WO2022009657A1 - 有価金属を回収する方法 - Google Patents
有価金属を回収する方法 Download PDFInfo
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- WO2022009657A1 WO2022009657A1 PCT/JP2021/023472 JP2021023472W WO2022009657A1 WO 2022009657 A1 WO2022009657 A1 WO 2022009657A1 JP 2021023472 W JP2021023472 W JP 2021023472W WO 2022009657 A1 WO2022009657 A1 WO 2022009657A1
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- WIPO (PCT)
- Prior art keywords
- melt
- partial pressure
- alloy
- oxygen partial
- melting
- Prior art date
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 106
- 239000002184 metal Substances 0.000 title claims abstract description 106
- 238000000034 method Methods 0.000 title claims abstract description 85
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 81
- 239000001301 oxygen Substances 0.000 claims abstract description 81
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000000956 alloy Substances 0.000 claims abstract description 59
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 59
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 150000002739 metals Chemical class 0.000 claims abstract description 53
- 239000000155 melt Substances 0.000 claims abstract description 49
- 238000002844 melting Methods 0.000 claims abstract description 47
- 230000008018 melting Effects 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 47
- 239000002893 slag Substances 0.000 claims abstract description 46
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 37
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011574 phosphorus Substances 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 229910052802 copper Inorganic materials 0.000 claims abstract description 23
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 23
- 238000005259 measurement Methods 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 41
- 239000010949 copper Substances 0.000 claims description 34
- 229910001416 lithium ion Inorganic materials 0.000 claims description 31
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 30
- 239000002699 waste material Substances 0.000 claims description 23
- 229910017052 cobalt Inorganic materials 0.000 claims description 14
- 239000010941 cobalt Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000000463 material Substances 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 30
- 230000003647 oxidation Effects 0.000 description 30
- 238000007254 oxidation reaction Methods 0.000 description 30
- 239000003638 chemical reducing agent Substances 0.000 description 22
- 229910052799 carbon Inorganic materials 0.000 description 21
- 229910052742 iron Inorganic materials 0.000 description 19
- 239000007800 oxidant agent Substances 0.000 description 18
- 238000011084 recovery Methods 0.000 description 18
- 229910052782 aluminium Inorganic materials 0.000 description 16
- 238000000926 separation method Methods 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- 239000010926 waste battery Substances 0.000 description 13
- 239000012535 impurity Substances 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000009853 pyrometallurgy Methods 0.000 description 7
- 238000003723 Smelting Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- 238000010309 melting process Methods 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000005987 sulfurization reaction Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229940043430 calcium compound Drugs 0.000 description 2
- 150000001674 calcium compounds Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000004868 gas analysis Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000002801 charged material Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
Images
Classifications
-
- 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
- B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
-
- 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
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/16—Remelting metals
-
- 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
- B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0002—Preliminary treatment
- C22B15/001—Preliminary treatment with modification of the copper constituent
- C22B15/0013—Preliminary treatment with modification of the copper constituent by roasting
- C22B15/0015—Oxidizing 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0028—Smelting or converting
- C22B15/0052—Reduction smelting or converting
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0026—Pyrometallurgy
- C22B15/0056—Scrap treating
-
- 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
- C22B23/005—Preliminary treatment of ores, e.g. by roasting or by the Krupp-Renn process
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/10—Dry methods smelting of sulfides or formation of mattes by solid carbonaceous reducing agents
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
-
- 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
- C22B5/00—General methods of reducing to metals
- C22B5/02—Dry methods smelting of sulfides or formation of mattes
- C22B5/18—Reducing step-by-step
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B2101/00—Type of solid waste
- B09B2101/15—Electronic waste
- B09B2101/16—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 method for recovering valuable metals.
- a well-known lithium-ion battery has a structure in which a negative electrode material, a positive electrode material, a separator, and an electrolytic solution are enclosed in an outer can.
- the outer can is made of a metal such as iron (Fe) or aluminum (Al).
- the negative electrode material is made of a negative electrode active material (graphite or the like) fixed to a negative electrode current collector (copper foil or the like).
- the positive electrode material is made of a positive electrode active material (lithium nickel oxide, lithium cobalt oxide, etc.) fixed to a positive electrode current collector (aluminum foil, etc.).
- the separator is made of a polypropylene porous resin film or the like.
- the electrolytic solution contains an electrolyte such as lithium hexafluorophosphate (LiPF 6).
- lithium-ion batteries One of the main uses of lithium-ion batteries is hybrid vehicles and electric vehicles. Therefore, it is expected that a large amount of on-board lithium-ion batteries will be discarded in the future according to the life cycle of the automobile. There are also lithium-ion batteries that are discarded as defective products during manufacturing. It is required to reuse such used batteries and defective batteries generated during manufacturing (hereinafter, “waste lithium ion batteries”) as resources.
