JP7246570B2 - 混合金属塩の製造方法 - Google Patents
混合金属塩の製造方法 Download PDFInfo
- Publication number
- JP7246570B2 JP7246570B2 JP2022517107A JP2022517107A JP7246570B2 JP 7246570 B2 JP7246570 B2 JP 7246570B2 JP 2022517107 A JP2022517107 A JP 2022517107A JP 2022517107 A JP2022517107 A JP 2022517107A JP 7246570 B2 JP7246570 B2 JP 7246570B2
- Authority
- JP
- Japan
- Prior art keywords
- ions
- metal salt
- manganese
- cobalt
- mixed metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 85
- 239000002184 metal Substances 0.000 title claims description 85
- 150000003839 salts Chemical class 0.000 title claims description 54
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- 238000000605 extraction Methods 0.000 claims description 44
- 229910052782 aluminium Inorganic materials 0.000 claims description 41
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 31
- 229910001416 lithium ion Inorganic materials 0.000 claims description 31
- 239000010941 cobalt Substances 0.000 claims description 29
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 29
- 229910017052 cobalt Inorganic materials 0.000 claims description 28
- 238000002386 leaching Methods 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 239000003929 acidic solution Substances 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- -1 aluminum ions Chemical class 0.000 claims description 23
- 229910001437 manganese ion Inorganic materials 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- 239000002699 waste material Substances 0.000 claims description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 20
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 20
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 20
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 20
- 229910001453 nickel ion Inorganic materials 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 12
- 238000001556 precipitation Methods 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 239000008346 aqueous phase Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001424 calcium ion Inorganic materials 0.000 claims description 5
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 229910001415 sodium ion Inorganic materials 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 238000006386 neutralization reaction Methods 0.000 description 20
- 238000000034 method Methods 0.000 description 16
- 229910052742 iron Inorganic materials 0.000 description 15
- 150000002739 metals Chemical class 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 10
- 239000007774 positive electrode material Substances 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000003002 pH adjusting agent Substances 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007873 sieving Methods 0.000 description 3
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005406 washing 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
