CN113195121A - 有价金属的回收方法 - Google Patents
有价金属的回收方法 Download PDFInfo
- Publication number
- CN113195121A CN113195121A CN201980084279.7A CN201980084279A CN113195121A CN 113195121 A CN113195121 A CN 113195121A CN 201980084279 A CN201980084279 A CN 201980084279A CN 113195121 A CN113195121 A CN 113195121A
- Authority
- CN
- China
- Prior art keywords
- recovery
- cobalt
- extraction
- ions
- nickel
- 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.)
- Granted
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000002739 metals Chemical class 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 102
- 238000000605 extraction Methods 0.000 claims abstract description 102
- 239000000243 solution Substances 0.000 claims abstract description 78
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 65
- 239000010941 cobalt Substances 0.000 claims abstract description 65
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000011084 recovery Methods 0.000 claims abstract description 62
- 239000003929 acidic solution Substances 0.000 claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 42
- 229910001429 cobalt ion Inorganic materials 0.000 claims abstract description 41
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000004090 dissolution Methods 0.000 claims abstract description 29
- 239000002699 waste material Substances 0.000 claims abstract description 27
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 24
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 22
- 238000000638 solvent extraction Methods 0.000 claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 239000003792 electrolyte Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 39
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 11
- 230000008025 crystallization Effects 0.000 claims description 11
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 9
- 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 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910001415 sodium ion Inorganic materials 0.000 claims description 8