- Patent Document 1 with respect to a process for separating cobalt from lithium present in the charge containing Li-ion battery or battery scrap, by adjusting the oxygen input to the bus 10 -18 ⁇ 10 -14 atm of
- the upper limit (10-14 atm) eliminates the formation and loss of cobalt oxide in the slag, and the lower limit ( 10-18 atm) oxidizes elements such as aluminum and carbon to the effect that a target oxygen pressure is preferred. It is stated that it is guaranteed (claim 1 and [0018] of Patent Document 1).
- Patent Document 2 regarding a method of recovering a valuable metal from a lithium ion waste battery containing nickel and cobalt, strict adjustment of the degree of oxidation is performed by adjusting the amount of oxygen, the oxidation time and the temperature in the preliminary oxidation step.
- By adjusting the degree of oxidation it is possible to separate almost the entire amount of aluminum oxide as slag in the slag separation step, to perform additional oxidation treatment for a short time in the melting step, and to perform additional oxidation treatment in the melting step. It is described that it is possible to finely adjust the degree of oxidation more finely (claim 1, [0033] and [0036] of Patent Document 2).
- Patent Document 1 Although the mass balance of Cu, Ni, Fe, Co, Al, Si, and Ca is examined (Table 1 of Patent Document 1), a large amount (28%) of iron remains in the alloy. is doing. Moreover, Patent Document 1 does not recognize the problem of phosphorus contamination in alloys. Further, in Patent Document 1, the oxidation level (PO 2 ) is determined by directly analyzing the gas on the melting bath (Patent Document 1 [0022]), but in such a method, the oxygen partial pressure is determined. It is difficult to measure accurately and control this. Therefore, in particular, there is a problem that the uptake of phosphorus into the alloy cannot be prevented. In fact, as a result of investigation by the present inventor, it was found that phosphorus and iron may be mixed in the alloy under the oxygen partial pressure condition of less than 10-14 atm, which is preferable in Patent Document 1.
- Patent Document 2 further provides a dephosphorus step after the melting step and the slag separation step, and phosphorus is separated from the alloy in this dephosphorus step (claim 2). 1 and [0039] to [0046]).
- phosphorus can be removed by such a method, in order to further reduce the production cost, a process that enables removal of phosphorus and iron while eliminating the need for a phosphorus removal step is desirable.
- Patent Document 2 does not disclose the measures required to realize such a process.
- the present inventor conducted a diligent study in view of such circumstances.
- the oxygen partial pressure in the melt is directly measured using an oxygen analyzer, and the oxygen partial pressure is controlled based on the obtained measurement results to strictly control the oxygen partial pressure. It was found that it can be controlled, and thereby the uptake of phosphorus and iron into the alloy can be suppressed while preventing the oxidation of the valuable metal, and as a result, the valuable metal can be recovered more efficiently.
- the present invention has been completed based on such knowledge, and it is possible to strictly control the oxygen partial pressure required for heating and melting the raw materials, thereby recovering valuable metals more efficiently.
- the challenge is to provide a method that can be done.
- the present invention includes the following aspects (1) to (6).
- the expression "-" includes the numerical values at both ends thereof. That is, "X to Y” is synonymous with “X or more and Y or less”.
- a method for recovering valuable metals (Cu, Ni, Co), the following steps; a step of preparing an alloy containing at least phosphorus (P), iron (Fe) and valuable metals as a raw material, and A step of heating and melting the raw material to form a melt and then making the melt into a melt containing an alloy and a slag, and a step of separating the slag from the melt and recovering an alloy containing a valuable metal.
- the valuable metal is composed of at least one metal or alloy selected from the group consisting of copper (Cu), nickel (Ni), cobalt (Co) and combinations thereof. Either way.
- a method capable of strictly controlling the oxygen partial pressure when the raw material is heated and melted, whereby the valuable metal can be recovered more efficiently.
- the present embodiment A specific embodiment of the present invention (hereinafter referred to as "the present embodiment") will be described.
- the present invention is not limited to the following embodiments, and various modifications can be made without changing the gist of the present invention.
- the method for recovering the valuable metal (Cu, Ni, Co) of the present embodiment is as follows: a step of preparing an alloy containing at least phosphorus (P), iron (Fe) and a valuable metal as a raw material (preparation step). ), The prepared raw material is heated and melted to form a melt, and then the melt is made into a melt containing an alloy and slag (melting step), and the slag is separated from the obtained melt. It has a step of recovering an alloy containing a valuable metal (slag separation step). Further, when the raw material is heated and melted, the oxygen partial pressure in the melt is directly measured by using an oxygen analyzer, and the oxygen partial pressure is controlled based on the obtained measurement result.
- This embodiment is a method for recovering valuable metals from a container containing at least phosphorus (P), iron (Fe) and valuable metals.
- the valuable metal is to be recovered and is at least one kind of metal or alloy selected from the group consisting of copper (Cu), nickel (Ni), cobalt (Co) and combinations thereof.