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0488—Flow sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/005—Selection of auxiliary, e.g. for control of crystallisation nuclei, of crystal growth, of adherence to walls; Arrangements for introduction thereof
- B01D9/0054—Use of anti-solvent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/0059—General arrangements of crystallisation plant, e.g. flow sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D9/00—Crystallisation
- B01D9/02—Crystallisation from solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
-
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/32—Carboxylic acids
-
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/32—Carboxylic acids
- C22B3/326—Ramified chain carboxylic acids or derivatives thereof, e.g. "versatic" acids
-
- 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
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/001—Dry processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid 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
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
一の実施形態に係る混合金属塩の製造方法は、マンガンイオンと、コバルトイオン及びニッケルイオンのうちの少なくとも一種とを含む混合金属塩を製造する方法であって、リチウムイオン電池廃棄物の電池粉を浸出工程に供して得られた酸性溶液で、少なくともマンガンイオン及びアルミニウムイオンと、コバルトイオン及びニッケルイオンのうちの少なくとも一種とを含む当該酸性溶液について、前記酸性溶液中のアルミニウムイオンを溶媒に抽出して除去するAl除去工程と、前記Al除去工程で得られる抽出残液を、pHが10.0未満になる条件で中和し、マンガンの金属塩と、コバルト及びニッケルのうちの少なくとも一種の金属塩とを含む混合金属塩を析出させる析出工程とを含む。
対象とするリチウムイオン電池廃棄物は、正極活物質として少なくともコバルト及び/又はニッケルとマンガンとを含み、携帯電話その他の種々の電子機器等で使用され得るリチウムイオン二次電池で、電池製品の寿命や製造不良またはその他の理由によって廃棄されたものである。このようなリチウムイオン電池廃棄物から有価金属を回収することは、資源の有効活用の観点から好ましい。またここでは、有価金属であるコバルト及び/又はニッケルとマンガンとを高純度で回収し、リチウムイオン二次電池の製造に再度使用できるものとすることを目的とする。
破砕処理には、種々の公知の装置ないし機器を用いることができるが、特に、リチウムイオン電池廃棄物を切断しながら衝撃を加えて破砕することのできる衝撃式の粉砕機を用いることが好ましい。この衝撃式の粉砕機としては、サンプルミル、ハンマーミル、ピンミル、ウィングミル、トルネードミル、ハンマークラッシャ等を挙げることができる。なお、粉砕機の出口にはスクリーンを設置することができ、それにより、リチウムイオン電池廃棄物は、スクリーンを通過できる程度の大きさにまで粉砕されると粉砕機よりスクリーンを通じて排出される。
電池粉は浸出工程に供される。浸出工程では、上述した電池粉を、硫酸等の酸性浸出液に添加して浸出させる。浸出工程は公知の方法ないし条件で行うことができるが、pHは0.0~2.0とすること、酸化還元電位(ORP値、銀/塩化銀電位基準)を0mV以下とすることが好適である。
たとえば、浸出後液中のコバルト濃度は0g/L~50g/L、ニッケル濃度は0g/L~50g/L、マンガン濃度は1g/L~50g/L、アルミニウム濃度は0.010g/L~10g/L、鉄濃度は0.1g/L~5g/Lである場合がある。リチウム濃度は、たとえば0g/L~7.0g/Lである場合がある。カルシウム濃度は、たとえば0g/L~1.0g/Lである場合がある。
次いで、浸出後液に対して中和工程を行うことができる。中和工程では、はじめに、浸出後液に水酸化ナトリウム等のアルカリを添加して所定のpHになるように中和する。これにより、浸出後液に溶解していたアルミニウムの一部が沈殿する。そして、フィルタープレスやシックナー等を用いた固液分離により、当該アルミニウムの一部を含む残渣を除去することができる。
ここでは、アルカリの添加によりpHを4.0~6.0とすることがより好ましい。またここで、浸出後液の酸化還元電位(ORPvsAg/AgCl)は-500mV~100mVとすることが好ましい。液温は50℃~90℃とすることが好適である。
酸化剤は、鉄を酸化できるものであれば特に限定されないが、例えば二酸化マンガンを用いることができる。酸化剤として用いる二酸化マンガンは試薬でもよいし、二酸化マンガンを含む正極活物質や正極活物質を浸出して得られるマンガン含有浸出残渣でもよい。
酸化剤の添加後は、水酸化ナトリウム、炭酸ナトリウム、アンモニア等のアルカリを添加して、pHを所定の範囲に調整することができる。
中和工程の後、上記の酸性溶液中のアルミニウムイオンを溶媒に抽出して除去するAl除去工程を行う。ここでは、酸性溶液中のマンガンイオンを抽出残液(水相)に残しつつ、アルミニウムイオンを溶媒(有機相)に抽出する。これにより、アルミニウムイオンが除去されて、少なくとも、コバルトイオン及び/又はニッケルイオンと、マンガンイオンとを含む抽出残液が得られる。ここで、Al除去工程後に得られる抽出残液中のコバルトイオンの含有量及び/又はニッケルイオン含有量と、マンガンイオンの含有量はそれぞれ、質量基準で、中和後液(酸性溶液)中の各イオンの含有量の80%以上であることが好ましく、より好ましくは90%以上である。
