery.
- the oxidation process was performed in a state where the waste battery was melted in the dry process, so in order to appropriately adjust the degree of oxidation in the oxidation process,
- the melting process was required to be a batch process in which the next process was started again from the beginning after the oxidation process of all the waste batteries simultaneously processed in the furnace was completed.
- the waste battery that has been subjected to the oxidation treatment in advance in the oxidation step ST20 can be continuously treated in the dry process by continuously putting it into the melting furnace. A large amount of processing is possible.
- the present invention can be suitably used when it is at least 1 t or more per day, preferably 10 t or more per day.
- the type of waste battery is not particularly limited, but a rare metal such as cobalt or lithium can be recovered, and its use has been expanded to automobile batteries, etc., and a lithium ion battery that requires a large-scale recovery process is the present invention. It can illustrate preferably as a process target.
- a roasting step and an oxidation step were provided prior to the melting step, and then a melting step was provided to perform the melting treatment.
- Sample A battery pack (18650 type) having a size of 10 cm in width, 20 cm in length, and 2 cm in thickness, in which six lithium ion cells having a diameter of 18 mm and a length of 65 mm are stored. Of these, the total carbon amount was about 100 g (carbon as negative electrode active material: 56 g, carbon derived from other organic substances: 44 g).
- Roasting step The sample was put into a vertical furnace heated to 500 ° C. and roasted for 30 minutes.
- the waste battery and the ashed battery pack after the baking were taken out and arranged in a magnesia dish.
- the total carbon amount is about 60 g (carbon as negative electrode active material: 56 g, carbon derived from other organic matter: 4 g), and the total carbon amount is 60% of the initial amount (about carbon derived from other organic matter). It decreased to 9.1% of the initial stage).
- the time of the oxidation process in an oxidation process was 1.5 hours and 2 hours, it confirmed that the non-recoverable element in an alloy phase fell.
- the alloy composition obtained when melting after oxidation for 1 hour is Fe 36% and P 0.08% by weight, but the alloy composition obtained when melting after oxidation for 2 hours Of Fe was 3.2% by weight and P ⁇ 0.01%.
- Comparative Example 1 After the same baking process as in the example was performed on the same sample as in the example, the same melting process as in Example 1 was performed without performing the oxidation process. The contents were not completely melted, and a large amount of powdery residue mixed with unburned carbon powder and unmelted flux was recovered. Therefore, it is understood that an oxidation step is essential when recovering valuable materials from a waste battery at a temperature of about 1500 ° C. which is a preferable temperature range in actual operation.
