WO2022039039A1 - 硫化物の処理方法 - Google Patents
硫化物の処理方法 Download PDFInfo
- Publication number
- WO2022039039A1 WO2022039039A1 PCT/JP2021/029115 JP2021029115W WO2022039039A1 WO 2022039039 A1 WO2022039039 A1 WO 2022039039A1 JP 2021029115 W JP2021029115 W JP 2021029115W WO 2022039039 A1 WO2022039039 A1 WO 2022039039A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sulfide
- treatment
- nickel
- pulverized
- cobalt
- Prior art date
Links
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 238000000034 method Methods 0.000 title claims abstract description 80
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 160
- 238000011282 treatment Methods 0.000 claims abstract description 96
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 80
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000010949 copper Substances 0.000 claims abstract description 79
- 229910052802 copper Inorganic materials 0.000 claims abstract description 78
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 74
- 239000010941 cobalt Substances 0.000 claims abstract description 74
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000002386 leaching Methods 0.000 claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 47
- 239000002253 acid Substances 0.000 claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- 239000000155 melt Substances 0.000 claims abstract description 10
- 238000010298 pulverizing process Methods 0.000 claims abstract description 10
- 239000002699 waste material Substances 0.000 claims description 63
- 229910052751 metal Inorganic materials 0.000 claims description 31
- 239000002184 metal Substances 0.000 claims description 31
- 239000002245 particle Substances 0.000 claims description 25
- 230000003472 neutralizing effect Effects 0.000 claims description 19
- 239000007800 oxidant agent Substances 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000006386 neutralization reaction Methods 0.000 claims description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000003568 thioethers Chemical class 0.000 claims 2
- 238000003672 processing method Methods 0.000 claims 1
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 230000001180 sulfating effect Effects 0.000 abstract 3
- 239000000243 solution Substances 0.000 description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- 238000000926 separation method Methods 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 7
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 150000004763 sulfides Chemical class 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000002893 slag Substances 0.000 description 5
- 239000010926 waste battery Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000002950 deficient Effects 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 polypropylene Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- ZWYFTKPEHRQCCW-HNNXBMFYSA-N 3-(2-chlorophenyl)-1-(2-{[(1s)-2-hydroxy-1,2-dimethylpropyl]amino}pyrimidin-4-yl)-1-(4-methoxyphenyl)urea Chemical compound C1=CC(OC)=CC=C1N(C=1N=C(N[C@@H](C)C(C)(C)O)N=CC=1)C(=O)NC1=CC=CC=C1Cl ZWYFTKPEHRQCCW-HNNXBMFYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- USHGRFXQYJEHII-UHFFFAOYSA-M [O-]P(O)(O)=O.[Li+].F.F.F.F.F.F Chemical compound [O-]P(O)(O)=O.[Li+].F.F.F.F.F.F USHGRFXQYJEHII-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/10—Hydrochloric acid, other halogenated acids or salts thereof
-
- 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
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/065—Nitric acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- 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 treating a sulfide containing nickel and / or cobalt and copper.
- LOB lithium-ion batteries
- the LIB is a negative electrode material in which a negative electrode active material such as graphite is fixed to the surface of a negative electrode current collector using a copper foil inside an outer can made of a metal such as aluminum or iron or a plastic such as vinyl chloride.
- a positive electrode material in which a positive electrode active material such as lithium nickelate or lithium cobaltate is fixed to a positive electrode current collector made of an aluminum foil is charged together with a separator made of a porous resin film of polypropylene and the like, and lithium hexafluoride phosphate is charged. It has a structure impregnated with an organic solvent containing an electrolyte such as (LiPF 6 ) as an electrolytic solution.
- waste LIBs include those generated as defective products in the manufacturing process. These waste LIBs contain valuable components such as nickel, cobalt and copper, and it is desired to recover and reuse those valuable components for effective utilization of resources.
- Patent Document 1 discloses a method of recovering a valuable metal by using a dry treatment.
- a copper alloy containing nickel or the like can be obtained.
- the method using the dry treatment has a problem that energy for heating to a high temperature is required, but has an advantage that various impurities can be treated in a simple process and separated at once.
- the obtained slag has relatively stable chemical properties, there is no concern about causing environmental problems, and there is an advantage that it is easy to dispose of.