- 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 claims description 7
- 239000000284 extract Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 30
- 238000006386 neutralization reaction Methods 0.000 description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 238000002386 leaching Methods 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- 239000008346 aqueous phase Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000012074 organic phase Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- -1 phosphate ester Chemical class 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 9
- 229940044175 cobalt sulfate Drugs 0.000 description 9
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical group CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000008151 electrolyte solution Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 2
- MJUVQSGLWOGIOB-UHFFFAOYSA-N 2-[(Z)-hydroxyiminomethyl]-4-nonylphenol Chemical compound OC1=C(C=N/O)C=C(C=C1)CCCCCCCCC MJUVQSGLWOGIOB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-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
- 238000001354 calcination Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- UWGTVLYQSJNUFP-SILNSSARSA-N 4-dodecyl-2-[(Z)-hydroxyiminomethyl]phenol Chemical compound [H]\C(=N\O)C1=C(O)C=CC(CCCCCCCCCCCC)=C1 UWGTVLYQSJNUFP-SILNSSARSA-N 0.000 description 1
- UHSURKDCQCGNGM-UHFFFAOYSA-N 5-(2-hydroxyimino-2-phenylethyl)nonan-2-ol Chemical compound CCCCC(CCC(C)O)CC(=NO)C1=CC=CC=C1 UHSURKDCQCGNGM-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 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
- NMNFDTCOWIDEAV-UHFFFAOYSA-N OP(O)=O.OP(O)=O Chemical compound OP(O)=O.OP(O)=O NMNFDTCOWIDEAV-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052656 albite Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 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