- Comparative Example 2 the same sample as in the example was subjected to the oxidation step similar to the example without performing the roasting step, and then the melting step. As a result, an unmelted portion remained in the slag after the test, and the presence of carbon was recognized in the unmelted material.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Sustainable Development (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Processing Of Solid Wastes (AREA)
- Secondary Cells (AREA)
Abstract
Description
図1に示すように、この有価金属回収方法は、焙焼工程ST10と、酸化工程ST20と、乾式工程S20と、湿式工程S30とからなる。このように、本実施例における有価金属回収方法は乾式工程S20において合金を得て、その後に湿式工程S30によって有価金属元素を分離回収するトータルプロセスである。なお、本発明における廃電池とは、使用済み電池のみならず、工程内の不良品等も含む意味である。また、処理対象に廃電池を含んでいればよく、廃電池以外のその他の金属や樹脂等を適宜加えることを排除するものではない。その場合にはその他の金属や樹脂を含めて本発明の廃電池である。
まず、本発明の特徴である焙焼工程ST10について説明する。焙焼工程ST10は、有価金属回収方法におけるその他の各工程に先行して行われる前処理工程であり、廃電池を300℃~600℃の温度で焙焼することにより、プラスチックケース等に含まれる有機性炭素を減少させるプロセスである。このため、炭化物が残留され難いという観点から、焙焼は空気や酸素を含む気体による酸化焙焼であることが好ましいが、窒素雰囲気下等の還元性雰囲気での焙焼を排除するものではない。なお、焙焼時間は特に限定されないが、焙焼工程ST10後の有機物由来の炭素が、焙焼工程ST10前の有機物由来の炭素に対して10質量%以下となるように調整することが好ましい。これにより、後の酸化工程における酸化度のバラツキを抑えることができる。尚、ここでいう有機物由来の炭素とは、廃電池に含まれる全ての有機性炭素のうち、電池パックのプラスチックケースに由来するプラスチック成分、隔膜に由来するポリオレフィン等の樹脂、電解質に由来する有機溶媒にリチウム塩を溶解させた有機電解液等を含むが、電池の負極活物質であるカーボンは含まれない。以下、本明細書において有機物由来の炭素という場合、上述した炭素のことをいうものとする。
<酸化工程ST20>
以上説明した実施形態においては、焙焼工程ST10と酸化工程ST20は、それぞれの工程のために用意した別個の炉内で逐次的に行うことにより、上述の効果を奏するものであるが、両工程は、単一の炉内で連続的に行うことも可能である。例えばキルン等の同一の加熱炉内に、300℃~600℃の温度帯と1100℃~1200℃の温度帯を、それぞれ設けることにより(図示せず)、焙焼工程ST10と酸化工程ST20を単一の加熱炉内において連続的に行うことができる。
乾式工程S20においては、酸化工程ST20で酸化処理の行われた廃電池を1500℃付近で熔融する熔融工程ST21を行う。熔融工程ST21は従来公知の電気炉等で行うことができる。
本実施形態においては乾式工程S20の最後に合金を冷却して得る際に、これを粒状物(ショット化合金又は単にショットともいう)として得る。これにより、後の湿式工程S30における溶解工程ST31を短時間で行なうことができる。
廃電池からの有価金属回収プロセスは、特許文献1のように合金として回収したままでは意味がなく、有価金属元素として回収する必要がある。廃電池を乾式工程で予め処理することによって、上記のような有価金属のみの合金とすることで、後の湿式工程を単純化することができる。このとき、この湿式での処理量は投入廃電池の量にくらべて質量比で1/4から1/3程度まで少なくなっていることも湿式工程との組み合わせを有利にする。
従来、乾式工程と湿式工程を組み合わせたトータルプロセスにおいては、乾式工程において、廃電池を熔融した状態で酸化処理を行っていたため、酸化処理における酸化度を適切に調整するために、乾式工程内の熔融工程は、溶炉内で同時に処理する全ての廃電池の酸化処理を終えてから、改めて次の工程を最初から開始するというバッチ処理とする必要があった。本発明の有機金属回収方法によれば、予め酸化工程ST20によって酸化処理を終えた廃電池を連続的に溶融炉に投入することにより、乾式工程において廃電池を連続的に処理できるため、従来より大量の処理が可能である。少なくとも1日あたり1t以上、好ましくは1日あたり10t以上である場合に本発明を好適に使用できる。
試料:直径18mm、長さ65mmのサイズのリチウムイオン単電池6本が格納された幅10cm、長さ20cm、厚み2cmのサイズで重量300gの電池パック(18650タイプ)。このうちの全炭素の炭素量は約100g(負極活物質であるカーボン:56g、その他の有機物由来の炭素:44g)であった。
焙焼工程:試料を500℃に加熱した竪型炉に投入し、30分間焙焼した。30分間の焙焼工程後、焙焼後廃電池及び灰化した電池パックを取り出し、これをマグネシア皿に並べた。このうちの全炭素の炭素量は約60g(負極活物質であるカーボン:56g、その他の有機物由来の炭素:4g)であり、全炭素量は初期の60%(その他の有機物由来の炭素については初期の9.1%)まで減少した。