- waste LIB is treated by dry treatment
- most of the valuable components, especially cobalt are distributed to the slag, and it is inevitable that a loss will occur.
- the metal obtained by the dry treatment is an alloy in which valuable components coexist, in order to reuse it, a purification treatment for separating each component from the alloy and removing impurities is required.
- the separation and purification of each element by the dry method as compared with the wet method has a drawback that the separation level remains at the crude separation level or the cost is high, and the practicality is low.
- hydrometallurgical methods that use acid or treatments such as neutralization treatment and solvent extraction treatment consume less energy and have the advantage of being able to separate the mixed valuable components individually and directly recover them in high-purity grade.
- acid or treatments such as neutralization treatment and solvent extraction treatment consume less energy and have the advantage of being able to separate the mixed valuable components individually and directly recover them in high-purity grade.
- the waste LIB is treated by a wet treatment, the hexafluorophosphate anion contained in the waste LIB is a difficult-to-treat product that cannot be completely decomposed even with high-temperature, high-concentration sulfuric acid. Yes, the valuable components are mixed in the leached acid solution.
- hexafluorophosphate anion is a water-soluble carbonic acid ester, it is difficult to recover phosphorus and fluorine from the aqueous solution after recovering valuable resources, so that the release to public sea areas is suppressed. Therefore, it is necessary to take various measures.
- waste LIB itself is difficult to leached, and it is not easy to leached valuable components at a sufficient leaching rate.
- waste LIB is forcibly leached out using an acid with strong oxidizing power, a large amount of components such as aluminum, iron, and manganese that are not the target of recovery are leached out together with valuable components, and these are neutralized.
- the amount of neutralizing agent added for treatment and the amount of wastewater to be handled increase.
- the above-mentioned waste LIB which is difficult to treat by the dry treatment or the wet treatment alone, is uniformly removed by removing impurities as much as possible by a method combining the dry treatment and the wet treatment, that is, a dry treatment such as roasting the waste LIB. Attempts have been made to obtain a waste LIB treated product and wet-treat the obtained treated product to separate it into a valuable component and other components.
- the obtained solution contains high-concentration copper and relatively low-concentration nickel or cobalt.
- nickel and cobalt can be easily separated from known methods such as solvent extraction, but it is difficult to separate a large amount of copper from nickel and cobalt easily and at low cost.
- the present invention has been made in view of such circumstances, for example, from a sulfide containing copper and nickel and / or cobalt obtained by subjecting a waste LIB to a dry treatment, nickel and /.
- the present inventors have made extensive studies to solve the above-mentioned problems.
- the sulfide containing copper and nickel and / or cobalt (the sulfide to be treated) is pulverized so as to have a predetermined particle size or less, and the condition that the sulfide agent coexists with the obtained pulverized sulfide. It has been found that the above-mentioned problems can be solved by performing a sulfurization treatment with an acid below, and the present invention has been completed.
- the first aspect of the present invention is a method for treating a sulfide containing copper and nickel and / or cobalt.
- the pulverized sulfide is pulverized to obtain a pulverized sulfide having a particle size of 800 ⁇ m or less, and the pulverized sulfide is leached with an acid under the condition that a sulfide agent coexists.
- a method for treating sulfide which comprises a leaching step of obtaining a leaching solution.
- the second aspect of the present invention is, in the first invention, a method for treating a sulfide to obtain a leachate by subjecting it to a leachate treatment with at least one selected from sulfuric acid, hydrochloric acid, and nitric acid in the leachate step.
- the third aspect of the present invention is the method for treating sulfide, which further comprises a reduction step of subjecting the leachate to a reduction treatment using a metal lower than copper in the first or second invention. ..
- a solution containing nickel and / or cobalt is prepared by adding an oxidizing agent and a neutralizing agent to the solution obtained in the reduction step.
- Fifth of the present invention is a method for treating a sulfide in which the oxidizing agent is one or more selected from hydrogen peroxide and hypochlorous acid in the fourth invention.
- the sixth aspect of the present invention is the method for treating sulfide, wherein the neutralizing agent is one or more selected from sodium hydroxide and potassium hydroxide in the fourth or fifth invention.
- the sulfide is sulfurized by adding a sulfurizing agent to a melt obtained by reducing and heating a waste lithium ion battery. A method of treating sulfides that are produced by this.
