WO2024014540A1 - Procédé d'élimination d'impuretés et procédé de récupération de métaux - Google Patents
Procédé d'élimination d'impuretés et procédé de récupération de métaux Download PDFInfo
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- WO2024014540A1 WO2024014540A1 PCT/JP2023/026110 JP2023026110W WO2024014540A1 WO 2024014540 A1 WO2024014540 A1 WO 2024014540A1 JP 2023026110 W JP2023026110 W JP 2023026110W WO 2024014540 A1 WO2024014540 A1 WO 2024014540A1
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- Prior art keywords
- ions
- metal
- solution
- lithium
- containing solution
- Prior art date
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 131
- 239000002184 metal Substances 0.000 title claims abstract description 131
- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000012535 impurity Substances 0.000 title claims abstract description 56
- 150000002739 metals Chemical class 0.000 title claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 196
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 159
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 86
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 85
- -1 fluoride ions Chemical class 0.000 claims abstract description 61
- 238000000909 electrodialysis Methods 0.000 claims abstract description 51
- 238000000926 separation method Methods 0.000 claims abstract description 37
- 238000002386 leaching Methods 0.000 claims abstract description 35
- 239000002699 waste material Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000002253 acid Substances 0.000 claims abstract description 26
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 23
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 18
- 239000003929 acidic solution Substances 0.000 claims abstract description 15
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 44
- 229910001453 nickel ion Inorganic materials 0.000 claims description 39
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 37
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 32
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 30
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 22
- 239000011574 phosphorus Substances 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 19
- 238000000638 solvent extraction Methods 0.000 claims description 19
- 238000006386 neutralization reaction Methods 0.000 claims description 15
- 229910001437 manganese ion Inorganic materials 0.000 claims description 12
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- 229940085991 phosphate ion Drugs 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical class 0.000 claims description 3
- 238000000605 extraction Methods 0.000 description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 38
- 239000002904 solvent Substances 0.000 description 24
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 22
- 239000011572 manganese Substances 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 18
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 17
- 229910052748 manganese Inorganic materials 0.000 description 17
- 229910017052 cobalt Inorganic materials 0.000 description 16
- 239000010941 cobalt Substances 0.000 description 16
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 16
- 238000005201 scrubbing Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 14
- 229910052744 lithium Inorganic materials 0.000 description 14
- 239000006182 cathode active material Substances 0.000 description 11
- 238000010612 desalination reaction Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 9
- 238000002425 crystallisation Methods 0.000 description 9
- 230000008025 crystallization Effects 0.000 description 9
- 238000007781 pre-processing Methods 0.000 description 8
- 239000003011 anion exchange membrane Substances 0.000 description 7
- 238000005341 cation exchange Methods 0.000 description 7
- 238000007873 sieving Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 150000007522 mineralic acids Chemical class 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000008151 electrolyte solution Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000000717 retained effect Effects 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 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 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical group C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 2
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 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
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- MJUVQSGLWOGIOB-GHRIWEEISA-N 2-[(E)-hydroxyiminomethyl]-4-nonylphenol Chemical compound [H]\C(=N/O)C1=CC(CCCCCCCCC)=CC=C1O MJUVQSGLWOGIOB-GHRIWEEISA-N 0.000 description 1
- 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
- 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
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000013522 chelant 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
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- FLTRNWIFKITPIO-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe] FLTRNWIFKITPIO-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/445—Ion-selective electrodialysis with bipolar membranes; Water splitting
-
- 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
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- 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
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
-
- 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
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/14—Alkali metal compounds
- C25B1/16—Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms
-
- 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
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/04—Specific process operations in the feed stream; Feed pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/06—Specific process operations in the permeate stream
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2311/00—Details relating to membrane separation process operations and control
- B01D2311/26—Further operations combined with membrane separation processes
- B01D2311/2643—Crystallisation
-
- 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
- This specification discloses a method for removing impurities, and a method for recovering metals.
- the process of recovering valuable metals from lithium ion battery waste can include, for example, roasting or other predetermined dry processes of lithium ion battery waste, and wet processes of the battery powder obtained after the dry processes.
- metals such as cobalt, nickel, manganese, lithium, aluminum, and iron in the battery powder are leached with an acid to obtain a metal-containing solution containing the metals dissolved.
- Aluminum ions, iron ions, manganese ions, and the like are then sequentially or simultaneously removed from the metal-containing solution by neutralization or solvent extraction, as described, for example, in Patent Literature 1.