- the present embodiment is mainly a recovery method by a pyrometallurgical process. It may be composed of a dry smelting process and a wet smelting process. The details of each process will be described below.
- a container is prepared and a raw material is obtained.
- the container is to be processed to recover valuable metals, and is made from copper (Cu), nickel (Ni), cobalt (Co) and combinations thereof in addition to phosphorus (P) and iron (Fe).
- the charge may contain these components (P, Fe, Cu, Ni, Co) in the form of a metal or an element, or may contain them in the form of a compound such as an oxide.
- the container may contain other inorganic components and organic components other than these components (P, Fe, Cu, Ni, Co).
- the target of the container is not particularly limited. Examples include waste lithium ion batteries, electronic components including dielectric or magnetic materials, and electronic devices.
- the form is not limited as long as it is suitable for processing in a subsequent step.
- the container In the preparatory step, the container may be subjected to a treatment such as crushing treatment to form a suitable form. Further, in the preparation step, the container may be subjected to a treatment such as a heat treatment or a sorting treatment to remove unnecessary components such as water and organic substances.
- the prepared raw material is melted and separated into an alloy (metal) and slag. Specifically, the raw material is heated and melted to form a melt. This melt contains the alloy and slag in a molten state. Then, the obtained melt is made into a melt. This melt contains the alloy and slag in a solidified state. Alloys mainly contain valuable metals. Therefore, each of the valuable metal and other components can be separated as an alloy and slag. This is because metals with low added value (such as Al) have high oxygen affinity, whereas valuable metals have low oxygen affinity.
- Al aluminum (Al), lithium (Li), carbon (C), manganese (Mn), phosphorus (P), iron (Fe), cobalt (Co), nickel (Ni) and copper (Cu) are common. It is oxidized in the order of Al>Li>C>Mn>P>Fe>Co>Ni> Cu. That is, aluminum (Al) is most easily oxidized, and copper (Cu) is least easily oxidized. Therefore, low-value-added metals (Al and the like) are easily oxidized to slag, and valuable metals (Cu, Ni, Co) are reduced to metal (alloys). In this way, low-value-added metals and valuable metals can be separated into slag and alloys.
- the oxygen partial pressure in the melt is directly measured by using an oxygen analyzer, and the oxygen partial pressure is controlled based on the obtained measurement result.
- the degree of redox of the melt can be strictly controlled, and as a result, valuable metals and impurities can be separated with high accuracy.
- the degree of redox of the raw material carbon amount, oxidation number and amount of metal
- the redox of the melt can be simply adjusted by adjusting the blending amount at the time of raw material preparation. It is possible in principle to control the degree.
- the raw materials are not uniform. Sampling error occurs during raw material analysis, and this error makes it difficult to control the degree of redox to the target value.
- Patent Document 1 proposes a method of analyzing gas on a melting bath.
- a method of analyzing gas on a melting bath has a large measurement error and cannot be said to be highly reliable. That is, the oxygen partial pressure is not in an equilibrium state inside the melting furnace in which oxygen is being introduced, and is constantly fluctuating. Therefore, the oxygen partial pressure fluctuates greatly depending on the location and time. Further, when the atmospheric gas contains dust, the dust may adhere to the probe of the gas analysis measuring instrument and hinder accurate measurement. Therefore, it is difficult to accurately determine the degree of redox (oxygen partial pressure) of the melt by the method of gas analysis on the melting bath.
- the oxygen partial pressure of the melt since the oxygen partial pressure of the melt is directly measured, the obtained measured value accurately reflects the redox degree of the actual melt. Therefore, if the redox degree of the melt deviates from the target value, the oxygen partial pressure is controlled by introducing a reducing agent or an oxidizing agent, whereby the redox degree of the melt is accurately set to the target value. Can be matched. As a result, even when elements having similar oxygen affinities such as phosphorus and cobalt are contained in the melt, it is possible to accurately separate them.
- the method for measuring the oxygen partial pressure in the melt is not particularly limited.
- a method of using an oxygen analyzer provided in an oxygen sensor (oxygen probe) and inserting the sensor so that the tip of the oxygen sensor is immersed in the melt can be mentioned.
- the oxygen sensor a known sensor such as a zirconia solid electrolytic sensor may be used.
- the method is not limited.
- the oxygen partial pressure may be controlled by a known method.
- a reducing agent or an oxidizing agent may be introduced into a raw material or a melt obtained by melting the raw material.
- a material having a high carbon grade graphite powder, graphite grains, coal, coke, etc.
- carbon monoxide can be used.
- a component having a high carbon grade among the raw materials can also be used as a reducing agent.
- an oxidizing gas (air, oxygen, etc.) or a material having a low carbon grade can be used.
- a component having a low carbon grade among the raw materials can also be used as an oxidizing agent.
- the reducing agent and the oxidizing agent may be introduced by a known method.