- Eighth of the present invention is a method of recovering valuable metal from a waste lithium ion battery, which is produced by sulfurizing a melt obtained by reducing and heating the waste lithium ion battery. And / or includes a step of obtaining a leachate by leaching a sulfide containing cobalt with an acid, and in the step, the sulfide is subjected to a pulverization treatment to obtain a pulverized sulfide having a particle size of 800 ⁇ m or less.
- This is a method for recovering valuable metal from a waste lithium ion battery, in which the pulverized sulfide is leached with an acid under the condition that a sulfide agent coexists.
- a ninth method of the present invention is a method for recovering valuable metals from a waste lithium ion battery, in which the melt obtained by reducing and heating the waste lithium ion battery is sulfurized to form copper, nickel and /.
- it includes a dry treatment step of obtaining a sulfide containing cobalt and a wet treatment step of leaching the sulfide with an acid, and in the wet treatment step, the particle size is formed by crushing the sulfide.
- nickel and cobalt can be efficiently and selectively separated from sulfides containing copper and nickel and / or cobalt.
- the present embodiment a specific embodiment of the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail.
- the present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the object of the present invention.
- the notation "X to Y" (X and Y are arbitrary numerical values) means "X or more and Y or less”.
- the sulfide treatment method of the present invention is a sulfide treatment method containing copper and nickel and / or cobalt, and is a method for selectively separating nickel and / or cobalt from the sulfide. ..
- the sulfide to be treated is, for example, copper and nickel produced by a dry treatment in which a waste lithium ion battery (waste LIB) is reduced and heated and melted, and a sulfurizing agent such as elemental sulfur is added to the obtained melt to sulphurize. And / or a sulfide containing cobalt.
- the sulfide treatment method of the present invention comprises a pulverization step of obtaining a pulverized sulfide having a particle size of 800 ⁇ m or less by subjecting the sulfide to a pulverization treatment, and the obtained pulverized sulfide. It is characterized by including a leaching step of performing a leaching treatment with an acid under a condition in which a sulfurizing agent coexists to obtain a leachate.
- the particle size of the sulfide is set to 800 ⁇ m or less, and the pulverized sulfide is subjected to leaching treatment with an acid in the presence of a sulfide agent. Since nickel and cobalt can be leached at a good leaching rate and copper can be precipitated as copper sulfide for copper, nickel and cobalt can be leached into the leachate very selectively, which is effective with copper. It becomes possible to separate into.
- a waste lithium ion battery for example, a waste lithium ion battery (waste LIB) is reduced and heated and melted, and a sulfurizing agent such as simple sulfur is added to the obtained melt to sulfide.
- a sulfurizing agent such as simple sulfur is added to the obtained melt to sulfide.
- examples include sulfides produced by dry treatment.
- it may be a sulfide produced by dry processing a waste battery containing copper and nickel and / cobalt other than the lithium ion battery.
- the present invention is not limited to a battery, and may be a sulfide produced by dry-treating a material containing copper and nickel and / cobalt.
- Waste batteries including waste LIBs are waste due to deterioration of automobiles or electronic devices, battery scraps generated at the end of battery life, or waste batteries such as defective products in the battery manufacturing process. Used batteries or batteries. It means that the battery is discarded because it is a defective product at the time of manufacture.
- Sulfide treatment method ⁇ As a specific embodiment of the present invention (hereinafter, referred to as “the present embodiment”), a sulfide containing copper and nickel and / or cobalt obtained by dry treatment of waste LIB is treated. A more specific explanation will be given by taking the case of the target as an example.
- the sulfide treatment method includes a crushing step S1 in which the sulfide is pulverized to obtain a pulverized sulfide, and a leaching step S2 in which the pulverized sulfide is leached with an acid.
- a crushing step S1 in which the sulfide is pulverized to obtain a pulverized sulfide
- a leaching step S2 in which the pulverized sulfide is leached with an acid.
- an oxidizing agent is added and a neutralizing agent is added to perform an oxidation neutralization treatment.
- the sulfide obtained by subjecting the waste LIB to a dry treatment is specifically a sulfurizing agent such as elemental sulfur in the obtained melt obtained by reducing and heating the waste LIB. It is a sulfide containing copper and nickel and / or cobalt, which is obtained by adding and sulfurizing.
- the waste LIB is put into a roasting furnace and oxidatively roasted at a temperature of about 300 ° C. to 1000 ° C., and then the obtained roasted product (roasting) is performed.