酸化工程:上記マグネシア皿を再び竪型炉に入れ、窒素雰囲気下において1200℃に加熱した。その後、電池上方より空気を2l/分で噴き付けた状態で1時間保持して酸化処理を行った。1時間後に空気の噴き付けを停止し、窒素を充分に通気して窒素雰囲気として冷却した後、マグネシア皿を竪型炉から取り出した。
熔融工程:酸化工程後の試料に、45gの試薬CaOと45gの試薬SiO2を加え、窒素雰囲気下で1500℃に加熱した。熔融工程においては、追加の酸化工程を設けなくとも内容物は完全に熔融した。
合金分離及びスラグ分離:冷却後にスラグと合金を分離回収して、ICP法により分析した合金中への金属鉄と金属コバルトの分配率(質量%)を測定した。インプット重量に対し、Feは30%、Coは95%が合金として回収された。また、実施例の試験後のスラグは、均一熔融しており、表面には残留カーボンは認められなかった。
ST20 酸化工程
S20 乾式工程
ST21 熔融工程
ST22 スラグ分離
ST23 合金分離
ST24 排ガス処理
ST25 脱リン工程
ST26 合金ショット化工程
S30 湿式工程
ST31 溶解工程
ST32 元素分離工程
1 キルン
10 キルン本体
11 駆動ギヤ
12 バーナーパイプ
13 搬入口
14 排出口
Claims (5)
- 廃電池からの有価金属回収方法であって、
前記廃電池を300℃以上600℃未満の温度で焙焼する焙焼工程と、
前記焙焼工程によって焙焼した廃電池を1100℃以上1200℃以下で焙焼して酸化処理を行う酸化工程と、
前記酸化工程後の廃電池を熔融して、スラグと、有価金属の合金と、を分離して回収する乾式工程と、を備える有価金属回収方法。 - 前記乾式工程中の熔融工程において、追加の酸化処理を行う追加酸化工程を備える請求項1に記載の有価金属回収方法。
- 前記焙焼工程と前記酸化工程とを、単一の加熱炉内の温度を逐次変動させることにより、前記単一の加熱炉内で行う請求項1又は2に記載の有価金属回収方法。
- 前記焙焼工程と前記酸化工程とを、単一の加熱炉内を複数の区域に分けて、該区域ごとに異なる温度に加熱することにより、前記単一の加熱炉内で行う請求項1又は2に記載の有価金属回収方法。
- 前記廃電池はプラスチックケースが付随する電池パックである請求項1から4のいずれかに記載の有価金属回収方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP12792342.3A EP2687614B1 (en) | 2011-06-03 | 2012-02-15 | Method for recovering valuable metals |
US14/112,230 US8992662B2 (en) | 2011-06-03 | 2012-02-15 | Method for recovering valuable metals |
KR1020137025033A KR101410557B1 (ko) | 2011-06-03 | 2012-02-15 | 유가 금속 회수 방법 |
CN201280017953.8A CN103459624B (zh) | 2011-06-03 | 2012-02-15 | 有价金属的回收方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-125211 | 2011-06-03 | ||
JP2011125211A JP5360135B2 (ja) | 2011-06-03 | 2011-06-03 | 有価金属回収方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012164976A1 true WO2012164976A1 (ja) | 2012-12-06 |
Family
ID=47258844
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/053475 WO2012164976A1 (ja) | 2011-06-03 | 2012-02-15 | 有価金属回収方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US8992662B2 (ja) |
EP (1) | EP2687614B1 (ja) |
JP (1) | JP5360135B2 (ja) |
KR (1) | KR101410557B1 (ja) |
CN (1) | CN103459624B (ja) |
WO (1) | WO2012164976A1 (ja) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019135321A (ja) * | 2018-02-05 | 2019-08-15 | 住友金属鉱山株式会社 | 廃リチウムイオン電池からの有価金属の回収方法 |
CN112652807A (zh) * | 2020-12-18 | 2021-04-13 | 中北大学 | 一种利用路易斯酸选择性回收废旧锂离子电池正极材料中锂的方法 |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102014116378B4 (de) | 2014-11-10 | 2016-07-28 | Schott Ag | Verfahren zum Herstellen eines glaskeramischen Ionenleiters |
JP6708468B2 (ja) * | 2015-04-17 | 2020-06-10 | Jx金属株式会社 | リチウムイオン電池の処理方法 |
WO2018100254A1 (fr) * | 2016-11-29 | 2018-06-07 | Eco'ring | Procédé de fusion de piles et accumulateurs portables usagés et installation pour la mise en oeuvre du procédé |
JP6963746B2 (ja) * | 2017-07-26 | 2021-11-10 | 住友金属鉱山株式会社 | スクラップからの有価金属リサイクル方法 |
KR101803859B1 (ko) * | 2017-08-09 | 2017-12-04 | 주식회사 현대특수로 | 배터리 재료 회수용 처리장치 |
JP6589966B2 (ja) * | 2017-11-22 | 2019-10-16 | 住友金属鉱山株式会社 | リチウムイオン電池廃材の処理方法 |
JP7006438B2 (ja) * | 2018-03-26 | 2022-01-24 | 住友金属鉱山株式会社 | 熔融分離装置、廃リチウムイオン電池からのアルミニウムの分離方法、及び廃リチウムイオン電池からの有価物の回収方法 |
JP2019186000A (ja) * | 2018-04-09 | 2019-10-24 | 日本磁力選鉱株式会社 | 二次電池の処理方法 |
CN108754153A (zh) * | 2018-06-26 | 2018-11-06 | 汉能新材料科技有限公司 | 铜铟镓硒废芯片的回收方法及回收系统 |
CN108796227A (zh) * | 2018-07-05 | 2018-11-13 | 汉能新材料科技有限公司 | 铜铟镓硒废芯片的高效回收方法 |
CN112423913B (zh) * | 2018-07-12 | 2023-05-23 | 住友金属矿山株式会社 | 合金粉和合金粉的制造方法 |
CN109193064B (zh) * | 2018-10-31 | 2020-12-04 | 湖南江冶新能源科技股份有限公司 | 一种废旧动力锂电池有价成分分选回收的方法 |
CN113242908A (zh) * | 2018-11-26 | 2021-08-10 | 巴斯夫欧洲公司 | 通过浸出液中注入氢气的电池回收 |
WO2020203937A1 (ja) * | 2019-04-03 | 2020-10-08 | 株式会社神戸製鋼所 | 有価金属の回収方法 |
JP7400589B2 (ja) * | 2020-03-30 | 2023-12-19 | 住友金属鉱山株式会社 | 廃リチウムイオン電池からの有価金属の回収方法 |
JP7359062B2 (ja) * | 2020-03-30 | 2023-10-11 | 住友金属鉱山株式会社 | 廃リチウムイオン電池からの有価金属の回収方法 |
JP7400590B2 (ja) * | 2020-03-30 | 2023-12-19 | 住友金属鉱山株式会社 | 廃リチウムイオン電池からの有価金属の回収方法 |
JP7354903B2 (ja) * | 2020-03-30 | 2023-10-03 | 住友金属鉱山株式会社 | 廃リチウムイオン電池からの有価金属の回収方法 |
JP6958659B2 (ja) * | 2020-04-07 | 2021-11-02 | 住友金属鉱山株式会社 | 有価金属を回収する方法 |
KR102459353B1 (ko) * | 2020-07-14 | 2022-10-28 | 주식회사 에코비트프리텍 | 폐리튬배터리의 폭발이 억제 가능한 건식 방전 장치 |
CN111733328B (zh) * | 2020-07-17 | 2021-04-27 | 中南大学 | 一种回收废旧锂离子电池中有价金属的方法 |
US20240186604A1 (en) * | 2021-03-30 | 2024-06-06 | Jx Nippon Mining & Metals Corporation | Treatment method for battery waste |
WO2022224719A1 (ja) * | 2021-04-23 | 2022-10-27 | 住友金属鉱山株式会社 | 有価金属の製造方法 |
JP7238939B2 (ja) * | 2021-04-23 | 2023-03-14 | 住友金属鉱山株式会社 | 有価金属の製造方法 |
JP7215521B2 (ja) * | 2021-06-15 | 2023-01-31 | 住友金属鉱山株式会社 | 有価金属の製造方法 |
JP7215522B2 (ja) * | 2021-06-15 | 2023-01-31 | 住友金属鉱山株式会社 | 有価金属の製造方法 |
KR102450852B1 (ko) * | 2022-04-29 | 2022-10-07 | (주)에코프로머티리얼즈 | 폐전지 친환경 재활용을 위한 파쇄시스템 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04128324A (ja) * | 1990-09-19 | 1992-04-28 | Mitsui Mining & Smelting Co Ltd | カドミウムの回収方法 |
JPH1060551A (ja) * | 1996-08-06 | 1998-03-03 | Ind Technol Res Inst | ニッケルとカドミウムを含む廃棄物から鉄を分離する方法 |
JPH10330855A (ja) * | 1997-06-02 | 1998-12-15 | Nisso Kinzoku Kagaku Kk | リチウムイオン二次電池からの有価物の回収方法 |
JP2010231925A (ja) * | 2009-03-26 | 2010-10-14 | Nippon Denko Kk | マンガン系リチウムイオン二次電池の有価資源回収方法その装置 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3614242A1 (de) * | 1986-04-26 | 1987-10-29 | Metallgesellschaft Ag | Verfahren zur ausarbeitung von klein-batterien |
DE59510135D1 (de) * | 1994-06-20 | 2002-05-02 | Ct Umwelttechnik Ag Winterthur | Verfahren zur rezyklierung von batterien, insbesondere trockenbatterien |
JPH1088250A (ja) | 1996-09-10 | 1998-04-07 | Sumitomo Metal Mining Co Ltd | 使用済みニッケル水素2次電池からの有価金属の回収方法 |
KR100322038B1 (ko) | 1998-12-24 | 2002-07-31 | 포항종합제철 주식회사 | 플라즈마를이용한폐전지로부터의유가금속회수방법 |
JP4491085B2 (ja) * | 1999-06-01 | 2010-06-30 | 多摩化学工業株式会社 | 二次電池廃材からの正極材回収方法及びこれを用いた非水電解液二次電池の製造方法 |
KR100438473B1 (ko) | 2000-03-24 | 2004-07-03 | 미쓰이 긴조꾸 고교 가부시키가이샤 | 유가금속의 회수방법 |
US7169206B2 (en) | 2004-04-19 | 2007-01-30 | Umicore | Battery recycling |
WO2010085635A2 (en) * | 2009-01-22 | 2010-07-29 | Nu-Iron Technology, Llc | Production of iron from metallurgical waste |
-
2011
- 2011-06-03 JP JP2011125211A patent/JP5360135B2/ja active Active
-
2012
- 2012-02-15 US US14/112,230 patent/US8992662B2/en active Active
- 2012-02-15 WO PCT/JP2012/053475 patent/WO2012164976A1/ja active Application Filing
- 2012-02-15 KR KR1020137025033A patent/KR101410557B1/ko active IP Right Grant
- 2012-02-15 CN CN201280017953.8A patent/CN103459624B/zh active Active
- 2012-02-15 EP EP12792342.3A patent/EP2687614B1/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04128324A (ja) * | 1990-09-19 | 1992-04-28 | Mitsui Mining & Smelting Co Ltd | カドミウムの回収方法 |
JPH1060551A (ja) * | 1996-08-06 | 1998-03-03 | Ind Technol Res Inst | ニッケルとカドミウムを含む廃棄物から鉄を分離する方法 |
JPH10330855A (ja) * | 1997-06-02 | 1998-12-15 | Nisso Kinzoku Kagaku Kk | リチウムイオン二次電池からの有価物の回収方法 |
JP2010231925A (ja) * | 2009-03-26 | 2010-10-14 | Nippon Denko Kk | マンガン系リチウムイオン二次電池の有価資源回収方法その装置 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019135321A (ja) * | 2018-02-05 | 2019-08-15 | 住友金属鉱山株式会社 | 廃リチウムイオン電池からの有価金属の回収方法 |
CN112652807A (zh) * | 2020-12-18 | 2021-04-13 | 中北大学 | 一种利用路易斯酸选择性回收废旧锂离子电池正极材料中锂的方法 |
Also Published As
Publication number | Publication date |
---|---|
KR101410557B1 (ko) | 2014-06-20 |
CN103459624A (zh) | 2013-12-18 |
JP5360135B2 (ja) | 2013-12-04 |
EP2687614B1 (en) | 2015-07-22 |
EP2687614A4 (en) | 2014-05-07 |
JP2012251220A (ja) | 2012-12-20 |
US8992662B2 (en) | 2015-03-31 |
CN103459624B (zh) | 2015-02-25 |
KR20130112069A (ko) | 2013-10-11 |
US20140102256A1 (en) | 2014-04-17 |
EP2687614A1 (en) | 2014-01-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5360135B2 (ja) | 有価金属回収方法 | |
JP5434934B2 (ja) | 有価金属回収方法 | |
KR101501864B1 (ko) | 유가 금속 회수 방법 | |
JP5857572B2 (ja) | 有価金属回収方法 | |
JP5853585B2 (ja) | 有価金属回収方法 | |
EP2703504B1 (en) | Method for recovering valuable metal | |
JP5569457B2 (ja) | 有価金属回収方法 | |
JP5360118B2 (ja) | 有価金属回収方法 | |
JP5625767B2 (ja) | 有価金属回収方法 | |
JP5434935B2 (ja) | 有価金属回収方法 | |
JP7363207B2 (ja) | 有価金属を回収する方法 | |
JP7363206B2 (ja) | 有価金属を回収する方法 | |
WO2023026854A1 (ja) | 電気炉、有価金属の製造方法 | |
WO2024070500A1 (ja) | 有価金属の製造方法 | |
JP2023028122A (ja) | 有価金属の製造方法 | |
JP2021155761A (ja) | 有価金属を回収する方法及びマグネシア耐火物 | |
JP2021155762A (ja) | 有価金属を回収する方法及びマグネシア耐火物 |
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: 12792342 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20137025033 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012792342 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14112230 Country of ref document: US |