- Cobalt ions and nickel ions in the metal-containing solution are then separated by solvent extraction. After separating the nickel ions by extraction, a metal-containing solution is obtained in which lithium ions remain.
- the neutralization and solvent extraction as described above employ a pH adjusting agent for adjusting a pH by increasing it.
- the pH adjusting agent can be used by separately preparing sodium hydroxide or the like, it is desirable to use a lithium hydroxide solution prepared from the metal-containing solution obtained after solvent extraction of cobalt ions and/or nickel ions or other metals. This can prevent contamination of sodium or the like derived from the separately prepared pH adjusting agent, and also the cost of the pH adjusting agent to be reduced.
- the metal-containing solution contains impurities such as fluoride ions. If such a metal-containing solution is used as a lithium hydroxide solution and circulated in a metal recovery process using it as a pH adjusting agent, there is a risk that the impurities as described above are accumulated and concentrated, affecting the process.
- This specification provides a method for removing impurities that can effectively remove impurities such as fluoride ions, and a method for recovering metals.
- a method for removing impurities disclosed herein is a method for removing impurities from a metal-containing solution obtained by leaching battery powder of lithium ion battery waste with an acid, the method comprising: a metal separation step of separating other metal ions from the metal-containing solution containing lithium ions and the other metal ions; and, after the metal separation step, an electrodialysis step of subjecting the metal-containing solution containing lithium ions and fluoride ions as impurities, to electrodialysis using a bipolar membrane to obtain a lithium hydroxide solution and an acidic solution, wherein the lithium hydroxide solution is used as a pH adjusting agent in the metal separation step.
- the method for recovering metals disclosed herein is a method for recovering metals from battery powder of lithium ion battery waste, the method comprising using the method for removing impurities as described above.
- Fig. 1 is a flow chart showing an example of a method for recovering metals including an impurity removal method according to an embodiment.
- Fig. 2 is a flow chart showing an example of a preprocessing step for obtaining battery powder from lithium ion battery waste.
- Fig. 3 is a cross-sectional view schematically showing an example of a bipolar membrane electrodialysis device that can be used in an electrodialysis step included in an impurity removal method according to an embodiment.
- Fig. 4 is a view showing components of each solution before and after electrodialysis in Example.
- An embodiment of the method for removing impurities is a method for removing impurities from a metal-containing solution obtained by leaching battery powder of lithium ion battery waste with an acid.
- the method includes: a metal separation step of separating other metal ions from the metal-containing solution containing lithium ions and the other metal ions; and, after the metal separation step, an electrodialysis step of subjecting the metal-containing solution containing lithium ions and fluoride ions as impurities to electrodialysis using a bipolar membrane to obtain a lithium hydroxide solution and an acidic solution.
- the lithium hydroxide solution is used as a pH adjusting agent in the metal separation step.
- the method for recovering metals carries out, as a wet process, the acid leaching step of leaching the battery powder of the lithium ion battery waste with an acid to obtain a metal-containing solution, and the metal separation step and the electrodialysis step as described above.
- the lithium hydroxide solution obtained in the electrodialysis step is optionally concentrated and then used as a pH adjusting agent in the metal separation step.
- the metal separation step includes neutralization, solvent extraction of manganese and/or aluminum ions (Mn etc. Extraction), solvent extraction of cobalt ions, and solvent extraction of nickel ions.
- at least one of the neutralization and multiple solvent extraction processes may be omitted.
- the lithium ion battery waste of interest is lithium ion secondary batteries which can be used in various electronic devices such as mobile phones and which have been discarded due to the expired life of the product, manufacturing defects or other reasons.
- the recovery of valuable metals from such lithium ion battery waste is preferred in terms of effective utilization of resources.
- the lithium ion battery waste has a housing containing aluminum as an exterior that wraps around the lithium ion secondary battery.
- the housing include those made only of aluminum and those containing aluminum, iron, aluminum laminate, and the like.
- the lithium ion battery waste may also contain, in the above housing, cathode active materials composed of one single metal oxide containing lithium and one selected from the group consisting of nickel, cobalt and manganese, or a composite metal oxides containing lithium and two or more of those, or the like, and aluminum foils (cathode substrates) to which the cathode active materials are applied and fixed by, for example, polyvinylidene fluoride (PVDF) or other organic binders.
- PVDF polyvinylidene fluoride
- the lithium ion battery waste may contain copper, iron, or the like.
- the housing of the lithium ion battery waste generally contains an electrolytic solution having an electrolyte such as lithium hexafluorophosphate dissolved in an organic solvent.
- an electrolytic solution having an electrolyte such as lithium hexafluorophosphate dissolved in an organic solvent.
- an organic solvent for example, ethylene carbonate, diethyl carbonate or the like may be used as the organic solvent.
- the lithium ion battery waste is subjected to preprocessing as a dry process.
- the preprocessing may include at least one of roasting, crushing and sieving.
- the lithium ion battery waste becomes battery powder through the preprocessing.
- the roasting, crushing, and sieving in the preprocessing step may optionally be performed, respectively, or they may be performed in any order. In the example shown in Fig. 2, the roasting, crushing and sieving are performed in this order.
- the battery powder means a powder obtained by subjecting the lithium ion battery waste to any process to concentrate cathode material components.
- the battery powder may be obtained as a powder by crushing and sieving the lithium ion battery waste with or without a heat treatment to concentrate the cathode material components.
- the above lithium ion battery waste is heated.
- metals such as lithium and cobalt contained in the lithium ion battery waste is changed to an easily dissolvable form.
- the lithium ion battery waste is preferably heated by maintaining it in a temperature range of, for example, from 450°C to 1000°C, further in a temperature range of from 600°C to 800°C, for 0.5 to 4 hours.
- the roasting can be carried out in either an air atmosphere or an inert atmosphere such as nitrogen, and in the air atmosphere and the inert atmospheres in this order or vice versa.
- the roasting can be of batch type or continuous type.
- the batch type includes a stationary furnace
- the continuous type includes a rotary kiln furnace, and other various types of furnaces can also be used.
- the electrolytic solution is removed from the lithium ion battery waste because the electrolytic solution is evaporated, or the like.
- the components of the internal electrolyte are sequentially evaporated, starting with the component having a lower boiling point.
- the resin such as the organic binder is decomposed or vaporized. Even if a part of the electrolyte and the organic binder is thus removed, a certain component such as fluorine contained in the electrolyte and the organic binder remains and may be contained in the battery powder obtained after the preprocessing step.
- the electrolytic solution is removed and rendered harmless, and the organic binder is decomposed to promote separation between the aluminum foil and the cathode active material during crushing and sieving, which will be described below.
- the roasting changes the composition of the cathode active material, the roasted material is also referred to as the cathode active material.
- the crushing can be carried out to remove cathode materials and the like from the housing of the lithium ion battery waste.
- the crushing selectively separates the cathode active materials from the aluminum foils to which the cathode active materials are applied, while destroying the housing of the lithium ion battery waste.
- an impact-type crusher that can crush lithium ion battery waste by applying an impact while cutting it.
- the impact-type crusher include a sample mill, a hammer mill, a pin mill, a wing mill, a tornado mill, and a hammer crusher.
- a screen can be installed at an outlet of the crusher, whereby the lithium ion battery waste is discharged from the crusher through the screen when crushed to a size that can pass through the screen.
- the sieving is performed by sieving it using a sieve having an appropriate opening.
- aluminum or copper remains on the sieve, and battery powder from which Al or Cu has been removed to some extent can be obtained under the sieve.
- the battery powder obtained in the preprocessing step contains lithium, and in addition to lithium, at least one other metal selected from the group consisting of cobalt, nickel, manganese, aluminum, iron and copper.
- the battery powder contains lithium and at least one of nickel and cobalt.
- the lithium content of the battery powder is 2% to 8% by mass
- the cobalt content is 1% to 30% by mass
- the nickel content is 1% to 30% by mass
- the manganese content is 1% to 30% by mass
- the aluminum content is 1% to 10% by mass
- the iron content is 1% to 5% by mass
- the copper content is 1% to 10% by mass.
- the battery powder may also contain 0.1% by mass to 10% by mass of fluorine.
- the battery powder can be brought into contact with water prior to an acid leaching step as described below, in order to extract substantially only lithium from the battery powder. Lithium in the battery powder is thus leached into the water. In this case, the battery powder as the water leached residue is subjected to the acid leaching step.
- the equipment is required, and the processing time increases by performing both the water leaching and the acid leaching in the acid leaching step, as well as it may be necessary to manage the roasting conditions for effectively leaching lithium with water. Further, even with such management, the leaching rate of lithium with water may not be significantly increased. Therefore, the battery powder obtained as described above may be subjected to acid leaching in the acid leaching step without the water leaching. When the water leaching is not carried out, the lithium ion concentration in the liquid can be easily maintained at a higher level in wet processes after the acid leaching step.
- the acid leaching step can be performed by a known method or conditions, but a pH is preferably 0.0 to 2.0, and an oxidation-reduction potential (ORP value, based on silver/silver chloride potential) may be 0 mV or less.
- ORP value based on silver/silver chloride potential
- a leached residue that has remained after the acid leaching can be separated from the metal-containing solution by means of solid-liquid separation such as filtration using a known apparatus and method such as a filter press and a thickener. Most of the copper in the battery powder may be contained in the leached residue.
- the solid-liquid separation may be omitted, and the metal separation step such as neutralization may be performed after leaching without solid-liquid separation.
- the acid leaching step provides the metal-containing solution containing lithium ions and other metal ions.
- the other metal ions may be at least one selected from the group consisting of cobalt ions, nickel ions, manganese ions, aluminum ions, iron ions and copper ions, typically cobalt ions and/or nickel ions.
- the metal-containing solution may also contain fluoride ions.
- the metal-containing solution obtained in the acid leaching step has a cobalt ion concentration of 10 g/L to 50 g/L, a nickel ion concentration of 10 g/L to 50 g/L, a manganese ion concentration of 0 g/L to 50 g/L, an aluminum ion concentration of 1.0 g/L to 20 g/L, an iron ion concentration of 0.1 g/L to 5.0 g/L, a copper ion concentration of 0.005 g/L to 0.2 g/L, and a fluoride ion concentration of 0.01 g/L to 20 g/L.
- the metal-containing solution is subjected to the metal separation step described below.
- the metal separation step carries out neutralization of increasing the pH of the metal-containing solution to separate a neutralized residue to obtain a neutralized solution.
- the neutralization may include an aluminum removal stage and an iron removal stage. However, if the metal-containing solution does not contain aluminum ions and/or iron ions, the aluminum removal step and/or iron removal step may be omitted.
- the pH of the metal-containing solution is increased to precipitate at least a part of the aluminum ions and remove them by solid-liquid separation.
- the pH is increased in the range of 2.5 to 5.0, particularly 3.0 to 4.5 with a pH adjusting agent at a solution temperature of 50°C to 90°C, the aluminum ions can be effectively separated while suppressing precipitation of nickel ions and/or cobalt ions.
- a phosphate ion source is added during a period to the end of the aluminum removal step.
- aluminum ions and phosphate ions in the metal-containing solution react with each other to precipitate aluminum ions as aluminum phosphate or the like, which can be removed by solid-liquid separation.
- the timing of addition of the phosphate ion source is not particularly limited. If the phosphate ions are present in the metal-containing solution during the aluminum removal step, the above reaction will occur during the aluminum removal step.
- the phosphate ion sources include, for example, phosphoric acid (H 3 PO 4 ).
- an oxidizing agent is added and a pH adjusting agent is further added to increase the pH.
- the iron ions are oxidized from divalent to trivalent, and precipitated as a solid such as an oxide or iron hydroxide (Fe(OH) 3 ), which can be removed by solid-liquid separation.
- An oxidation-reduction potential (ORP value, based on silver/silver chloride potential) during oxidation is preferably 300 mV to 900 mV.
- the oxidizing agent is not particularly limited as long as it can oxidize iron, but it may preferably be manganese dioxide, a cathode active material, and/or a manganese-containing leached residue obtained by leaching a cathode active material.
- the manganese-containing leached residue obtained by leaching the cathode active material with the acid may include manganese dioxide.
- the cathode active material or the like When used as the oxidizing agent, it causes a precipitation reaction which converts manganese dissolved in the liquid to manganese dioxide, so that the precipitated manganese can be removed together with iron.
- Examples of the pH adjusting agent used in neutralization in the above aluminum removal stage and iron removal step include lithium hydroxide, sodium hydroxide, sodium carbonate, and ammonia.
- a lithium hydroxide solution obtained in an electrodialysis step as described below is preferably used. In this case, lithium ions are circulated in the wet processes.
- the metal-containing solution can be subjected to solvent extraction to extract and remove the manganese ions, through the above neutralization if necessary.
- the metal-containing solution contains aluminum ions, the manganese ions as well as the aluminum ions are extracted and removed.
- an extracting agent containing a phosphoric acid-based extracting agent specifically a phosphate ester-based extracting agent
- a phosphate ester-based extracting agent examples include di-2-ethylhexylphosphoric acid (abbreviated name: D2EHPA or trade name: DP8R).
- D2EHPA di-2-ethylhexylphosphoric acid
- DP8R trade name: DP8R
- the extracting agent may be a mixture of the phosphate ester-based extracting agent and an oxime-based extracting agent.
- the oxime-based extracting agent is preferably aldoxime or based on aldoxime. Specific examples include 2-hydroxy-5-nonylacetophenone oxime (trade name: LIX84), 5-dodecyl salicylaldoxime (trade name: LIX860), a mixture of LIX84 and LIX860 (trade name: LIX984), 5-nonyl salicylaldoxime (trade name: ACORGAM5640) and the like.
- the extracting agent may be diluted with an aromatic, paraffinic, naphthenic, or other hydrocarbon organic solvent to a concentration of 10% to 30% by volume and used as a solvent.
- an equilibrium pH is preferably 2.3 to 3.5, and more preferably 2.5 to 3.0.
- the pH adjusting agent used at this time it is preferable to use an aqueous lithium hydroxide solution obtained in an electrodialysis step as described below.
- the solvent which has extracted the manganese ions may contain cobalt ions, nickel ions, and lithium ions, these ions that may be contained in the solvent are extracted into an aqueous phase by scrubbing, stripping, and scavenging.
- the scrubbing solution can be, for example, a sulfuric acid solution and can have a pH of 2.0 to 3.0.
- the stripping solution can be, for example, a sulfuric acid solution and can have a pH of 0.0 to 1.0.
- the scrubbed solution, the stripped solution, and the scavenged solution is preferably used in the manganese extraction step (for example, the scrubbed solution is mixed with the metal-containing solution and the mixture is used as a extracting solution to be subjected to the solvent extraction in the manganese extraction step, or the stripped solution is used for the scrubbing in the manganese extraction step, or the scavenged solution is used as the stripping solution in the manganese extraction step).
- the scrubbed solution may contain large amounts of fluoride ions and phosphorus.
- cobalt Extraction and Crystallization For example, after manganese ions are extracted, cobalt ions can be extracted and separated from a manganese extracted solution (metal-containing solution) by solvent extraction.
- a solvent containing a phosphoric acid-based extracting agent especially a phosphonate ester-based extracting agent
- a phosphonate ester-based extracting agent for the extraction of the cobalt ions.
- 2-ethylhexyl 2-ethylhexylphosphonate (trade name: PC-88A, Ionquest 801) is preferable from the viewpoint of separation efficiency between nickel and cobalt.
- the extracting agent may be diluted with a hydrocarbon-based organic solvent so as to have a concentration of 10% by volume to 30% by volume and used as a solvent.
- the metal-containing solution as the cobalt extracted solution and the metal-containing solution to be subjected to the subsequent electrodialysis step tend to contain phosphorus as an impurity.
- the equilibrium pH during extraction is preferably 5.0 to 6.0, and more preferably 5.0 to 5.5. If the pH is less than 5.0, cobalt ions may not be sufficiently extracted into the solvent.
- the pH adjusting agent at this time it is preferable to use an aqueous lithium hydroxide solution obtained in the electrodialysis step as described later.
- the solvent which has extracted the cobalt ions may be subjected to one or more scrubbing processes using a scrubbing solution to remove nickel ions and lithium ions that may be contained in the solvent.
- the scrubbing solution can be, for example, a sulfuric acid solution and can have a pH of 3.5 to 5.5.
- the scrubbed solution may contain nickel ions and lithium ions. Therefore, a part or all of the scrubbed solution is mixed with the manganese extracted solution and it is used as an extracting solution to be subjected to the extraction of the cobalt ions.
- the nickel ions and lithium ions can be circulated or retained in the wet processes without losing them.
- the scrubbed solution may contain large amounts of fluoride ions and phosphorus.
- the fluoride ions and phosphorus removed from the solvent by scrubbing are returned to the metal-containing solution, which may tend to leave fluoride ions and phosphorus until the electrodialysis step.
- the solvent used to extract the cobalt ions does not contain nickel ions or lithium ions, the scrubbing step may not be performed.
- a stripping solution used for the stripping may be any inorganic acid such as sulfuric acid, hydrochloric acid, and nitric acid, but sulfuric acid is preferable when a sulfate is obtained in the next crystallization.
- it is carried out under pH conditions such that all the cobalt ions transfer from the solvent to the stripping solution as much as possible. More particularly, the pH is preferably in the range of 2.0 to 4.0, and more preferably in the range of 2.5 to 3.5.
- the stripped solution can be subjected to crystallization.
- the stripped solution is heated to, for example, 40°C to 120°C and concentrated.
- the cobalt ions are crystallized to obtain a cobalt salt such as cobalt sulfate.
- the cobalt salt thus obtained preferably has a nickel content of 5 ppm by mass or less, and have sufficiently removed the nickel, so that it can be effectively used as a raw material for producing lithium ion secondary batteries and other batteries.
- the crystallized solution may contain uncrystallized cobalt ions and lithium ions.
- the crystallized solution is mixed with the stripped solution before the crystallization and used for recrystallization, or used for adjusting the cobalt ion concentration of the scrubbing solution used for the solvent which has extracted the cobalt ions, or mixed with the manganese extracted solution and used for the extraction of the cobalt ions.
- the cobalt ions and lithium ions can be circulated or retained and concentrated in the wet processes without losing them.
- the cobalt extracted solution (metal-containing solution) after the cobalt ions have been extracted can be subjected to solvent extraction to extract nickel ions.
- a carboxylic acid-based extracting agent is preferably used to separate nickel ions from the cobalt extracted solution.
- the carboxylic acid-based extracting agent include neodecanoic acid and naphthenic acid. Among them, the neodecanoic acid is preferred because of its ability to extract nickel ions.
- the extracting agent may be diluted with an aromatic, paraffinic, naphthenic, or other hydrocarbon organic solvent to a concentration of 10% to 30% by volume and used as a solvent.
- the equilibrium pH during the extraction is preferably 6.0 to 8.0, and more preferably 6.8 to 7.2.
- the pH adjusting agent used to adjust the pH at this time is preferably an aqueous lithium hydroxide solution obtained in an electrodialysis step as described below.
- the solvent which has extracted the nickel ions may optionally be subjected to one or more scrubbing processes using a scrubbing solution to remove lithium ions that may be contained in the solvent.
- the scrubbing solution can be, for example, a sulfuric acid solution and can have a pH of 5.0 to 6.0.
- the resulting scrubbed solution may contain lithium ions. Therefore, it is preferable that a part or all of the scrubbed solution is mixed with the cobalt extracted solution and it is used as the extracting solution to be subjected to the extraction of the nickel ions.
- the lithium ions can be circulated or retained and concentrated in the wet processes without losing them.
- the solvent used to extract the nickel ions does not contain lithium ions, the scrubbing may not be performed.
- the solvent is then subjected to stripping using a stripping solution such as sulfuric acid, hydrochloric acid, or nitric acid.
- a stripping solution such as sulfuric acid, hydrochloric acid, or nitric acid.
- the sulfuric acid is particularly preferred if crystallization is then performed.
- the pH is preferably in the range of 1.0 to 3.0, and more preferably 1.5 to 2.5. Although the O/A ratio and the number of times can be determined as needed, the O/A ratio is 5 to 1, and more preferably 4 to 2.
- the extracted solution such as a nickel sulfate solution
- electrolysis and dissolution can be carried out as needed, and the solution can be then heated to 40°C to 120°C in the crystallization to crystalize the nickel ions as a nickel salt such as nickel sulfate.
- the crystallized solution may contain uncrystallized nickel ions and lithium ions. Therefore, the crystallized solution is mixed with the stripped solution before the crystallization and used for recrystallization, or used for adjusting the nickel ion concentration of the scrubbing solution with respect to the solvent which has extracted the nickel ions, or mixed with the cobalt extracted solution and used for the extraction of the nickel ions.
- the nickel ions and lithium ions can be circulated or retained and concentrated in the wet processes without losing them.
- the nickel extracted solution from which the nickel ions have been extracted mainly contains lithium ions and may be added to the acidic leaching solution in the leaching step. This allows the lithium ions contained in the nickel extracted solution to be circulated in a series of steps from the acid leaching step to the nickel extraction. Preferably, after the lithium ion concentration in the nickel extracted solution has been increased to some extent by thus circulating the lithium ions, an electrodialysis step as described below can be carried out.
- the metal-containing solution such as the extracted nickel solution obtained in the metal separation step described above is one in which lithium ions and metals other than impurities are sufficiently separated, and mainly contains lithium ions.
- the metal-containing solution contains fluoride ions (F - ) as impurities derived from, for example, the electrolytic solution contained in the battery powder.
- the impurities may also include phosphorus (P).
- Phosphorus in particular, tends to be contained, which is derived from the contamination of the phosphoric acid-based extractant used upon multiple solvent extraction processes such as manganese extraction and cobalt extraction in the liquid.
- the metal-containing solution may contain a relatively large amount of phosphorus as an impurity.
- Other impurities may include silicon derived from, for example, glass fibers in the lithium ion battery waste.
- the metal-containing solution may contain trace amounts of cations such as nickel ions and magnesium ions that could not be completely separated in the metal separation step.
- the nickel ions and magnesium ions are cations like lithium ions, and exhibit the same behavior as lithium ions during electrodialysis, so that it is difficult to separate them from lithium ions.
- hydroxides of nickel and magnesium may be generated in the resulting lithium hydroxide solution, and the electrodialysis cannot be continued due to troubles of the steps. Therefore, in such a case, it is desirable to wash the metal-containing solution to remove cations such as nickel ions and magnesium ions prior to the electrodialysis which will be described below.
- the washing can be carried out using an ion exchange resin or a chelate resin, for example.
- the metal-containing solution prior to the electrodialysis step may, for example, have a lithium ion concentration of 1.0 g/L to 30.0 g/L, a fluoride ion concentration of 0.01 g/L to 5.0 g/L, a phosphorus concentration of 0.001 g/L to 1.0 g/L, and a silicon concentration of 0.001 g/L to 1.0 g/L.
- lithium hydroxide solution When a lithium hydroxide solution is obtained from the above metal-containing solution, application of carbonation, chemical conversion, or the like causes impurities to remain in the lithium hydroxide solution without being removed.
- the use of the lithium hydroxide solution containing larger amounts of impurities as a pH adjusting agent in the metal separation step is undesirable because not only lithium ions but also impurities are circulated or accumulated in the wet processes.
- the metal-containing solution is subjected to the electrodialysis step to obtain a lithium hydroxide solution and an acidic solution from the metal-containing solution.
- the metal-containing solution is subjected to the electrodialysis step to obtain a lithium hydroxide solution and an acidic solution from the metal-containing solution.
- the electrodialysis step can be performed, for example, using a commercially available bipolar membrane electrodialysis device.
- a bipolar membrane electrodialysis device 1 (hereinafter, also referred to as a “electrodialysis device”) shown in Fig.3 has, in a cell, a positive electrode 2 and a negative electrode 3; and a bipolar membrane 4, an anion exchange membrane 5, a cation exchange membrane 6, and a bipolar membrane 7, which are arranged in this order between the positive electrode 2 and the negative electrode 3 from the positive electrode 2 side to the negative electrode 3 side.
- Each of the bipolar membranes 4 and 7 is constructed by laminating a cation exchange layer and an anion exchange layer.
- the metal-containing solution is placed in the desalination chamber R1, and pure water is also placed in each of the acidic chamber R2 and the alkaline chamber R3, and a predetermined voltage is applied to the positive electrode 2 and the negative electrode 3.
- lithium ions (Li + ) in the metal-containing solution in the desalination chamber R1 pass through the cation exchange membrane 6 and move to the alkaline chamber R3.
- water (H 2 O) is decomposed by the bipolar membrane 7 and hydroxide ions (OH - ) are present, so that a lithium hydroxide solution is obtained.
- the anions of the inorganic acid in the metal-containing solution in the desalination chamber R1 pass through the anion exchange membrane 5 and move to the acidic chamber R2.
- an acidic solution such as a sulfuric acid solution is generated by the anions and hydrogen ions (H + ) generated from water (H 2 O) by the bipolar membrane 4.
- the lithium hydroxide solution obtained in the alkaline chamber R3 contains substantially no inorganic acid anions.
- the anions of the inorganic acid are sulfate ions (SO 4 2- ) in the illustrated example, but they may be nitrate ions (NO 3 - ) or chloride ions (Cl - ) depending on the type of the acid used in the acid leaching step.
- the lithium salt is separated from the metal-containing solution as described above, and a desalinated solution remains.
- the anion concentration of the inorganic acid tends to be higher in the acidic solution than in the lithium hydroxide solution, and tends to be higher in the desalinated solution than in the lithium hydroxide solution.
- the impurity fluoride ions in the metal-containing solution move from the desalination chamber R1 to the acidic chamber R2 through the anion exchange membrane 5 and are contained in the acidic solution.
- the silicon as an impurity can also migrate into the acidic solution.
- a lithium hydroxide solution substantially free of fluoride ions and silicon is obtained in the alkaline chamber R3. Therefore, the fluoride ion concentration of the lithium hydroxide solution is lower than that of the acidic solution.
- the lithium hydroxide solution obtained by electrodialysis contains substantially no phosphorus. Therefore, the phosphorus concentration of the desalinated solution remaining in the desalination chamber R1 after the lithium salt is separated from the metal-containing solution is higher than the phosphorus concentration of the lithium hydroxide solution.
- the lithium hydroxide solution from which impurities have been removed by electrodialysis as described above can be effectively used as a pH adjusting agent in the metal separation step.
- the lithium hydroxide solution may optionally be used as a pH adjusting agent after increasing the lithium ion concentration of the lithium hydroxide solution by heat concentration or the like.
- a part of the lithium hydroxide solution obtained in the electrodialysis step can be subjected to a crystallizing step.
- the lithium hydroxide solution is returned to the wet process as a pH adjusting agent as described above, the lithium in the battery powder newly added to the wet process may gradually increase the lithium ion concentration in the liquid.
- the crystallizing step may be performed to recover lithium hydroxide.
- a crystallizing operation such as heat concentration or vacuum distillation can be performed in order to crystallize lithium hydroxide.
- heat concentration a higher temperature during crystallizing leads to faster progression of the process, which is preferable.
- the temperature of the crystallized product after crystallizing can be a temperature of less than 60°C at which water in the crystallized product is not released. This is because anhydrous lithium hydroxide from which the water has been released is deliquescent and thus difficult to be handled.
- the lithium hydroxide solution obtained in the electrodialysis step contains substantially no inorganic acid anions such as sulfate ions. Therefore, the lithium hydroxide produced in the crystallization step will have higher purity and improved quality.
- a pulverization process or the like can be then performed in order to adjust the above lithium hydroxide to required physical properties.
- the metal-containing solution obtained by leaching the battery powder with sulfuric acid was subjected to neutralization, manganese extraction, cobalt extraction and nickel extraction to separate each metal.
- the separated metal-containing solution was then subjected to electrodialysis using a bipolar membrane electrodialysis device (manufactured by ASTOM Corporation) having a structure as shown in Fig. 3.
- a bipolar membrane electrodialysis device manufactured by ASTOM Corporation
- the metal-containing solution having each composition shown in Fig. 4 pure water, and an electrode solution were introduced into the desalination chamber, the alkaline chamber, the acidic chamber, and the electrode chamber, respectively.
- the electrodialysis was carried out under the condition of a constant voltage of 32V.
- bipolar membrane electrodialysis device positive electrode 3 negative electrode 4, 7 bipolar membrane 5 anion exchange membrane 6 cation exchange membrane R1 desalination chamber R2 Acidic chamber R3 alkaline chamber
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Abstract
L'invention concerne un procédé d'élimination d'impuretés qui permet d'éliminer efficacement des impuretés telles que des ions fluorure, et un procédé de récupération de métaux. Le procédé d'élimination d'impuretés d'une solution contenant des métaux obtenue par la lixiviation d'une poudre de batterie de déchets de batterie au lithium-ion avec un acide comprend : une étape de séparation de métaux consistant à séparer d'autres ions métalliques de la solution contenant des métaux contenant des ions lithium et les autres ions métalliques ; et, après l'étape de séparation de métaux, une étape d'électrodialyse consistant à soumettre la solution contenant des métaux contenant des ions lithium, et des ions fluorure en tant qu'impuretés, à une électrodialyse à l'aide d'une membrane bipolaire pour obtenir une solution d'hydroxyde de lithium et une solution acide, la solution d'hydroxyde de lithium étant utilisée en tant qu'agent d'ajustement de pH à l'étape de séparation de métaux.
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EP3950978A1 (fr) * | 2019-03-29 | 2022-02-09 | JX Nippon Mining & Metals Corporation | Procédé pour traiter des déchets de batterie lithium-ion |
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JPH1197076A (ja) * | 1997-09-18 | 1999-04-09 | Toshiba Corp | 電池の処理方法 |
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