- the latter product is put into a melting furnace such as a graphite crucible or a magnesium crucible and subjected to a reduction heat treatment for melting under high temperature conditions of about 1100 ° C to 1400 ° C.
- a sulfurizing agent of a liquid or gas such as simple sulfur (solid sulfur), sodium hydrogen sulfide, sodium sulfide, or hydrogen sulfide gas is added to the melt obtained by reduction heating fusion to perform sulfurization treatment.
- a sulfide containing copper and nickel and / or cobalt which are metal components constituting the waste LIB, can be obtained.
- most of copper is in the form of sulfide, and nickel, cobalt, and some unsulfided copper coexist in the form of containing metal, some oxygen, and the like. Are collectively referred to as "sulfides".
- a sulfide containing copper and nickel and / or cobalt is pulverized to a predetermined particle size or less to obtain a pulverized sulfide.
- the sulfide is pulverized so that the particle size is 800 ⁇ m or less.
- the leaching rate can be increased when the pulverized sulfide is subjected to the treatment in the leaching step S2 of the next step.
- Nickel and cobalt leaching efficiency can be increased.
- acid leaching is performed in the presence of a sulfide agent, so that copper can be efficiently immobilized as copper sulfide in the sulfide. It can be separated by selectively leaching nickel and / or cobalt into the resulting leachate.
- the particle size of the sulfide is preferably pulverized to 700 ⁇ m or less, and more preferably 500 ⁇ m or less.
- the lower limit of the particle size is not particularly limited, but if the particle size is too small, handling becomes difficult and hydrogen sulfide gas or the like may be generated in the leaching treatment, which is not preferable. From this point of view, the lower limit of the particle size is preferably 100 ⁇ m or more.
- the method (crushing method) in the crushing treatment is not particularly limited as long as the particle size of the sulfide can be crushed to 800 ⁇ m or less.
- it can be crushed by a method using a known crushing device such as a jaw crusher or a vibration mill.
- the particle size of the pulverized sulfide can be measured by, for example, a laser diffraction / scattering method.
- the pulverized sulfide is subjected to a leaching treatment with an acid to obtain a leachate.
- the leaching treatment is performed under the condition that the sulfurizing agent coexists.
- nickel and / or cobalt contained in the pulverized sulfide is leached to obtain a leachate.
- pulverized sulfide of 800 ⁇ m or less is used as the target of the leaching treatment. Since most of the copper is a sulfide contained in the form of a sulfide, the leaching rate can be increased as compared with, for example, a corrosion resistant alloy based on copper. Further, by performing the leaching treatment on the pulverized sulfide prepared to have a particle size of 800 ⁇ m or less, the leaching rate by the acid can be increased and the leaching rate can be improved.
- the leaching rate can be increased, unsulfided copper contained in the pulverized sulfide is also leached together with nickel and / or cobalt, and even if the leaching rate is increased, the separability from copper is lowered.
- the leached copper can be reduced and separated, but if the concentration of copper in the leachate is too high, the reduction treatment takes time and a large amount of copper is reduced.
- the amount of the reducing agent used is large, it is preferable to separate copper as much as possible at the time of the leachate from the viewpoint of productivity.
- the sulfurizing agent in the leaching treatment, is brought into contact with the acid in the coexisting state, so that the copper contained in the pulverized sulfide is sulfurized by the sulfurizing agent.
- the copper sulfide contained in the pulverized sulfide is directly precipitated as solid copper sulfide in the leachate.
- both copper sulfide contained in the pulverized sulfide and unsulfided copper are effectively precipitated or precipitated as copper sulfide, and only nickel and cobalt contained in the pulverized sulfide are selectively selected. It can be leached into the leachate, and in addition to improving the leaching rate, copper can be separated from nickel and cobalt extremely effectively.
- sulfuric acid As the acid, sulfuric acid, hydrochloric acid, nitric acid and the like can be used, and these acids can be used alone or in combination of two or more. Further, chloride may be contained in sulfuric acid and used as an acid. Among them, it is preferable to use sulfuric acid. From the viewpoint of realizing the so-called "battery-to-battery", which is an ideal circulation method for recycling waste LIB and reusing it as a LIB raw material, by using sulfuric acid as an acid, a sulfate that is easy to use as a positive electrode material for lithium-ion batteries. The exudate can be obtained in the form of.
- the amount of acid is 1 equivalent or more, preferably 1.2 equivalents or more, more preferably 1.2 equivalents or more and 11 equivalents or less, relative to the total amount of nickel and / or cobalt contained in the pulverized sulfide.
- the reaction rate can be increased by increasing the acid concentration.
- sulfurizing agent used for the leachation treatment sodium hydrosulfide or elemental sulfur can be used.
- elemental sulfur it is preferable to pulverize it appropriately so that the reaction can proceed easily.
- the amount of the sulfurizing agent is preferably 1 equivalent or more with respect to the amount of copper contained in the pulverized sulfide.
- the ORP redox potential
- the pH is preferably controlled to 0.5 or more and 1.6 or less.
- the end point of the leachate reaction can be determined by measuring the redox potential (ORP) of the leachate to determine the end point of nickel and / or cobalt leaching.
- ORP redox potential
- the leachate obtained in the leaching step S2 is subjected to a reduction treatment using a reducing agent to obtain a reduced liquid containing nickel and / or cobalt.
- a reduction treatment using a reducing agent to obtain a reduced liquid containing nickel and / or cobalt.
- copper contained in the pulverized sulfide is leached out by an acid together with nickel and / or cobalt and dissolved in the solution, and a part of the copper is dissolved in the solution without reacting with the sulfide agent. It may remain inside.
- a small amount of copper remaining in the leachate is reduced to form a copper-containing precipitate, and the generated precipitate is separated by solid-liquid separation to obtain a reducing liquid containing nickel and / or cobalt. obtain.
- a metal lower than copper can be used as the reducing agent. Copper in the leachate can be reduced by bringing a metal, which is lower than copper, into contact with the leachate. As a metal lower than copper, it is preferable to use a metal containing nickel and / or cobalt.
- the sulfide treatment method according to the present embodiment selectively recovers nickel and / or cobalt in the leachate, and reduces nickel and / or a metal containing cobalt, which is the target of recovery in the reduction treatment. By using it as an agent, it is industrially advantageous because it is not necessary to separately recover the reducing agent in the subsequent step.
- sulfide can be used in addition to the above-mentioned metal.
- the sulfide may be a solid, a liquid, or a gas (gaseous). Further, it may be a mixture of the above-mentioned metal and sulfur.
- ORP redox potential
- oxidative neutralization process In the oxidative neutralization step S4, a solution containing nickel and / or cobalt by adding an oxidant to the reducing solution obtained in the reduction step S3 and performing an oxidative neutralization treatment by adding a neutralizing agent. (Neutralizing solution) is obtained. Specifically, in the oxidation-neutralization step S4, an oxidizing agent is added to the reducing solution to cause an oxidation reaction, and a neutralizing agent is added to control the pH of the solution within a predetermined range to produce waste LIB. Produces iron and / or phosphorus precipitates of origin.
- an oxidizing agent such as hydrogen peroxide or hypochlorous acid.
- ORP oxidation-reduction potential
- an oxidizing agent is added to the solution to control the ORP (with silver / silver chloride as a reference electrode) in the range of 380 mV or more and 430 mV or less.
- a neutralizing agent is added to control the pH of the solution, preferably in the range of 3.8 or more and 4.5 or less.
- a neutralizing agent is added to control the pH of the solution, preferably in the range of 3.8 or more and 4.5 or less.
- the neutralizing agent is not particularly limited, but it is preferable to use an alkali such as sodium hydroxide or potassium hydroxide.
- the oxidizing agent may be added after the neutralizing agent is added to the reducing solution, or the oxidizing agent and the neutralizing agent may be added to the reducing solution at the same time, and in particular, It is preferable to add the neutralizing agent after adding the oxidizing agent to the reducing solution.
- an oxidizing agent is added to a reducing solution whose pH has become high due to the addition of a neutralizing agent, iron is not sufficiently oxidized when iron is contained as an impurity, and Fe (OH) 3 is added. Precipitates (iron precipitates) may not be produced and impurities may be insufficiently separated.
- a method for recovering valuable metals from waste lithium-ion batteries will be described.
- a sulfide containing copper and nickel and / or cobalt is obtained by sulfurizing a melt obtained by reducing and heating waste LIB (dry treatment step), and the sulfide is leached with an acid. By doing so, a leachate is obtained (wet treatment step).
- a sulfide containing copper and nickel and / or cobalt obtained by dry-treating the waste LIB is subjected to a pulverization treatment to obtain a pulverized sulfide having a particle size of 800 ⁇ m or less, and the pulverized sulfide is obtained. It is characterized in that the substance is leached with an acid under the condition that a sulfurizing agent coexists. In this way, nickel and / or cobalt can be selectively separated from the sulfide containing copper and nickel and / or cobalt, and the valuable metal contained in the waste LIB can be effectively recovered. Become. These treatments are the same as those described in the above-mentioned sulfide treatment method.
- Example 1 A waste lithium ion battery (waste LIB) is heated and melted and reduced, and a sulfurizing agent is added to the obtained melt to sulphurize to obtain a sulfide containing copper, nickel and cobalt, and this sulfurization is obtained. A treatment was performed to separate copper, nickel and cobalt contained in sulfide, with the product as a treatment target.
- waste LIB waste lithium ion battery
- a sulfide containing copper, nickel and cobalt was pulverized with a jaw crusher and a vibration mill to obtain a pulverized sulfide having a particle size of 800 ⁇ m or less.
- the particle size of the pulverized sulfide is an average particle size measured by a laser diffraction / scattering method using a particle size distribution measuring device (manufactured by Shimadzu Corporation, SALD-7000).
- Table 1 below shows the results of the metal grade obtained by analyzing the obtained pulverized sulfide using an ICP analyzer.
- the concentration of Cu in the leachate was as low as 3 g / L. From this, it is possible to efficiently and selectively perform leaching treatment with an acid under the condition that a sulfide agent coexists with the pulverized sulfide having a predetermined particle size containing nickel and / or cobalt and copper. , Copper and nickel and cobalt can be separated.
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Abstract
Description
前記硫化物に対して粉砕処理を施すことにより粒径が800μm以下の粉砕硫化物を得る粉砕工程と、前記粉砕硫化物に対して、硫化剤が共存する条件下で、酸による浸出処理を施して浸出液を得る浸出工程と、を含む、硫化物の処理方法である。
本発明の硫化物の処理方法は、銅とニッケル及び/又はコバルトとを含む硫化物の処理方法であり、その硫化物から、選択的にニッケル及び/又はコバルトを分離するようにする方法である。処理対象の硫化物は、例えば、廃リチウムイオン電池(廃LIB)を還元加熱熔融し、得られた熔体に単体硫黄等の硫化剤を添加して硫化する乾式処理により生成する、銅とニッケル及び/又はコバルトを含む硫化物である。
以下では、本発明の具体的な実施形態(以下、「本実施の形態」という)として、廃LIBに対して乾式処理を経て得られる、銅とニッケル及び/又はコバルトとを含む硫化物を処理対象とする場合を一例として、より具体的に説明する。
粉砕工程S1では、銅とニッケル及び/又はコバルトとを含む硫化物を所定の粒径以下に粉砕して粉砕硫化物を得る。具体的には、硫化物を粒径が800μm以下となるように粉砕する。
浸出工程S2では、粉砕硫化物に対して酸による浸出処理を施して浸出液を得る。このとき、硫化剤が共存する条件下で浸出処理を施すことを特徴としている。このような方法によれば、粉砕硫化物に含まれるニッケル及び/又はコバルトを浸出させて浸出液を得る。
還元工程S3では、浸出工程S2で得られた浸出液に対して、還元剤を用いて還元処理を施してニッケル及び/又はコバルトを含む還元液を得る。ここで、上述した浸出工程S2における処理では、ニッケル及び/又はコバルトとともに、粉砕硫化物に含まれる銅が酸により浸出して溶液中に溶解し、硫化剤と反応せずにその一部が溶液中に残存することがある。そこで、還元工程S3では、浸出液に残存する微量の銅を還元して銅を含む沈殿物を生成させ、生成した沈殿物を固液分離により分離して、ニッケル及び/又はコバルトを含む還元液を得る。
酸化中和工程S4では、還元工程S3で得られた還元液に酸化剤を添加するとともに中和剤を添加することにより酸化中和処理を施すことで、ニッケル及び/又はコバルトと、を含む溶液(中和液)を得る。具体的に、酸化中和工程S4では、還元液に酸化剤を添加して酸化反応を生じさせるとともに、中和剤を添加して溶液のpHを所定の範囲に制御することで、廃LIBに由来する鉄及び/又はリンの沈殿物を生成する。
廃リチウムイオン電池(廃LIB)から有価金属を回収する方法について説明する。この方法は、廃LIBを還元加熱熔融して得られる熔体を硫化することにより銅とニッケル及び/又はコバルトとを含有する硫化物を得て(乾式処理工程)、この硫化物を酸で浸出することによって浸出液を得る(湿式処理工程)。
廃リチウムイオン電池(廃LIB)を加熱熔融して還元し、得られた熔体に硫化剤を添加して硫化することにより、銅とニッケル及びコバルトとを含有する硫化物を得て、この硫化物を処理対象として、硫化物に含まれる銅とニッケル及びコバルトとを分離する処理を行った。
まず、銅とニッケル及びコバルトとを含有する硫化物を、ジョークラッシャー及び振動ミルで粉砕して、粒径800μm以下の粉砕硫化物を得た。なお、粉砕硫化物の粒径は、粒子径分布測定装置(島津製作所製,SALD-7000)を用いてレーザー回折散乱法にて測定した平均粒径である。また、下記表1に、得られた粉砕硫化物についてICP分析装置を用いて分析して求めたメタル品位の結果を示す。
次に、粉砕硫化物中のニッケル、及び粉砕硫化物を浸出するのに十分な硫酸を用意した。そして、粉砕硫化物中に含まれる銅量に対して、1当量となる量の硫化剤(硫黄)を添加し、粉砕硫化物を硫化剤が共存する条件下で、スラリー濃度100g/Lとして酸による浸出処理を施した。この浸出液についてICP分析装置により分析した。各元素成分の分析値(g/L)を表2に示す。
浸出終了時に固液分離して、得られた浸出液に対して還元剤(ニッケル硫化物)を用いて還元処理を施して、ろ過を行い固液分離し、濾液(還元液)を得た。この還元液についてICP分析装置により分析した。各元素成分の分析値(g/L)を表2に示す。
次に、得られた還元液に濃度30%過酸化水素水(酸化剤)を添加し、過酸化水素水(酸化剤)を添加した後に苛性ソーダ水溶液(中和剤)を添加することで酸化還元電位(ORP)を、銀塩化銀電極を参照電極とする値で400mV以上、pH4以上として酸化中和処理を施した。反応後、ろ過を行って固液分離し、濾液(中和液)を得た。この濾液(中和液)についてICP分析装置により分析した。各元素成分の分析値(g/L)を表2に示す。
Claims (9)
- 銅とニッケル及び/又はコバルトとを含む硫化物の処理方法であって、
前記硫化物に対して粉砕処理を施すことにより粒径が800μm以下の粉砕硫化物を得る粉砕工程と、
前記粉砕硫化物に対して、硫化剤が共存する条件下で、酸による浸出処理を施して浸出液を得る浸出工程と、
を含む、硫化物の処理方法。 - 前記浸出工程では、硫酸、塩酸、硝酸から選ばれる少なくとも1種以上による浸出処理を施して浸出液を得る
請求項1に記載の硫化物の処理方法。 - 前記浸出液に対し、銅よりも卑な金属を用いて還元処理を施す還元工程をさらに含む、
請求項1又は2に記載の硫化物の処理方法。 - 前記還元工程で得られた溶液に、酸化剤を添加するとともに中和剤を添加することにより、ニッケル及び/又はコバルトを含む溶液を得る酸化中和工程をさらに含む、
請求項3に記載の硫化物の処理方法。 - 前記酸化剤は、過酸化水素及び次亜塩素酸から選ばれる1種以上である、
請求項4に記載の硫化物の処理方法。 - 前記中和剤は、水酸化ナトリウム及び水酸化カリウムから選ばれる1種以上である、
請求項4又は5に記載の硫化物の処理方法。 - 前記硫化物が、廃リチウムイオン電池を還元加熱熔融して得られる熔体に硫化剤を添加して硫化することによって生成されるものである
請求項1乃至6のいずれかに記載の硫化物の処理方法。 - 廃リチウムイオン電池から有価金属を回収する方法であって、
前記廃リチウムイオン電池を還元加熱熔融して得られる熔体を硫化して生成する、銅とニッケル及び/又はコバルトとを含む硫化物を酸で浸出することによって浸出液を得る工程を含み、
前記工程では、
前記硫化物に対して粉砕処理を施すことにより粒径が800μm以下の粉砕硫化物とし、該粉砕硫化物に対して硫化剤が共存する条件下で酸による浸出処理を施す、
廃リチウムイオン電池からの有価金属の回収方法。 - 廃リチウムイオン電池から有価金属を回収する方法であって、
前記廃リチウムイオン電池を還元加熱熔融して得られる熔体を硫化して、銅とニッケル及び/又はコバルトとを含む硫化物を得る乾式処理工程と、