- the reducing agent or oxidizing agent is a solid substance, it may be added to a raw material or a melt.
- the reducing agent or the oxidizing agent is a gaseous substance, it may be introduced from an introduction port such as a lance provided in the melting furnace.
- the timing of introducing the reducing agent and the oxidizing agent is not limited.
- a reducing agent or an oxidizing agent may be introduced at the same time when the raw material is put into the melting furnace, or a reducing agent or an oxidizing agent may be introduced when the raw material is melted into a melt.
- a reducing agent or an oxidizing agent is introduced into the melting furnace at the same time as the raw material, and the oxygen partial pressure in the melt is measured at the stage where the raw material is melted into a melt, and based on the obtained results, the oxygen partial pressure is measured. Decide whether to introduce additional reducing or oxidizing agents. If the measured value of oxygen partial pressure deviates from the target value, an additional reducing agent or oxidizing agent may be introduced, while if it is close to the target value, it is not necessary to additionally introduce it.
- the oxygen partial pressure in ⁇ to 10 -12.5 (atm) or more 10 -8.0 (atm) within the following range. This makes it possible to recover valuable metals more efficiently. If the oxygen partial pressure is less than 10 -12.5 (atm), the degree of reduction of the melt is too strong, and impurities phosphorus and iron may be reduced and mixed in the alloy. On the other hand, if the oxygen partial pressure exceeds 10-8.0 (atm), cobalt, which is a valuable metal, may be oxidized and incorporated into slag. More preferably, the oxygen partial pressure is controlled within the range of 10 -12.5 (atm) or more and 10 -11.0 (atm) or less.
- Flux may be introduced (added) to the raw material during the treatment in the melting step.
- the flux preferably contains an element that incorporates an impurity element to form a basic oxide having a low melting point. Since phosphorus becomes an acidic oxide when oxidized, the more basic the slag formed in the melting step, the easier it is for the slag to take in phosphorus and remove it.
- the calcium compound include calcium oxide (CaO) and calcium carbonate (CaCO 3 ).
- the heating temperature at the time of heating and melting the raw material is not particularly limited, but it is preferably 1300 ° C. or higher and 1500 ° C. or lower. By setting the heating temperature to 1300 ° C. or higher, valuable metals (Cu, Co, Ni) are sufficiently melted to form an alloy in a state where the fluidity is enhanced. Therefore, the alloy and the slag can be efficiently separated in the slag separation step described later.
- the heating temperature is more preferably 1350 ° C. or higher. On the other hand, if the heating temperature exceeds 1500 ° C., heat energy is wasted, and refractories such as crucibles and furnace walls are heavily consumed, which may reduce productivity.
- the heating temperature is more preferably 1450 ° C. or lower.
- a step (preheating step) of preheating the raw material (oxidative roasting) to make a preheated product (oxidative roasting product) may be provided before the melting step.
- the raw material is preheated to reduce the amount of carbon contained in the raw material.
- the preheating step if the preheating step is not provided, carbon may hinder the agglutination and integration of the molten fine particles and the resulting separation of the alloy (metal) and the slag, and the recovery rate of the valuable metal may decrease.
- the aggregation and integration of the molten fine particles (valuable metal) in the melting step progresses, and the recovery rate of the valuable metal is further improved. It will be possible to increase to.
- phosphorus (P) and iron (Fe) are impurities that are relatively easily reduced, if carbon is excessively present, phosphorus and iron may be reduced and incorporated into the alloy together with valuable metals. By removing excess carbon in advance, it is possible to prevent phosphorus and iron from being mixed into the alloy.
- the carbon content of the preheated product is preferably less than 1% by mass.
- the preheating step it is desirable to perform treatment (oxidation roasting) at an oxidation degree capable of oxidizing a metal (Al or the like) having a low added value contained in a raw material (container or the like).
- the degree of oxidation is easily controlled by adjusting the treatment temperature, time and / or atmosphere of the preheating. Therefore, the degree of oxidation can be adjusted more strictly by the preheating step, and the variation in oxidation can be suppressed.
- the degree of oxidation is adjusted as follows. As mentioned above, aluminum (Al), lithium (Li), carbon (C), manganese (Mn), phosphorus (P), iron (Fe), cobalt (Co), nickel (Ni) and copper (Cu) are Generally, it is oxidized in the order of Al> Li> C> Mn> P> Fe> Co> Ni> Cu. In the preheating treatment in the preheating step, the oxidation proceeds until the entire amount of aluminum (Al) is oxidized. Oxidation may be promoted until a part of iron (Fe) is oxidized, but the degree of oxidation is maintained to such an extent that cobalt (Co) is not oxidized and distributed to slag.
- Preheating is preferably performed in the presence of an oxidizing agent.
- This makes it possible to efficiently remove the oxidation of carbon (C), which is an impurity, and oxidize aluminum (Al).