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 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
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Images
Classifications
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- 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
- 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
-
- 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
-
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0476—Separation of nickel from cobalt
- C22B23/0484—Separation of nickel from cobalt in acidic type 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
- 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
- C22B3/04—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
-
- 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
- C22B3/30—Oximes
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- 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
- C22B3/324—Naphthenic acids
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- 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
- C22B3/26—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
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
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- 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
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
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- 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
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
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Abstract
本发明的方法是从对含有锂离子二次电池的正极材料的废弃物实施湿式处理而获得且含有钴离子、镍离子及杂质的酸性溶液中回收作为有价金属的钴及镍中的至少钴的方法,其中包括:Co回收用第一萃取步骤,从上述酸性溶液中,通过溶剂萃取而萃取并且反萃取钴离子;Co回收用电解步骤,以Co回收用第一萃取步骤所获得的反萃取后液作为电解液,通过电解而获得电解钴;Co回收用溶解步骤,利用酸使上述电解钴溶解;及Co回收用第二萃取步骤,从Co回收用溶解步骤所获得的钴溶解液,通过溶剂萃取而萃取并且反萃取钴离子。
Description
技术领域
本说明书涉及一种回收作为有价金属的钴或镍的方法,是从对含有锂离子二次电池的正极材料的废弃物实施湿式处理而获得且含有钴离子、镍离子及杂质的酸性溶液中回收作为有价金属的钴或镍。
背景技术