前記硫化物に対して酸で浸出処理を施す湿式処理工程と、を含み、
前記湿式処理工程では、
前記硫化物を粉砕することにより粒径が800μm以下の粉砕硫化物とし、
前記粉砕硫化物に対して、硫化剤が共存する条件下で、酸による浸出処理を施す、
廃リチウムイオン電池からの有価金属の回収方法。
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CN202180018347.7A CN115210392A (zh) | 2020-08-17 | 2021-08-05 | 硫化物的处理方法 |
KR1020237005911A KR20230039736A (ko) | 2020-08-17 | 2021-08-05 | 황화물의 처리 방법 |
EP21858186.6A EP4197662A4 (en) | 2020-08-17 | 2021-08-05 | SULFIDE TREATMENT PROCESS |
CA3187383A CA3187383A1 (en) | 2020-08-17 | 2021-08-05 | Method for treating sulfide |
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Citations (5)
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JPS56134505A (en) * | 1980-02-18 | 1981-10-21 | Anglo Amer Corp South Africa | Method of treating sulfide mat |
JPS63259033A (ja) | 1986-04-24 | 1988-10-26 | フアルコンブリツジ・リミテツド | オ−トクレ−ブ内での銅からのニツケル分離方法 |
JP2012107264A (ja) * | 2010-11-15 | 2012-06-07 | Sumitomo Metal Mining Co Ltd | 銅イオンの分離方法、及び電気ニッケルの製造方法 |
JP2012172169A (ja) | 2011-02-18 | 2012-09-10 | Sumitomo Metal Mining Co Ltd | 有価金属回収方法 |
JP2020029586A (ja) * | 2018-08-21 | 2020-02-27 | 住友金属鉱山株式会社 | 銅とニッケル及びコバルトの分離方法 |
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AU2006326812A1 (en) * | 2005-12-23 | 2007-06-28 | G. Bryn Harris | Process for recovering iron as hematite from a base metal containing ore material |
JP6897466B2 (ja) * | 2017-09-29 | 2021-06-30 | 住友金属鉱山株式会社 | 銅とニッケルおよびコバルトの分離方法 |
JP6939506B2 (ja) * | 2017-12-18 | 2021-09-22 | 住友金属鉱山株式会社 | 銅とニッケルおよびコバルトの分離方法 |
DE102018102026A1 (de) * | 2018-01-30 | 2019-08-01 | Duesenfeld Gmbh | Verfahren zum Verwerten von Lithium-Batterien |
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JPS56134505A (en) * | 1980-02-18 | 1981-10-21 | Anglo Amer Corp South Africa | Method of treating sulfide mat |
JPS63259033A (ja) | 1986-04-24 | 1988-10-26 | フアルコンブリツジ・リミテツド | オ−トクレ−ブ内での銅からのニツケル分離方法 |
JP2012107264A (ja) * | 2010-11-15 | 2012-06-07 | Sumitomo Metal Mining Co Ltd | 銅イオンの分離方法、及び電気ニッケルの製造方法 |
JP2012172169A (ja) | 2011-02-18 | 2012-09-10 | Sumitomo Metal Mining Co Ltd | 有価金属回収方法 |
JP2020029586A (ja) * | 2018-08-21 | 2020-02-27 | 住友金属鉱山株式会社 | 銅とニッケル及びコバルトの分離方法 |
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JP2022033492A (ja) | 2022-03-02 |
KR20230039736A (ko) | 2023-03-21 |
US20230295766A1 (en) | 2023-09-21 |
CN115210392A (zh) | 2022-10-18 |
CA3187383A1 (en) | 2022-02-24 |
EP4197662A1 (en) | 2023-06-21 |
EP4197662A4 (en) | 2024-10-02 |
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