- the oxidizing agent is not particularly limited, but an oxygen-containing gas (air, pure oxygen, oxygen-enriched gas, etc.) is preferable because it is easy to handle.
- the amount of the oxidizing agent introduced is preferably, for example, about 1.2 times the chemical equivalent required for oxidation of each substance to be oxidized.
- the heating temperature for preheating is preferably 700 ° C or higher and 1100 ° C or lower. At 700 ° C. or higher, the carbon oxidation efficiency can be further increased and the oxidation time can be shortened. Further, at 1100 ° C. or lower, the heat energy cost can be suppressed and the efficiency of preheating can be improved.
- the preheating temperature may be 800 ° C. or higher. Further, the preheating temperature may be 900 ° C. or lower.
- Preheating can be performed using a known roasting furnace. Further, it is preferable to use a furnace (preliminary furnace) different from the melting furnace used in the subsequent processing in the melting step and perform the processing in the preliminary furnace.
- a furnace preliminary furnace
- any type of furnace can be used as long as it is a furnace capable of supplying an oxidizing agent (oxygen or the like) while roasting the charged material and performing an oxidation treatment inside the furnace.
- a conventionally known rotary kiln and tunnel kiln can be mentioned.
- slag separation process In the slag separation step, the slag is separated from the melt obtained in the melting step, and the alloy containing the valuable metal is recovered. Slag and alloy have different specific densities. Therefore, since slag having a smaller specific gravity than the alloy collects on the upper part of the alloy, it can be easily separated and recovered by specific gravity separation.
- a sulfurization step for sulfurizing the obtained alloy and a crushing step for crushing the obtained sulfide or alloy may be provided.
- a wet smelting process may be applied to an alloy containing a valuable metal obtained through such a dry smelting process. Impurity components can be removed, valuable metals (Cu, Ni, Co) can be separated and purified, and each can be recovered by a wet smelting process. Examples of the treatment in the hydrometallurgy process include known methods such as neutralization treatment and solvent extraction treatment.
- the oxygen partial pressure of the melt can be strictly controlled, whereby the uptake into the alloy of phosphorus and iron can be suppressed while preventing the oxidation of the valuable metal.
- the phosphorus content (phosphorus grade in metal) of the alloy is set to 0.50% by mass or less, 0.10% by mass or less, 0.05% by mass or less, 0.03% by mass or less, or 0.01% by mass or less. can do.
- the iron content (iron grade in metal) of the alloy can be 2.0% by mass or less, 1.0% by mass or less, 0.5% by mass or less, or 0.1% by mass or less.
- the recovery rate of the valuable metal can be 90.0% by mass or more, 95.0% by mass or more, 97.0% by mass or more, 99.0% by mass or more, or 99.5% by mass or more.
- the recovery rate of the valuable metal is calculated according to the following equation (1) using the finally obtained alloy and the content of the valuable metal contained in the slag.
- the container of the present embodiment is not particularly limited as long as it contains a valuable metal, but preferably contains a waste lithium ion battery.
- the waste lithium ion battery contains lithium (Li) and valuable metals (Cu, Ni, Co), and also contains low value-added metals (Al, Fe) and carbon components. Therefore, by using a waste lithium ion battery as a container, valuable metals can be efficiently separated and recovered.
- the waste lithium-ion battery is not only a used lithium-ion battery, but also a lithium-ion battery such as a defective product generated in the manufacturing process such as a positive electrode material constituting the battery, a residue inside the manufacturing process, and generated waste. It is a concept that includes waste materials in the manufacturing process. Therefore, the waste lithium-ion battery can also be called a lithium-ion battery waste material.
- FIG. 1 is a process diagram showing an example of a recovery method.
- this method includes a step of removing the electrolytic solution and the outer can of the waste lithium ion battery to obtain the waste battery contents (waste battery pretreatment step S1), and crushing the waste battery contents.
- the step of making a crushed product (first crushing step S2), the step of preheating the crushed product to make a preheated product (preheating step S3), and the step of melting the preheated product to make a melt (melting). It has a step S4) and a step of separating the slag from the melt and recovering the alloy (slag separation step).
- a sulfurization step of sulfurizing the obtained alloy and a second grinding step of pulverizing the obtained sulfide or alloy may be provided after the slag separation step. The details of each process will be described below.
- the waste battery pretreatment step (S1) is performed for the purpose of preventing the waste lithium ion battery from exploding, detoxifying it, and removing the outer can. Since the lithium ion battery is a closed system, it has an electrolytic solution and the like inside. Therefore, if the crushing process is performed as it is, there is a risk of explosion, which is dangerous. It is preferable to perform discharge treatment or electrolyte removal treatment by some method. Further, the outer can is often composed of the metals aluminum (Al) and iron (Fe), and it is relatively easy to recover the metal outer can as it is. By removing the electrolytic solution and the outer can in the waste battery pretreatment step (S1) in this way, it is possible to improve the safety and the recovery rate of valuable metals (Cu, Ni, Co).