近年来,从资源有效利用的观点出发,广泛研究了从因制品寿命或制造不良以及其他原因所废弃的含有锂离子电池的正极材料的废弃物中,通过湿式处理回收其中所含有的钴或镍的有价金属。
例如为了从含有锂离子二次电池的正极材料的废弃物中回收有价金属,通常将经过焙烧以及其他规定的步骤所获得的电池粉等添加于酸中进行浸取,制成溶解有可含有于其中的锂、镍、钴、锰、铁、铜、铝等的酸性溶液。
然后,通过多个阶段的溶剂萃取或中和等,依序或同时除去溶解于酸性溶液的各金属元素中的铁、铜及铝等,通过溶剂萃取对镍、钴、锰及锂等有价金属进行分离及浓缩,而获得溶解有各金属的溶液。镍或钴从各溶液中通过电解等进行回收(例如参照专利文献1~3)。
现有技术文献
专利文献
专利文献1:日本特开2010-180439号公报
专利文献2:美国专利申请案公开第2011/0135547号说明书
专利文献3:日本专利第5706457号公报
发明内容
发明所解决的课题
此处,如果能够通过上述的回收工艺,从含有锂离子二次电池的正极材料的废弃物中,以硫酸盐等与规定的无机酸的化合物的状态回收高纯度的钴或镍,则由于可将这些化合物用于锂离子二次电池的制造,因此在以有效地再利用作为有限的资源的循环型社会为目标的方面上较为理想。
在此,在利用酸使电池粉等溶解后实施规定的中和或溶剂萃取等而成的酸性溶液中,会有含有钠、铝、锰等这种杂质的情况。由于这种杂质会降低最终获得的钴或镍与无机酸的化合物的纯度,因此要求在回收钴或镍时尽可能地除去。
本说明书提出一种能够有效地除去规定的杂质的有价金属的回收方法。
解决课题的技术手段
本说明书中所记载的有价金属的回收方法,是从对含有锂离子二次电池的正极材料的废弃物实施湿式处理而获得且含有钴离子、镍离子及杂质的酸性溶液中,回收作为有价金属的钴及镍中的至少钴的方法,包括如下步骤:
Co回收用第一萃取步骤,从上述酸性溶液中,通过溶剂萃取而萃取并且反萃取钴离子;
Co回收用电解步骤,以Co回收用第一萃取步骤所获得的反萃取后液作为电解液,通过电解而获得电解钴;
Co回收用溶解步骤,利用酸使上述电解钴溶解;及
Co回收用第二萃取步骤,从Co回收用溶解步骤所获得的钴溶解液中,通过溶剂萃取而萃取并且反萃取钴离子。
发明效果
根据上述的有价金属的回收方法,尤其是通过包括利用酸使上述电解钴溶解的Co回收用溶解步骤,和从Co回收用溶解步骤所获得的钴溶解液中通过溶剂萃取而萃取并且反萃取钴离子的Co回收用第二萃取步骤,能够有效地除去规定的杂质。
附图说明
图1是表示一实施方式的有价金属的回收方法的流程图。
图2是表示用于获得图1的酸性溶液的步骤一例的流程图。
图3是表示实施例的方法的流程图。
具体实施方式
以下,对本说明书中所记载的实施方式详细地进行说明。
一个实施方式的有价金属的回收方法,是对于对含有锂离子二次电池的正极材料的废弃物实施湿式处理而获得且含有钴离子、镍离子及杂质的酸性溶液,进行如图1所例示的各步骤,从其中回收作为有价金属的钴及镍中的至少钴的方法。具体而言,此实施方式包括如下步骤:
Co回收用第一萃取步骤:从酸性溶液中,通过溶剂萃取而萃取并且反萃取钴离子;
Co回收用电解步骤:以Co回收用第一萃取步骤所获得的反萃取后液作为电解液,通过电解而获得电解钴;
Co回收用溶解步骤:利用酸溶解上述电解钴;及
Co回收用第二萃取步骤:从Co回收用溶解步骤所获得的钴溶解液中,通过溶剂萃取而萃取并且反萃取钴离子。
<酸性溶液>
为了获得酸性溶液,例如如图2所示,可在焙烧含有锂离子二次电池的正极材料的废弃物的焙烧步骤后,根据需要进行筛选步骤,并进行对于其筛下使用水等使锂溶解的锂溶解步骤;及利用酸来浸取锂溶解步骤的残渣的酸浸取步骤。可将此浸取后液作为酸浸取液。根据情况,也可以在酸浸取步骤后,对该浸取后液仅进行中和步骤,或仅进行Al、Mn萃取步骤,或者以中和步骤及Al、Mn萃取步骤的顺序进行该两个步骤,将其中和后液或萃取后液作为酸性溶液。以下分别进行详细叙述。但是,只要酸性溶液为对含有锂离子二次电池的正极材料的废弃物实施某些湿式处理而获得的,则不限于此处所记述。
(含有锂离子二次电池的正极材料的废弃物)
作为对象的含有锂离子二次电池的正极材料的废弃物(以下,也简称为“电池废弃物”),是能够在移动电话以及其他各种电子机器等使用的锂离子二次电池,因电池制品寿命或制造不良或其他原因而废弃的含有正极材料的废弃物。从这种电池废弃物中回收有价金属,从有效利用资源的观点出发而优选。另外,在此,其目的在于以高纯度回收作为有价金属的钴及镍,能够再次用于锂离子二次电池的制造。
在此,在该实施方式中,以至少含有钴及镍的电池废弃物作为对象。尤其是电池废弃物通常有含有30质量%以下的钴、30质量%以下的镍的情况。电池废弃物例如有含有0.1质量%~40.0质量%的钴、0.1质量%~15.0质量%的镍的情况。