析出工程では、上記のAl除去工程で得られる抽出残液を、pHが10.0未満になる条件で中和し、コバルト及び/又はニッケル並びに、マンガンの各金属塩を含む混合金属塩を析出させる。この場合、Al除去工程の直後の析出工程で混合金属塩が得られることになり、Al除去工程後に溶媒抽出を行うことを要しない。一方、たとえば、Al除去工程後に、コバルト及び/又はニッケル並びに、マンガンの二種又は三種の金属を抽出するとともに逆抽出する金属抽出工程を行い、さらにその後に析出工程を実施する場合は、当該抽出時に水酸化ナトリウム等のpH調整剤を使用することが必要になる。このような場合に比して、この実施形態では、pH調整剤の使用によるコストの増大を抑制することができる。しかも、この実施形態では、次に述べるように、混合金属塩への不純物の混入を抑えることもできる。
このような混合金属塩は、コバルト、ニッケル及びマンガンの各メタルよりも、低コストで容易に回収でき、しかもリチウムイオン電池の製造に好適に用いられ得る可能性がある。
Claims (6)
- マンガンイオンと、コバルトイオン及びニッケルイオンのうちの少なくとも一種とを含む混合金属塩を製造する方法であって、
リチウムイオン電池廃棄物の電池粉を浸出工程に供して得られた酸性溶液で、少なくともマンガンイオン及びアルミニウムイオンと、コバルトイオン及びニッケルイオンのうちの少なくとも一種とを含む当該酸性溶液について、前記酸性溶液中のマンガンイオンの少なくとも一部と、コバルトイオン及び/又はニッケルイオンの少なくとも一部とを水相に残しつつ、アルミニウムイオンを溶媒に抽出して除去するAl除去工程と、
前記Al除去工程で得られる抽出残液を、pHが10.0未満になる条件で中和し、マンガンの金属塩と、コバルト及びニッケルのうちの少なくとも一種の金属塩とを含む混合金属塩を析出させる析出工程と
を含む、混合金属塩の製造方法。 - 前記析出工程で、前記抽出残液の中和に水酸化ナトリウムを使用し、前記混合金属塩が、マンガンの水酸化物と、コバルト及びニッケルのうちの少なくとも一種の水酸化物とを含む、請求項1に記載の混合金属塩の製造方法。
- 前記酸性溶液がさらに、マグネシウムイオン、ナトリウムイオン、リチウムイオン及びカルシウムイオンからなる群から選択される一種以上の金属イオンを含み、
前記析出工程で、前記金属イオンを析出させずに液中に残す、請求項1又は2に記載の混合金属塩の製造方法。 - 前記析出工程で、前記抽出残液のpHを9.0以上にする、請求項1~3のいずれか一項に記載の混合金属塩の製造方法。
- 前記Al除去工程で、カルボン酸系抽出剤を含む溶媒を使用し、平衡pHを4.0~5.0とする、請求項1~4のいずれか一項に記載の混合金属塩の製造方法。
- 前記Al除去工程で、質量基準にて、前記酸性溶液中のマンガンイオンの少なくとも80%以上、および、コバルトイオン及びニッケルイオンのうちの少なくとも一種の少なくとも80%以上を水相に残す、請求項1~5のいずれか一項に記載の混合金属塩の製造方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2020076947 | 2020-04-23 | ||
JP2020076947 | 2020-04-23 | ||
PCT/JP2021/016381 WO2021215521A1 (ja) | 2020-04-23 | 2021-04-22 | 混合金属塩の製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2021215521A1 JPWO2021215521A1 (ja) | 2021-10-28 |
JP7246570B2 true JP7246570B2 (ja) | 2023-03-27 |
Family
ID=78269310
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2022517107A Active JP7246570B2 (ja) | 2020-04-23 | 2021-04-22 | 混合金属塩の製造方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US20230312369A1 (ja) |
EP (1) | EP4140956A4 (ja) |
JP (1) | JP7246570B2 (ja) |
KR (1) | KR20220132582A (ja) |
CN (1) | CN115087622A (ja) |
CA (1) | CA3173753A1 (ja) |
WO (1) | WO2021215521A1 (ja) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7060899B1 (ja) * | 2021-09-30 | 2022-04-27 | 株式会社アサカ理研 | 廃リチウムイオン電池からのリチウム回収システム |
WO2024014520A1 (en) * | 2022-07-14 | 2024-01-18 | Jx Metals Corporation | Method for removing aluminum and method for recovering metals |
CN115386727A (zh) * | 2022-07-21 | 2022-11-25 | 珠海格力绿色再生资源有限公司 | 一种锂电池的有价金属回收方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012211386A (ja) | 2011-03-23 | 2012-11-01 | Jx Nippon Mining & Metals Corp | アルミニウムの溶媒抽出方法 |
JP2016186113A (ja) | 2015-03-27 | 2016-10-27 | Jx金属株式会社 | リチウムイオン電池リサイクル原料からの金属の回収方法 |
JP2016194105A (ja) | 2015-03-31 | 2016-11-17 | Jx金属株式会社 | 金属混合水溶液からの金属の除去方法 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5706457B2 (ja) | 2013-02-27 | 2015-04-22 | Jx日鉱日石金属株式会社 | 金属混合溶液からの金属の分離回収方法 |
CN103199320B (zh) * | 2013-03-28 | 2015-05-27 | 四川天齐锂业股份有限公司 | 镍钴锰三元正极材料回收利用的方法 |
JP6334450B2 (ja) * | 2015-03-27 | 2018-05-30 | Jx金属株式会社 | リチウムイオン電池リサイクル原料からの金属の回収方法 |