- the specific method of waste battery pretreatment is not particularly limited. For example, a method of physically opening a waste battery with a needle-shaped cutting edge to remove an electrolytic solution can be mentioned. Another method is to heat the waste battery and burn the electrolytic solution to make it harmless.
- the crushed material may be sieved using a sieve shaker after crushing. good. Since aluminum (Al) is easily powdered by light pulverization, it can be efficiently recovered. Further, iron (Fe) contained in the outer can may be recovered by magnetic force sorting.
- the contents of the waste lithium ion battery are pulverized to obtain a pulverized product.
- This process aims to increase the reaction efficiency in the pyrometallurgical process. By increasing the reaction efficiency, the recovery rate of valuable metals (Cu, Ni, Co) can be increased.
- the specific pulverization method is not particularly limited. It can be crushed using a conventionally known crusher such as a cutter mixer.
- the waste battery pretreatment step and the first crushing step together correspond to the preparatory step described above.
- a sulfurization step or a crushing step may be provided after the slag separation step. Further, a wet smelting process may be performed on the obtained valuable metal alloy. The details of the sulfurization process, the pulverization process and the hydrometallurgy process are as described above.
- ⁇ Waste battery pretreatment process (preparation process)> As waste lithium-ion batteries, used batteries and defective products collected in the battery manufacturing process were prepared. Then, the waste lithium ion batteries are collectively immersed in salt water and discharged, then the water content is removed, and the batteries are roasted at 260 ° C. in the air to decompose and remove the electrolytic solution and the outer can to remove the battery contents. Obtained.
- the main elemental compositions of the battery contents are as shown in Table 1 below.
- pulverized product was put into a rotary kiln and preheated in the air at 800 ° C. for 180 minutes to obtain a raw material to be used for heating and melting.
- the oxygen partial pressure in the melt was directly measured using an oxygen analyzer, and the oxygen partial pressure was controlled to 10-12.3 (atm).
- an oxygen analyzer equipped with an oxygen probe (Kawaso Electric Industrial Co., Ltd., OXT-O) was used, and the probe was inserted so that the tip of the oxygen probe was directly immersed in the melt.
- This oxygen probe was equipped with a zirconia solid electrolytic sensor. Then, after waiting for the measured value of oxygen partial pressure to settle down, the measured value was read.
- the oxygen partial pressure was controlled by adjusting the amount of the reducing agent (graphite powder) added.
- Example 2 The oxygen partial pressure was controlled to 10-8.0 (atm) by changing the amount of the reducing agent (graphite powder) added in the melting step. Other than that, valuable metals were recovered in the same manner as in Example 1.
- Example 3 The oxygen partial pressure was controlled to 10-12.1. (Atm) by changing the amount of the reducing agent (graphite powder) added in the melting step. Moreover, the heating temperature was set to 1330 ° C. Other than that, valuable metals were recovered in the same manner as in Example 1.
- Example 4 The oxygen partial pressure was controlled to 10 -12.0 (atm) by changing the amount of the reducing agent (graphite powder) added in the melting step. Moreover, the heating temperature was set to 1480 ° C. Other than that, valuable metals were recovered in the same manner as in Example 1.
- Example 5 The oxygen partial pressure was controlled to 10-7.6 (atm) by changing the amount of the reducing agent (graphite powder) added in the melting step. Other than that, valuable metals were recovered in the same manner as in Example 1.
- Example 6 The oxygen partial pressure was controlled to 10-12.9 (atm) by changing the amount of the reducing agent (graphite powder) added in the melting step. Other than that, valuable metals were recovered in the same manner as in Example 1.
- the respective contents (mass%) of phosphorus (P) and iron (Fe) in the alloy (metal) were defined as phosphorus grade and iron grade.
- the recovery rate of valuable metals was calculated as follows. That is, the recovery rate of the valuable metal was calculated according to the following equation (1) using the content of the valuable metal (Cu, Ni, Co) in the alloy and the slag obtained by elemental analysis.
- Results Table 2 shows the phosphorus grade, iron grade and valuable metal recovery rate obtained for Examples 1 to 6. As can be seen from the results in Table 2, by adjusting the added amount and the heating temperature of the reducing agent, strictly control the oxygen partial pressure in the ⁇ over a range of 10 -12.9 ⁇ 10 -7.6 (atm) We were able to.
- the alloys obtained in Examples 1 to 4 have a high recovery rate of valuable metals contained in the battery of 95% or more, the phosphorus grade in the obtained alloy is less than 0.01% by mass, and the iron grade is 1. It was as low as less than 0.0% by mass. From this, it was found that valuable metals could be obtained with a high recovery rate and that phosphorus and iron could be effectively removed. On the other hand, Example 5 had a low recovery rate of valuable metals, and Example 6 was inferior in iron grade.
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Abstract
Description
本実施形態の方法では、準備工程で、装入物を準備して原料を得る。装入物は、有価金属を回収する処理対象となるものであり、リン(P)及び鉄(Fe)に加えて、銅(Cu)、ニッケル(Ni)、コバルト(Co)及びこれらの組み合わせからなる群から選ばれる少なくとも一種の有価金属を含有する。装入物はこれらの成分(P、Fe、Cu、Ni、Co)を金属や元素の形態で含んでもよく、あるいは酸化物等の化合物の形態で含んでもよい。また、装入物はこれらの成分(P、Fe、Cu、Ni、Co)以外の他の無機成分や有機成分を含んでもよい。
本実施形態の方法では、熔融工程において、準備した原料を熔融して、合金(メタル)とスラグとに分離する。具体的には、原料を加熱熔融して熔体にする。この熔体は、合金とスラグとを熔融した状態で含む。次いで、得られた熔体を熔融物にする。この熔融物は、合金とスラグとを凝固した状態で含む。合金は、有価金属を主として含む。そのため、有価金属とその他の成分のそれぞれを、合金及びスラグとして分離することが可能である。これは付加価値の低い金属(Al等)は酸素親和力が高いのに対し、有価金属は酸素親和力が低いからである。例えば、アルミニウム(Al)、リチウム(Li)、炭素(C)、マンガン(Mn)、リン(P)、鉄(Fe)、コバルト(Co)、ニッケル(Ni)及び銅(Cu)は、一般的にAl>Li>C>Mn>P>Fe>Co>Ni>Cuの順に酸化されていく。つまり、アルミニウム(Al)が最も酸化され易く、銅(Cu)が最も酸化されにくい。そのため、付加価値の低い金属(Al等)は容易に酸化されてスラグになり、有価金属(Cu、Ni、Co)は還元されて金属(合金)になる。このようにして、付加価値の低い金属と有価金属とを、スラグと合金とに分離することができる。
必要に応じて、熔融工程の前に、原料を予備加熱(酸化焙焼)して予備加熱物(酸化焙焼物)にする工程(予備加熱工程)を設けてもよい。予備加熱工程(酸化焙焼工程)では、原料を予備加熱してその原料に含まれる炭素量を減少させる。このような予備加熱工程を設けることで、原料(装入物等)が炭素を過剰に含む場合であっても、この炭素を酸化除去し、それにより、後続する熔融工程での有価金属の合金一体化を促進させることができる。すなわち、熔融工程では、有価金属は還元されて局所的な熔融微粒子になる。炭素は、熔融微粒子(有価金属)が凝集する際に物理的な障害となることがある。そのため、予備加熱工程を設けないと、熔融微粒子の凝集一体化及びそれによる合金(メタル)とスラグの分離を炭素が妨げ、有価金属の回収率が低下してしまう場合がある。これに対して、予め予備加熱工程を設けて原料中の炭素を除去しておくことで、熔融工程での熔融微粒子(有価金属)の凝集一体化が進行し、有価金属の回収率をより一層に高めることが可能になる。また、リン(P)及び鉄(Fe)は比較的に還元されやすい不純物であるため、炭素が過剰に存在すると、リン及び鉄が還元されて有価金属とともに合金に取り込まれてしまう恐れがある。過剰な炭素を予め除去しておくことで、合金へのリン及び鉄の混入を防ぐことができる。なお、予備加熱物の炭素量としては、1質量%未満であることが好ましい。
スラグ分離工程では、熔融工程で得られた熔融物からスラグを分離して、有価金属を含む合金を回収する。スラグと合金は比重が異なる。そのため、合金に比べ比重の小さいスラグは合金の上部に集まるので、比重分離により容易に分離回収することができる。
廃電池前処理工程(S1)は、廃リチウムイオン電池の爆発防止及び無害化並びに外装缶の除去を目的に行われる。リチウムイオン電池は密閉系であるため、内部に電解液などを有している。そのため、そのままの状態で粉砕処理を行うと、爆発の恐れがあり危険である。何らかの手法で放電処理や電解液除去処理を施すことが好ましい。また、外装缶は金属であるアルミニウム(Al)や鉄(Fe)から構成されることが多く、こうした金属製の外装缶はそのまま回収することが比較的容易である。このように、廃電池前処理工程(S1)で電解液及び外装缶を除去することで、安全性を高めるとともに、有価金属(Cu、Ni、Co)の回収率を高めることができる。
第1粉砕工程(S2)では廃リチウムイオン電池の内容物を粉砕して粉砕物を得る。この工程は、乾式製錬プロセスでの反応効率を高めることを目的にしている。反応効率を高めることで、有価金属(Cu、Ni、Co)の回収率を高めることができる。具体的な粉砕方法は、特に限定されるものではない。カッターミキサー等の従来公知の粉砕機を用いて粉砕することができる。なお、廃電池前処理工程と第1粉砕工程は、これらを併せて先述する準備工程に相当する。
予備加熱工程(酸化焙焼工程)(S3)では、第1粉砕工程(S2)で得られた粉砕物を予備加熱(酸化焙焼)して予備加熱物(酸化焙焼物)を得る。この工程の詳細は先述したとおりである。
熔融工程(S4)では、予備加熱工程(S3)で得られた予備加熱物を熔融して熔融物を得る。この工程の詳細は先述したとおりである。
スラグ分離工程では、熔融工程(S4)で得られた熔融物からスラグを分離して、合金を回収する。この工程の詳細は先述したとおりである。
[例1]
廃リチウムイオン電池を装入物に用いて有価金属を回収した。回収は以下の工程にしたがって行った。
廃リチウムイオン電池として、使用済み電池、及び電池製造工程で回収した不良品を準備した。そして、この廃リチウムイオン電池をまとめて塩水中に浸漬して放電させた後、水分を除去し、大気中260℃で焙焼して電解液及び外装缶を分解除去して、電池内容物を得た。電池内容物の主要元素組成は、下記表1に示されるとおりであった。
得られた電池内容物を粉砕機(商品名:グッドカッター、株式会社氏家製作所製)により粉砕して、粉砕物を得た。
得られた粉砕物をロータリーキルンに投入し、大気中800℃で180分間の条件で予備加熱を行い、加熱熔融に供する原料を得た。
予備加熱した粉砕物(加熱熔融に供する原料)に、フラックスとして酸化カルシウム(CaO)及び二酸化珪素(SiO2)を添加し、さらに還元剤として黒鉛粉を添加して、これらを混合した。得られた混合物をアルミナ製坩堝に装入し、これを抵抗加熱によって1400℃の温度で加熱熔融して熔体とした。その後、熔体を合金とスラグとを含む熔融物を得た。
得られた熔融物から、比重の違いを利用してスラグを分離して、熔融状態の合金を回収した。
熔融工程で還元剤(黒鉛粉)の添加量を変えて、酸素分圧を10-8.0(atm)に制御した。それ以外は例1と同様にして有価金属の回収を行った。
熔融工程で還元剤(黒鉛粉)の添加量を変えて、酸素分圧を10-12.1(atm)に制御した。また、加熱温度を1330℃にした。それ以外は例1と同様にして有価金属の回収を行った。
熔融工程で還元剤(黒鉛粉)の添加量を変えて、酸素分圧を10-12.0(atm)に制御した。また、加熱温度を1480℃にした。それ以外は例1と同様にして有価金属の回収を行った。
熔融工程で還元剤(黒鉛粉)の添加量を変えて、酸素分圧を10-7.6(atm)に制御した。それ以外は例1と同様にして有価金属の回収を行った。
熔融工程で還元剤(黒鉛粉)の添加量を変えて、酸素分圧を10-12.9(atm)に制御した。それ以外は例1と同様にして有価金属の回収を行った。
例1~例6において回収した合金(メタル)について、ICP分析装置(アジレント・テクノロジー株式会社、Agilent5100SUDV)を用いて元素分析を行った。この際、有価金属であるニッケル(Ni)、コバルト(Co)及び銅(Cu)と、メタルからの除去が難しい不純物たるリン(P)及び鉄(Fe)を分析元素とした。
例1~例6について得られたリン品位、鉄品位と有価金属回収率を表2に示す。表2の結果から分かるように、還元剤の添加量や加熱温度を調整することで、熔体の酸素分圧を10-12.9~10-7.6(atm)の範囲にわたって厳密に制御することができた。
Claims (6)
- 有価金属(Cu、Ni、Co)を回収する方法であって、以下の工程;
少なくともリン(P)、鉄(Fe)及び有価金属を含む装入物を原料として準備する工程と、
前記原料を加熱熔融して熔体にした後に、前記熔体を合金とスラグとを含む熔融物にする工程と、
前記熔融物からスラグを分離して、有価金属を含む合金を回収する工程と、を有し、
前記原料を加熱熔融する際に、酸素分析計を用いて熔体中の酸素分圧を直接測定し、得られた測定結果に基づき酸素分圧を制御する、方法。 - 前記酸素分圧を10-12.5(atm)以上10-8.0(atm)以下の範囲内に制御する、請求項1に記載の方法。
- 前記酸素分圧を10-12.5(atm)以上10-11.0(atm)以下の範囲内に制御する、請求項1又は2に記載の方法。
- 前記原料を加熱熔融する際の加熱温度を1300℃以上1500℃以下にする、請求項1~3のいずれか一項に記載の方法。
- 前記有価金属が、銅(Cu)、ニッケル(Ni)、コバルト(Co)及びこれらの組み合わせからなる群から選ばれる少なくとも一種の金属又は合金からなる、請求項1~4のいずれか一項に記載の方法。
- 前記装入物が廃リチウムイオン電池を含む、請求項1~5のいずれか一項に記載の方法。
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