锂离子二次电池具有含有铝的壳体作为将其周围包入的外装。作为该壳体,例如有仅由铝所构成的,或含有铝及铁、铝薄片等的。另外,锂离子二次电池有如下情况:在上述壳体内含有:正极活性物质,所述正极活性物质由选自由锂、镍、钴及锰所组成的群中的一种单独金属氧化物或两种以上的复合金属氧化物等所构成;和铝箔(正极基材),所述铝箔涂布有正极活性物质并通过例如聚偏二氟乙烯(PVDF)或其他有机粘合剂等紧固。另外,除此以外,有在锂离子二次电池中含有铜、铁等的情况。进而,在锂离子二次电池中,通常在壳体内含有电解液。作为电解液,例如有使用碳酸伸乙酯、碳酸二乙酯等的情况。
电池废弃物可以是由壳体所包围的形态,也可以是已实施破碎、分解或分离等任一处理而成为粉末状的形态。这种粉末状电池废弃物会呈现黑色。另一方面,在以由壳体所包围的形态的电池废弃物作为对象的情况时,可以在焙烧步骤后,进行用于从壳体取出正极材料及负极材料的破碎步骤。
(焙烧步骤)
在焙烧步骤中,对上述电池废弃物进行加热。该焙烧步骤,例如以使电池废弃物中所含有的锂、钴等金属变化为容易溶解的形态等为目的而进行。
在焙烧步骤中,优选对于电池废弃物进行如下加热:例如在450℃~1000℃,优选为600℃~800℃的温度范围保持0.5小时~4小时。该焙烧步骤可使用旋转窑以及其他各种炉,或在大气气氛下进行加热的炉等各种加热设备而进行。
(锂溶解步骤)
在锂溶解步骤中,使经过焙烧步骤的电池废弃物与水接触,使其中所含有的锂溶解。由此,能够在回收工艺的早期阶段使电池废弃物中所含有的锂分离。此处所使用的水可以是自来水、工业用水、蒸馏水、纯化水、离子交换水、纯水、超纯水等。
(酸浸取步骤)
在酸浸取步骤中,将上述锂溶解步骤所获得的残渣添加于硫酸等酸中而进行浸取。酸浸取步骤可利用公知的方法或条件进行,优选为酸性溶液的pH为0~2.0,酸性溶液的氧化还原电位(ORP值,银/氯化银电位基准)为0mV以下。
(中和步骤)
可以对于酸浸取步骤所获得的浸取后液进行下述中和步骤:在浸取后液中添加氢氧化钠、碳酸钠、氨等的碱,使pH上升。由此,可使浸取后液中的铝沉淀而将其除去。但是,该中和步骤也可以省略。
在中和步骤中,优选pH为4.0~6.0,ORP值(ORP vs Ag/AgCl)为-500mV~100mV,液温为50℃~90℃。
在中和步骤中,通常为了抑制由共沉淀所引起的钴或镍的损失,而设为浸取后液中所含有的一部分铝被除去的条件。由此,在中和后液中,铝的剩余部分会以溶解的状态残留。该铝的剩余部分能够由下一萃取步骤除去。中和步骤后的铝浓度一般为0.1g/L~1.0g/L,典型为0.3g/L~0.8g/L。
(Al、Mn萃取步骤)
在酸浸取步骤后,或者在进行中和步骤时,在中和步骤后,进行从浸取后液或中和后液中萃取铝的剩余部分及锰的Al、Mn萃取步骤。然后,此处,通过萃取铝的剩余部分及锰,从而获得除去这些后的萃取残液(水相)。该Al、Mn萃取步骤也可以省略。
在Al、Mn萃取步骤中,优选对于浸取后液或中和后液,使用含有磷酸酯系萃取剂及肟系萃取剂的混合萃取剂。此处,作为磷酸酯系萃取剂,例如可例举二-2-乙基己基磷酸(商品名:D2EHPA或DP8R)等。肟系萃取剂优选醛肟或醛肟为主成分。具体而言,例如有2-羟基-5-壬基苯乙酮肟(商品名:LIX84)、5-十二烷基柳醛肟(商品名:LIX860)、LIX84与LIX860的混合物(商品名:LIX984)、5-壬基柳醛肟(商品名:ACORGAM5640)等,其中,就价格方面等而言,优选为5-壬基柳醛肟。
在该溶剂萃取中,pH优选为2.3~3.5,更优选为2.5~3.0。
可将上述酸浸取步骤所获得的浸取后液、中和步骤所获得的中和后液或Al、Mn萃取步骤所获得的萃取残液作为下述Co回收用步骤中作为对象的酸性溶液。
这种酸性溶液有含有钴离子例如为0g/L~15g/L,典型为5g/L~10g/L的情况,另外,有含有镍离子例如为0g/L~50g/L,典型为5g/L~30g/L的情况。
另外,酸性溶液有含有选自由钠离子、铝离子、锰离子、锂离子所组成的群中的至少一种作为杂质的情况。其中,钠离子是有可能在中和步骤等这样的各种步骤中混入的杂质,而在下述步骤中将其有效地除去是重要的。在含有钠离子时,钠浓度例如为0.1g/L~30g/L,典型为10g/L~20g/L。在含有铝离子时,铝浓度例如为0.000g/L~0.050g/L,典型为0.010g/L~0.020g/L。在含有锰离子时,锰浓度例如为0.000g/L~0.100g/L,典型为0.010g/L~0.050g/L。在含有锂离子时,锂浓度例如为0.000g/L~2g/L,典型为0.100g/L~1.5g/L。除此以外,酸性溶液有含有铁离子和/或铜离子的情况,铁浓度为10mg/L以下,优选为0.005g/L以下,且铜浓度为10mg/L以下,优选为0.005g/L以下。
<Co回收用步骤>
(第一萃取步骤)
为了从上述酸性溶液中回收钴及镍中的钴或两者,而进行第一萃取步骤。该第一萃取步骤是通过溶剂萃取,萃取并且反萃取酸性溶液中的主要的钴离子,因此也称为Co回收用第一萃取步骤。
具体而言,优选进行如下溶剂萃取过程:使用膦酸酯系萃取剂,从酸性溶液中将钴离子萃取至作为溶剂的萃取剂(有机相)。作为膦酸酯系萃取剂,从镍与钴的分离效率的观点出发,优选为2-乙基己基膦酸2-乙基己酯(商品名:PC-88A,Ionquest801)。萃取时的pH优选为5.0~6.0,更优选为5.2~5.7。
接着,对含有萃取后的钴离子的萃取剂(有机相)进行反萃取。使用于反萃取的溶液可为硫酸、盐酸、硝酸等无机酸中的任一者,在通用性上优选为硫酸。此处,在尽可能地将所有的钴离子从有机相萃取至溶液(水相)中的pH的条件下进行。具体而言,pH优选为2~4的范围,进一步优选为2.5~3.5的范围。还有,关于O/A比及次数,可适宜决定。液温可为常温,优选为0℃~40℃。
萃取了钴离子后的萃取剂可在供于反萃取之前,使用洗涤液,进行将该萃取剂中所含有的酸性溶液冲洗的一次以上的洗涤。由此,可将有含于萃取剂中的情况的镍离子或钠离子等从萃取剂中除去。洗涤液例如可为硫酸酸性溶液,pH可为3.5~5.5。用于洗涤后的洗涤液,有含有钴离子的情况,因此为了减少钴的损失,可混合于Co回收用第一萃取步骤中欲萃取钴离子的酸性溶液。
(电解步骤)
上述Co回收用第一萃取步骤所获得的反萃取后液,在Co回收用电解步骤中用作电解液。然后,在该电解步骤中,通过使用该电解液的电解,使其中所含有的钴离子在电极析出而获得电解钴。
在电解步骤中,尤其是可有效地除去钠,进而可有效地除去铝或锰等。因此,在上述酸性溶液中,也可以含有钠离子或铝离子、锰离子,上述中和步骤和/或Al、Mn萃取步骤也可以省略。
电解步骤可利用公知的条件进行,例如可以分别调整液温为40℃~60℃,pH为1.5~2.0,并使电流密度为190A/m2~210A/m2而进行。
(溶解步骤)
在Co回收用溶解步骤中,利用硫酸、或硫酸及氧化剂等酸使电解步骤所获得的电解钴溶解而成为钴溶解液。此时,在电解钴中含有镍的情况下,镍也溶解,而获得含有钴离子及镍离子的钴溶解液。
溶解时的硫酸酸性溶液的pH可以为例如1~5,优选为2~4。若该pH过高,则有钴的浸取变得缓慢的顾虑,另外,若pH过低,则有添加于后续步骤的第二萃取步骤的pH调整剂的量增大的忧虑。
在此所获得的钴溶解液中的钴浓度,例如可以为10g/L~150g/L,优选为100g/L~130g/L。另外,钴溶解液中,使杂质浓度充分地降低至例如钠浓度为5mg/L以下,优选为1mg/L以下,铝及锰的合计浓度为1mg/L以下、优选为0.5mg/L以下的程度。关于铝及锰的合计浓度,在不含有铝及锰中的任一者或两者的情况下,是将其浓度设为零所算出的值。
(第二萃取步骤)
为了从溶解步骤所获得的钴溶解液中,使钴离子从镍离子分离而选择性地进行萃取,而进行通过溶剂萃取进行的第二萃取步骤(Co回收用第二萃取步骤)。还有,在Co回收用步骤中,镍离子可视为杂质处理。
还有在此,为了选择性地萃取钴离子,优选使用掩蔽镍离子而在萃取时残留于水相的掩蔽剂。作为该掩蔽剂,氨离子不掩蔽钴离子但掩蔽镍离子,因此特别有效。另外,氨离子也作为萃取时的pH调整剂发挥作用。
具体而言,能够在使钴溶解液与萃取剂接触之前或之后,在钴溶解液添加氨离子而调整pH,从而萃取钴离子。氨离子例如能够以氨水或氯化铵(NH4Cl)等形态进行添加。在添加氨水时,优选氨水的添加量以相对于钴溶解液的体积比计为1%~10%。
与钴溶解液接触的萃取剂也可以为膦酸(phosphonic acid)系萃取剂或磷酸(phosphoric acid)系萃取剂,优选为次膦酸(phosphinic acid)系萃取剂,其中,进一步优选包含双(2,4,4-三甲基戊基)次膦酸。具体而言,特别优选为SOLVAY公司的ALBRITECT TH1(商品名)或Cyanex272(商品名),但并不限定于此。由此,例如成为与2-乙基己基膦酸2-乙基己酯(PC-88A,Ionquest801)等萃取剂相比pH的低侧与高侧充分隔开的钴及镍的萃取曲线,萃取钴离子但不萃取镍离子的范围扩大。即,仅钴离子的选择性萃取变得更容易。在萃取剂含有双(2,4,4-三甲基戊基)次膦酸时,其纯度例如可设为95%以上。
萃取剂能够使用芳香族系、石蜡系、环烷系等烃系有机溶剂,以浓度成为10~30体积%的方式进行稀释而使用。
作为萃取顺序的一例,添加氨水等,并使钴溶解液(水相)与上述萃取剂(有机相)接触,利用混合机,例如以200~500rpm搅拌混合5~60分钟,使钴离子与萃取剂进行反应。此时的液温为15℃~60℃。其后,利用沉降器,利用比重差将所混合的有机相与水相分离。
溶剂萃取可反复进行,例如也可以为使有机相与水相对流接触的多段方式。O/A比(有机相相对于水相的体积比)一般为0.1~10。
萃取时的平衡pH优选为4~7,特别是进一步优选为5~6。由此,可使镍离子残留于水相,将钴离子有效地萃取至有机相。但是,恰当的pH范围会根据钴浓度或萃取剂的体积分率、油与水的相比、温度等的组合而变化,因此也可以有上述范围外的情况。
在萃取后,对含有钴离子的有机相进行反萃取。反萃取可通过如下方式进行:使用硫酸或盐酸的酸性水溶液等反萃取液,利用混合机等,以200~500rpm搅拌混合5~60分钟。
作为反萃取液,若考虑为下一步骤的硫酸钴的结晶化步骤,则优选使用硫酸。反萃取液的酸浓度优选调整至pH:1.0~3.0,更优选调整至pH:1.5~2.5。
反萃取可在15℃~60℃以下实施。
通过反萃取,钴离子能够从有机相移动至水相侧,从而获得含有钴离子的反萃取后液(水相)。在此,如上述,在萃取时使大量镍离子残留于水相,因此于反萃取后液几乎不含有镍离子。
萃取后液中的钴浓度例如成为1g/L~200g/L,典型为80g/L~100g/L。另外,萃取后液中的镍浓度可以为例如2mg/L以下,典型为1mg/L以下。
(结晶化步骤)
对萃取步骤所获得的反萃取后液,进行使其中所含有的钴离子结晶化的Co回收用结晶化步骤。在此,将反萃取后液加热至例如40℃~120℃进行浓缩,使钴离子作为硫酸钴结晶。
还有,反萃取后液通过经过上述步骤,钴离子以外的杂质被充分地除去。因此,在此实施方式中,可省略在第二萃取步骤后结晶化步骤之前进行用于除去杂质的清洗步骤。因此,在此实施方式中,可对第二萃取步骤所获得的反萃取后液,不经过该清洗步骤而进行结晶化步骤。
如此制造的硫酸钴,由于镍含量优选为5质量ppm以下,镍被充分地除去,因此可有效地用作制造锂离子二次电池及其他电池的原料。
<Ni回收用步骤>
(萃取步骤)
在Ni回收用萃取步骤中,对上述Co回收用第一萃取步骤所获得的萃取残液,优选使用羧酸系萃取剂,从其萃取残液中分离镍离子。作为羧酸系萃取剂,例如有新癸酸、环烷酸等,其中,出于镍离子的萃取能力的原因,优选为新癸酸。
在Ni回收步骤的溶剂萃取中,优选使pH为6.0~8.0,更优选为6.8~7.2。
萃取后,对含有镍离子的有机相,使用硫酸、盐酸或硝酸等反萃取液进行反萃取。通用性上,优选为硫酸。在此,在使Ni从有机相被100%萃取至酸性溶液(水相)的pH的条件下进行。具体而言,pH优选为1.0~3.0的范围,更优选为1.5~2.5。还有,关于O/A比及次数,可适宜决定,O/A比为5~1,更优选为4~2。通过增加反萃取次数,可提高目标金属浓度,成为电解步骤中有利的浓度。
(电解步骤)
在Ni回收用电解步骤中,以Ni回收用萃取步骤所获得的反萃取后液作为电解液,通过电解,使该电解液所含有的镍离子在电极析出而获得电解镍。
电解步骤可利用公知的条件进行,例如可分别调整为液温为40℃~60℃,pH为1.5~2.0,电流密度为190A/m2~210A/m2而进行。
(溶解步骤)
接着,进行Ni回收用溶解步骤,利用硫酸或硫酸及氧化剂等酸使Ni回收用溶解步骤所获得的电解镍溶解,而获得镍溶解液。此溶解结束时的pH可设为例如1~5,优选为2~4。
镍溶解液中的镍浓度例如为10g/L~150g/L,优选为100g/L~130g/L。
另外,镍溶解液的钠浓度优选为5mg/L以下,更优选为1mg/L以下,铝及锰的合计浓度为1mg/L以下,更优选为0.5mg/L以下。通过经过上述各步骤,可如上述那样充分地降低镍溶解液的杂质浓度。
(结晶化步骤)
在Ni回收用结晶化步骤中,将上述镍溶解液加热至例如40℃~120℃进行浓缩,使镍离子作为硫酸镍结晶。
此结晶化步骤所获得的硫酸钴几乎不含有杂质,适于用作制造锂离子二次电池的原料。
实施例
其次,试验性地实施如上述的方法并确认其效果,因此在以下进行说明。但是,此处的说明仅以例示为目的,并非限定于此的意图。
对酸性溶液进行图3所示的各步骤,而获得硫酸钴及硫酸镍。若更详细地叙述,则如下所述。
(酸性溶液)
对黑色粉末状的含有锂离子二次电池的正极材料的废弃物,如上述,依序进行焙烧、锂溶解、酸浸取、中和及Al、Mn萃取的各步骤,获得含有钴离子及镍离子的酸性溶液(溶液B)。将获得了此酸性溶液(溶液B)的Al、Mn萃取的前后的液中的各种金属浓度示于表1。在表1中,溶液A是进行Al、Mn萃取步骤的前的溶液。
[表1]
(Co回收用步骤)
对上述酸性溶液(溶液B)进行第一萃取步骤。第一萃取步骤的萃取条件,是使用2-乙基己基膦酸2-乙基己酯(商品名:PC-88A),萃取时的pH为5.5。由此,获得萃取有钴离子的萃取剂(溶剂a)。萃取残液(溶液C)中的各种金属浓度如表2所示。
[表2]
接着,对萃取有钴离子的萃取剂(溶剂a),进行使用洗涤液的洗涤,制成如表3所示般减少了镍离子等的溶剂b,其后,进行反萃取,获得表4所示的浓度的反萃取后液(溶液D)。洗涤是在pH4.5的条件下进行,反萃取是在pH2.0的条件下进行。
[表3]
[表4]
以上述反萃取后液(溶液D)作为电解液而进行电解步骤,利用硫酸使由此所获得的电解钴溶解后,对此钴溶解液(溶液E)进行第二萃取步骤。第二萃取步骤的萃取条件,是使用双(2,4,4-三甲基戊基)次膦酸而设为pH5.5,反萃取的条件设为pH2.0。将此第二萃取步骤的萃取前后的金属浓度,及反萃取后的金属浓度分别示于表5、6。还有,表5的溶液F是第二萃取步骤的萃取残液。
[表5]
[表6]
对第二萃取步骤的反萃取后液(溶液G),在80℃的条件下进行结晶化步骤,获得硫酸钴。硫酸钴的金属品质如表7所示。如表7所示,可知此硫酸钴是镍或钠等杂质充分减少且钴的纯度高者。
[表7]
(Ni回收用步骤)
进行如下萃取步骤:使用Co回收用步骤中的第一萃取步骤所获得的萃取残液(溶液C),萃取镍离子并且进行洗涤,进而进行反萃取。将此萃取步骤的萃取前后的金属浓度示于表8。另外,将洗涤前后的溶剂c及d的金属浓度示于表9。此时的萃取条件是使用新癸酸而设为pH7,反萃取条件设为pH2。由此,获得表10所示的金属浓度的反萃取后液(溶液I)。
[表8]
[表9]
[表10]
以上述萃取步骤的反萃取后液(溶液I)作为电解液而进行电解步骤,并且进行利用硫酸使由此获得的电解镍溶解的溶解步骤。
其后,通过在80℃的条件下进行浓缩的结晶化步骤,将溶解步骤所获得的镍溶解液制成硫酸镍。将此硫酸镍的成分示于表11。从表11可知,此处所获得的硫酸镍是杂质少且镍的纯度充分高者。
[表11]
Claims (8)
1.一种有价金属的回收方法,是从对含有锂离子二次电池的正极材料的废弃物实施湿式处理而获得且含有钴离子、镍离子及杂质的酸性溶液中回收作为有价金属的钴及镍中的至少钴的方法,其中包括如下步骤:
Co回收用第一萃取步骤,从所述酸性溶液中,通过溶剂萃取而萃取并且反萃取钴离子;
Co回收用电解步骤,以Co回收用第一萃取步骤所获得的反萃取后液作为电解液,通过电解而获得电解钴;
Co回收用溶解步骤,利用酸使所述电解钴溶解;及
Co回收用第二萃取步骤,从Co回收用溶解步骤所获得的钴溶解液中,通过溶剂萃取而萃取并且反萃取钴离子。
2.如权利要求1所述的有价金属的回收方法,其中,所述酸性溶液所含有的杂质中包含钠离子,
在Co回收用溶解步骤所获得的钴溶解液的钠浓度为5mg/L以下。
3.如权利要求1或2所述的有价金属的回收方法,其中,所述酸性溶液所含有的杂质中包含铝和/或锰,
在Co回收用溶解步骤所获得的钴溶解液的铝及锰的合计浓度为1mg/L以下。
4.如权利要求1~3中任一项所述的有价金属的回收方法,其中,还包括如下步骤:
Ni回收用萃取步骤,从Co回收用第一萃取步骤所获得的萃取残液中,通过溶剂萃取而萃取并且反萃取镍离子;
Ni回收用电解步骤,以Ni回收用萃取步骤所获得的反萃取后液作为电解液而进行电解;及
Ni回收用溶解步骤,使Ni回收用电解步骤所获得的电解镍溶解。
5.如权利要求4所述的有价金属的回收方法,其中,还包括Ni回收用结晶化步骤,在Ni回收用溶解步骤所获得的镍溶解液中,使该镍溶解液中所含有的镍离子结晶化。
6.如权利要求4或5所述的有价金属的回收方法,其中,所述酸性溶液所含有的杂质中包含钠离子,
在Ni回收用溶解步骤所获得的镍溶解液的钠浓度为5mg/L以下。
7.如权利要求4~6中任一项所述的有价金属的回收方法,其中,所述酸性溶液所含有的杂质中包含铝和/或锰,
在Ni回收用溶解步骤所获得的镍溶解液的铝及锰的合计浓度为1mg/L以下。
8.如权利要求1~7中任一项所述的有价金属的回收方法,其中,所述酸性溶液含有0.1g/L~30g/L的钠离子。
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