CN105789726A (zh) * | 2016-04-21 | 2016-07-20 | 苏州聚智同创环保科技有限公司 | 一种以废旧锂离子电池为原料制备镍钴锰三元材料前驱体的方法 |
US11961980B2 (en) * | 2017-03-31 | 2024-04-16 | Jx Metals Corporation | Lithium ion battery scrap treatment method |
CN107732352A (zh) * | 2017-10-12 | 2018-02-23 | 南通新玮镍钴科技发展有限公司 | 一种废锂离子电池正极材料回收利用的方法 |
KR20200096965A (ko) * | 2017-12-19 | 2020-08-14 | 바스프 에스이 | 금속 니켈을 사용한 침출물의 처리에 의한 배터리 재활용 |
-
2021
- 2021-04-22 CA CA3173753A patent/CA3173753A1/en active Pending
- 2021-04-22 US US17/918,307 patent/US20230312369A1/en active Pending
- 2021-04-22 KR KR1020227029225A patent/KR20220132582A/ko unknown
- 2021-04-22 WO PCT/JP2021/016381 patent/WO2021215521A1/ja unknown
- 2021-04-22 JP JP2022517107A patent/JP7246570B2/ja active Active
- 2021-04-22 EP EP21791969.5A patent/EP4140956A4/en active Pending
- 2021-04-22 CN CN202180014072.XA patent/CN115087622A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012211386A (ja) | 2011-03-23 | 2012-11-01 | Jx Nippon Mining & Metals Corp | アルミニウムの溶媒抽出方法 |
JP2016186113A (ja) | 2015-03-27 | 2016-10-27 | Jx金属株式会社 | リチウムイオン電池リサイクル原料からの金属の回収方法 |
JP2016194105A (ja) | 2015-03-31 | 2016-11-17 | Jx金属株式会社 | 金属混合水溶液からの金属の除去方法 |
Also Published As
Publication number | Publication date |
---|---|
EP4140956A4 (en) | 2024-05-01 |
EP4140956A1 (en) | 2023-03-01 |
CN115087622A (zh) | 2022-09-20 |
JPWO2021215521A1 (ja) | 2021-10-28 |
WO2021215521A1 (ja) | 2021-10-28 |
KR20220132582A (ko) | 2022-09-30 |
US20230312369A1 (en) | 2023-10-05 |
CA3173753A1 (en) | 2021-10-28 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6801090B2 (ja) | リチウムイオン電池スクラップの処理方法 | |
CN109072335B (zh) | 锂离子电池废料的处理方法 | |
JP7164763B2 (ja) | 金属混合溶液の製造方法及び、混合金属塩の製造方法 | |
JP7246570B2 (ja) | 混合金属塩の製造方法 | |
WO2017159745A1 (ja) | リチウムイオン電池スクラップの処理方法 | |
JP6735192B2 (ja) | リチウムイオン電池スクラップの処理方法 | |
JP7348130B2 (ja) | 金属含有溶液中のマグネシウムイオン除去方法及び、金属回収方法 | |
JP7198081B2 (ja) | 有価金属の回収方法 | |
WO2022130793A1 (ja) | リチウムイオン電池廃棄物の処理方法 | |
JP2023063319A (ja) | リチウムイオン電池廃棄物の処理方法および、硫酸塩の製造方法 | |
JP7317761B2 (ja) | リチウムイオン電池廃棄物の処理方法 | |
WO2020137995A1 (ja) | 有価金属の回収方法 | |
JP2013112859A (ja) | 硫酸マンガンの製造方法 | |
JP5902601B2 (ja) | 金属混合溶液中の金属の分離方法 | |
JP7383550B2 (ja) | マンガンイオン除去方法 | |
JP7303947B1 (ja) | コバルト溶液の製造方法、コバルト塩の製造方法、ニッケル溶液の製造方法、及びニッケル塩の製造方法 | |
JP7246536B1 (ja) | アルミニウムの除去方法 | |
WO2024053147A1 (ja) | 金属回収方法 | |
JP7185090B1 (ja) | リチウムイオン電池廃棄物の金属回収方法 | |
WO2024014522A1 (en) | Method for recovering metals | |
WO2024014540A1 (en) | Method for removing impurities, and method for recovering metals | |
JP2013209266A (ja) | 硫酸マンガンの製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20220324 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220906 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20221101 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20230214 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20230314 |
|
R151 | Written notification of patent or utility model registration |
Ref document number: 7246570 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |