WO2023054667A1 - 廃リチウムイオン電池からリチウムを回収する方法 - Google Patents
廃リチウムイオン電池からリチウムを回収する方法 Download PDFInfo
- Publication number
- WO2023054667A1 WO2023054667A1 PCT/JP2022/036663 JP2022036663W WO2023054667A1 WO 2023054667 A1 WO2023054667 A1 WO 2023054667A1 JP 2022036663 W JP2022036663 W JP 2022036663W WO 2023054667 A1 WO2023054667 A1 WO 2023054667A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- lithium
- alkali metal
- ion batteries
- recovering
- group
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 116
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 93
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 70
- 239000002699 waste material Substances 0.000 title claims abstract description 60
- 239000007864 aqueous solution Substances 0.000 claims abstract description 100
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 84
- 239000002253 acid Substances 0.000 claims abstract description 74
- 239000000243 solution Substances 0.000 claims abstract description 49
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims abstract description 48
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 47
- 239000011707 mineral Substances 0.000 claims abstract description 47
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 239000011149 active material Substances 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 27
- 238000000638 solvent extraction Methods 0.000 claims abstract description 24
- 150000002739 metals Chemical class 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 105
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 76
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 64
- 239000012266 salt solution Substances 0.000 claims description 64
- 229910003002 lithium salt Inorganic materials 0.000 claims description 54
- 159000000002 lithium salts Chemical class 0.000 claims description 54
- 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 52
- 229910052708 sodium Inorganic materials 0.000 claims description 52
- 239000011734 sodium Substances 0.000 claims description 52
- 238000000926 separation method Methods 0.000 claims description 49
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 46
- 238000000605 extraction Methods 0.000 claims description 45
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 40
- 229910052700 potassium Inorganic materials 0.000 claims description 40
- 239000011591 potassium Substances 0.000 claims description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 34
- 150000001340 alkali metals Chemical class 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 28
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 26
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 26
- 150000003839 salts Chemical class 0.000 claims description 19
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 238000010248 power generation Methods 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims 2
- 238000011084 recovery Methods 0.000 abstract description 35
- -1 alkali metal salt Chemical class 0.000 abstract description 16
- 238000004064 recycling Methods 0.000 abstract description 6
- 238000007781 pre-processing Methods 0.000 abstract 1
- 235000010755 mineral Nutrition 0.000 description 40
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 24
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 24
- 239000012528 membrane Substances 0.000 description 24
- 238000010979 pH adjustment Methods 0.000 description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 239000010941 cobalt Substances 0.000 description 18
- 229910017052 cobalt Inorganic materials 0.000 description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 18
- 239000011780 sodium chloride Substances 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 239000003960 organic solvent Substances 0.000 description 16
- 239000012074 organic phase Substances 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 12
- 229910052759 nickel Inorganic materials 0.000 description 12
- 239000001103 potassium chloride Substances 0.000 description 12
- 235000011164 potassium chloride Nutrition 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 239000002002 slurry Substances 0.000 description 11
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 9
- 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 9
- 239000003513 alkali Substances 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 208000028659 discharge Diseases 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 7
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 7
- 159000000001 potassium salts Chemical class 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000001223 reverse osmosis Methods 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 6
- 230000026731 phosphorylation Effects 0.000 description 6
- 238000006366 phosphorylation reaction Methods 0.000 description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 description 6
- 159000000000 sodium salts Chemical class 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 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 5
- 239000000460 chlorine Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- MGBKJKDRMRAZKC-UHFFFAOYSA-N 3-aminobenzene-1,2-diol Chemical compound NC1=CC=CC(O)=C1O MGBKJKDRMRAZKC-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 3
- 150000008041 alkali metal carbonates Chemical class 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- IPPTUFJBKCMXJL-UHFFFAOYSA-N C(C)C(CC(C(CCCC)CC)OP(O)=O)CCCC Chemical compound C(C)C(CC(C(CCCC)CC)OP(O)=O)CCCC IPPTUFJBKCMXJL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- KLMCZVJOEAUDNE-UHFFFAOYSA-N francium atom Chemical compound [Fr] KLMCZVJOEAUDNE-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000006166 lysate Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- 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
-
- 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
-
- 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
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
- C25C3/02—Electrolytic production, recovery or refining of metals by electrolysis of melts of alkali or alkaline earth metals
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Definitions
- the present invention relates to a method for recovering lithium from waste lithium-ion batteries, in which metal contained in active material powder obtained by pretreatment of waste lithium-ion batteries is separated by a wet process to recover lithium.
- the valuable metal obtained by pulverizing and classifying the waste lithium ion battery without heat treatment (roasting) or heat treatment Cobalt, nickel, manganese, and lithium are separated and purified from a powder containing (hereinafter referred to as active material powder) by a wet process (see, for example, Patent Documents 1 and 2).
- waste lithium-ion batteries refer to used lithium-ion batteries whose service life as a battery product has been exhausted, lithium-ion batteries discarded as defective products in the manufacturing process, and lithium-ion batteries that were used for commercialization in the manufacturing process. It means the remaining positive and negative electrode materials and the like.
- the present invention eliminates such disadvantages, enables lithium to be recovered at a high recovery rate, enables resource recycling, and requires a large amount of energy when recovering lithium from a low-concentration lithium salt aqueous solution. It is an object of the present invention to provide a system for recovering valuable metals from waste lithium ion batteries capable of simplifying the entire process without removing waste.
- the method for recovering lithium from waste lithium ion batteries of the present invention comprises dissolving an active material powder obtained by pretreating a waste lithium ion battery in a mineral acid to obtain a powder containing at least lithium.
- a dissolving step of obtaining an acid solution of the active material an alkali metal hydroxide adding step of adding an alkali metal hydroxide to the acid solution obtained in the dissolving step, and an alkali metal hydroxide adding step.
- the first aqueous alkali metal salt solution is electrolyzed using an ion-exchange membrane to produce an aqueous alkali metal hydroxide solution, an acid, and a second aqueous alkali metal salt solution that is more dilute than the first aqueous alkali metal salt solution. and reusing the alkali metal hydroxide aqueous solution obtained in the first electrolysis step in at least one selected from the group consisting of the alkali metal hydroxide addition step and the extraction step. and at least one selected from the group consisting of a mineral acid obtained by recovering the gas generated in the first electrolysis step and a mineral acid obtained in the anode chamber of the first electrolysis step in the dissolution step It is characterized by being reusable.
- the active material powder obtained by pretreatment of the waste lithium ion batteries is dissolved in a mineral acid, and the active material containing at least lithium is acidified. Obtain a lysate.
- the acid solution contains a valuable metal contained in the active material powder, and examples of the valuable metal include metals such as iron, aluminum, manganese, cobalt, and nickel in addition to the lithium. be able to.
- an alkali metal hydroxide is added to the acid solution.
- the pH of the acid solution can be adjusted (neutralized).
- At least one of the metals contained in the active material powder, excluding lithium, is extracted from the acid solution to which the alkali metal hydroxide is added.
- the metals can be separated by solvent extraction to obtain a first aqueous alkali metal salt solution.
- the first aqueous alkali metal salt solution is subjected to a first electrolysis step using an ion exchange membrane.
- an aqueous alkali metal hydroxide solution, an acid, and a second aqueous alkali metal salt solution that is thinner than the first aqueous alkali metal salt solution can be obtained.
- At least one selected from the group consisting of the alkali metal hydroxide addition step and the extraction step is used to partially remove the alkali metal hydroxide aqueous solution. reuse in. Furthermore, the said acid is used as said mineral acid.
- the method for recovering lithium from waste lithium ion batteries of the present invention since an alkali metal hydroxide is used as an alkali source, the recovery rate of lithium can be improved. No source compounds are excreted. Further, according to the method for recovering lithium from waste lithium ion batteries of the present invention, the first alkali metal salt aqueous solution obtained from the solvent extraction of the acid solution is subjected to the first electrolysis step. By returning the alkali metal hydroxide and the mineral acid to the step before the first electrolysis step, resource recycling can be performed.
- the second aqueous alkali metal salt solution it is preferable to concentrate the second aqueous alkali metal salt solution and add it to the first aqueous alkali metal salt solution. By doing so, the second aqueous alkali metal salt solution is recovered without being discharged, so that the recovery rate of lithium can be further improved, and resource recycling can be performed.
- the mineral acid includes, for example, at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid. is preferred.
- hydrochloric acid when used as the mineral acid, when the first aqueous alkali metal salt solution is subjected to the first electrolysis step using an ion exchange membrane, chlorine gas and hydrogen gas can be obtained. Therefore, it is preferable to react the chlorine gas and the hydrogen gas to produce hydrochloric acid, and use the produced hydrochloric acid as the mineral acid.
- the power used in the first electrolysis step preferably includes power obtained from renewable energy.
- Examples of electric power include electric power obtained by solar power generation and electric power obtained by wind power generation.
- FIG. 2 is an explanatory diagram showing the configuration of a method for recovering lithium from a waste lithium-ion battery according to the first embodiment
- FIG. 2 is an explanatory cross-sectional view showing the structure of an ion-exchange membrane electrolytic cell used in the method of recovering lithium from waste lithium-ion batteries of the first and third embodiments
- FIG. 5 is an explanatory diagram showing the configuration of a method for recovering lithium from a waste lithium ion battery according to the second embodiment
- FIG. 4 is an explanatory cross-sectional view showing the structure of an ion-exchange membrane electrolytic cell used in the method of recovering lithium from waste lithium-ion batteries according to the second and third embodiments
- FIG. 11 is an explanatory diagram showing the configuration of a method for recovering lithium from a waste lithium-ion battery according to the third embodiment; Explanatory drawing which shows the lithium phosphate method in 3rd Embodiment.
- the method of recovering valuable metals from waste lithium-ion batteries according to the first embodiment of the present invention uses active material powder 1 as a starting material.
- the active material powder 1 is first: A discharge treatment is performed in salt water to discharge all remaining electric charges. Next, after forming an opening in the housing of the waste lithium ion battery, for example, after heat treatment (roasting) at a temperature in the range of 100 to 800 ° C., or without heat treatment, a hammer mill, jaw crusher, etc. It can be obtained by pulverizing with a pulverizer and removing (classifying) the housing, current collector, etc. constituting the waste lithium ion battery by sieving.
- the waste lithium ion battery after the discharge treatment is pulverized with the pulverizer, the housing, current collector, etc. are removed by sieving, and then heat treatment is performed at a temperature in the above range to obtain an active material powder. 1 may be obtained.
- the heat treatment is performed at a temperature within the above range without performing the discharge treatment and the formation of the opening. Afterwards, or without heat treatment, it may be pulverized with the above-mentioned pulverizer, and the current collector and the like may be removed by sieving to obtain the active material powder 1. After removing by sieving, the active material powder 1 may be obtained by performing a heat treatment at a temperature within the above range.
- the active material powder 1 is dissolved in mineral acid to obtain an acid solution of the active material powder 1 containing at least lithium.
- the mineral acid includes, for example, one acid selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid, and preferably includes hydrochloric acid.
- the active material powder 1 contains valuable metals such as iron, aluminum, manganese, cobalt and nickel in addition to the lithium.
- lithium hydroxide LiOH
- the neutralized acid solution is then subjected to solvent extraction in STEP3.
- solvent extraction among the valuable metals, manganese, cobalt, and nickel, excluding lithium, are separately solvent-extracted, or iron and aluminum are separated and removed as respective metal sulfate aqueous solutions 2, and the first lithium salt is obtained.
- Aqueous solutions can be obtained.
- the lithium salt contained in the first lithium salt aqueous solution becomes lithium chloride when hydrochloric acid is used in the acid dissolution in STEP1.
- step 4 the first lithium salt aqueous solution is subjected to the first electrolysis step using an ion exchange membrane.
- electrolysis in the first electrolysis step using the ion exchange membrane is called membrane electrolysis.
- the membrane electrolysis in step 4 can be performed using, for example, an electrolytic bath 11 shown in FIG.
- the electrolytic cell 11 has an anode plate 12 on one inner surface and a cathode plate 13 on the inner surface facing the anode plate 12, the anode plate 12 is connected to the anode 14 of the power source, and the cathode plate 13 is the cathode of the power source. 15 is connected.
- the electrolytic cell 11 is partitioned by an ion exchange membrane 16 into an anode chamber 17 having an anode plate 12 and a cathode chamber 18 having a cathode plate 13 .
- water (H 2 O) is ionized into hydroxide ions (OH ⁇ ) and hydrogen ions (H + ), and the hydrogen ions generate hydrogen gas (H 2 ) on the cathode plate 13, Hydroxide ions combine with lithium to produce lithium hydroxide aqueous solution 3 .
- electric power obtained by renewable energy such as electric power obtained by solar power generation and electric power obtained by wind power generation can be used.
- hydrochloric acid can be obtained as the mineral acid 4 by reacting hydrogen gas (H 2 ) and chlorine gas (Cl 2 ) generated in the membrane electrolysis in the first electrolysis step.
- the acid 4 can be used for dissolving the active material powder 1 in STEP1.
- the lithium hydroxide aqueous solution 3 obtained by membrane electrolysis in the first electrolysis step can also be recovered as lithium hydroxide monohydrate (LiOH.H 2 O) by crystallization in STEP 5, and is carbonated in STEP 6. By doing so, it can also be recovered as lithium carbonate (Li 2 CO 3 ).
- the carbonation can be performed by reacting the lithium hydroxide aqueous solution 3 with carbon dioxide (CO 2 ).
- part of the lithium hydroxide aqueous solution 3 obtained by membrane electrolysis in the first electrolysis step is used as lithium hydroxide to be added to the acid solution in STEP 2, and It can be used for at least one application selected from the group consisting of use for solvent extraction.
- the lithium hydroxide aqueous solution 3 is used for solvent extraction in STEP 3
- the lithium hydroxide aqueous solution 3 is added to the extraction solvent. Since the extraction solvent used for solvent extraction in STEP 3 is a cation exchange extractant, if it is used continuously, the liquid properties will be biased toward the acidic side and the extraction rate will decrease. rate reduction can be suppressed.
- the lithium hydroxide aqueous solution 3 when used for solvent extraction in STEP 3, the lithium hydroxide aqueous solution 3 can be used for at least one of the solvent extractions of manganese, cobalt, and nickel, which are performed separately.
- the second aqueous lithium salt solution is concentrated in STEP7 and added to the first aqueous lithium salt solution. Concentration in STEP 7 can be performed using, for example, a reverse osmosis membrane (RO membrane).
- RO membrane reverse osmosis membrane
- the recovery method of the first embodiment since no alkali source other than lithium is supplied, a high-concentration lithium salt aqueous solution can be obtained.
- lithium hydroxide can be obtained by electrolyzing the high-concentration lithium salt aqueous solution in the first electrolysis step, the recovery rate of lithium can be improved.
- the lithium hydroxide obtained by the electrolysis in the first electrolysis step can be returned to the process as it is, thereby recycling resources. can be made possible.
- the recovery method of the second embodiment comprises adding at least one selected from the group consisting of sodium hydroxide and potassium hydroxide to the solution of the valuable metal obtained in the dissolving step (STEP 1). including the material addition step (STEP 2a).
- FIG. 3 shows the case where only sodium hydroxide is added as the alkali metal hydroxide.
- At least one addition selected from the group consisting of sodium hydroxide and potassium hydroxide consists of addition of at least one solid selected from the group consisting of sodium hydroxide and potassium hydroxide, aqueous sodium hydroxide solution and aqueous potassium hydroxide solution. It may be at least one addition selected from the group or at least one of these mixed forms.
- the valuable metal solution is neutralized in the alkali metal hydroxide addition step. Further iron hydroxide and aluminum hydroxide are sequentially precipitated by the addition of at least one of sodium hydroxide and potassium hydroxide to the solution of the valuable metal, and the iron and aluminum are separated from the solution of the valuable metal.
- At least one of iron, aluminum, manganese, cobalt, and nickel contained in the active material powder 1 is removed by solvent extraction from the solution obtained in the alkali metal hydroxide addition step.
- Lithium, sodium, manganese, cobalt, and nickel are contained in the solution of valuable metal neutralized in the alkali metal hydroxide addition step. If iron and aluminum have not been removed in the alkali metal hydroxide addition step, iron and aluminum are also included in the solution of valuable metals.
- the extraction step includes a first extraction step of extracting iron, aluminum, manganese, cobalt, or nickel from the solution of the valuable metal with a first organic solvent.
- the pH of the homogeneous mixture of the valuable metal solution and the first organic solvent is adjusted by the addition of an alkali, such as at least one of sodium hydroxide and potassium hydroxide, to provide a first metal-containing organic phase and a first organic solvent. 1 extraction bottoms are obtained in the first extraction step.
- the extraction step may include a second extraction step of extracting valuable metals not extracted in the first extraction step from the first extraction residue with a second organic solvent.
- the pH of the homogeneous mixture of the first extraction bottoms and the second organic solvent is adjusted by the addition of an alkali such as at least one of sodium hydroxide and potassium hydroxide to form a second metal-containing organic phase; A second extraction bottoms is obtained in the second extraction step.
- the extraction step may include third to fifth extraction steps for sequentially extracting the valuable metals that have not been extracted in the first and second extraction steps from the second extraction residue.
- organic solvents used in the extraction step include bis(2-ethylhexyl) hydrogen phosphate, 2-ethylhexyl(2-ethylhexyl) phosphonate, and bis(2,4,4-trimethylpentyl)phosphinic acid.
- the organic solvent may be diluted with a hydrocarbon such as kerosene.
- the iron-containing organic phase, the aluminum-containing organic phase, the manganese-containing organic phase, the cobalt-containing organic phase, and the nickel-containing organic phase are each subjected to back extraction with sulfuric acid to obtain metal sulfates (iron sulfate, aluminum sulfate, manganese sulfate). , cobalt sulfate, and nickel sulfate) aqueous solution 2 is recovered.
- the recovery method of the second embodiment is obtained in the extraction step, lithium as a residual liquid of solvent extraction, and lithium salt, sodium and potassium from an alkali metal mixed salt aqueous solution containing at least one of sodium and potassium.
- a separation step (STEP 4a) for separating each of the at least one salt.
- the separation step is not limited to a specific method, but is preferably carried out by at least one selected from the group consisting of a lithium phosphate method, an evaporative concentration method, and a solvent extraction method.
- the lithium phosphate method will be described with reference to FIG.
- aluminum phosphate and at least one alkali metal hydroxide (MOH) aqueous solution of sodium hydroxide and potassium hydroxide are added to the alkali metal mixed salt aqueous solution to produce lithium phosphate and aluminum hydroxide.
- MOH alkali metal hydroxide
- a phosphorylation step STP A
- MCl Alkali metal chloride
- the alkali metal hydroxide is preferably sodium hydroxide.
- FIG. 4 shows the case where only sodium hydroxide is used as the alkali metal hydroxide.
- the lithium phosphate method includes a first solid-liquid separation (STEP B) for solid-liquid separation of the solid produced in the phosphorylation step. Filtration is mentioned as the said 1st solid-liquid-separation process, for example.
- the solid matter separated in the first solid-liquid separation step may be washed.
- a pH adjustment step (STEP C) is included in which a mineral acid is added to a suspension obtained by suspending the solid matter in water to adjust the pH of the suspension to 2-3.
- the mineral acid is not limited to a specific mineral acid.
- the mineral acid contains at least one selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid.
- the mineral acid is preferably at least one selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid, more preferably hydrochloric acid, sulfuric acid, or nitric acid, and still more preferably hydrochloric acid.
- the lithium salt is lithium chloride and FIG. 4 describes this case.
- the lithium phosphate method includes a second solid-liquid separation step (STEP D) for solid-liquid separation of the aluminum phosphate and lithium salt aqueous solution obtained in the pH adjustment step. Filtration is mentioned as the said 2nd solid-liquid-separation process, for example.
- the aluminum phosphate obtained in the second solid-liquid separation step can be solid-liquid separated in a short time, and the solid-liquid separated aluminum phosphate is reused in the phosphorylation step.
- the pH of the lithium salt aqueous solution obtained in the second solid-liquid separation step is preferably adjusted in the pH adjustment step (STEP 5a) described later. Since the pH of the suspension is adjusted to 2 to 3 in the pH adjustment step (STEP C), the pH of the lithium salt aqueous solution is 2 to 3, and the pH is adjusted to the pH adjustment step (STEP 5a ), preferably adjusted to 6-8. In this case, unreacted aluminum and phosphorus precipitate and the purity of the lithium salt aqueous solution becomes higher.
- the lithium salt aqueous solution whose pH has been adjusted in the pH adjustment step (STEP 5a) is carbonated to obtain lithium carbonate, and a carbonation step (STEP 6a), which will be described later, is performed.
- At least one salt solution of sodium and potassium generated in the carbonation step contains at least one selected from the group consisting of sodium chloride and potassium chloride, a trace amount of lithium chloride, and a group consisting of sodium carbonate and potassium carbonate. At least one dissolves, and the pH of the at least one salt aqueous solution preferably selected from the group consisting of sodium and potassium is about 12.
- aqueous solution in which at least one selected from the group consisting of sodium chloride and potassium chloride is dissolved.
- the aqueous solution may be concentrated in (STEP 9) in the concentration step described later.
- FIG. 4 describes a case where the concentration step is performed.
- the filtrate in which the alkali metal chloride is dissolved and separated in the first solid-liquid separation step may be concentrated in the concentration step (STEP 9) described later.
- ⁇ Evaporative concentration method in the second embodiment> The lithium and at least one alkali metal mixed salt aqueous solution selected from the group consisting of sodium and potassium is evaporated and concentrated to comprise a sodium salt and a potassium salt, such as at least one selected from the group consisting of sodium chloride and potassium chloride. At least one selected from the group is sequentially crystallized and separated from the alkali metal mixed salt aqueous solution.
- At least one selected from the group consisting of sodium and potassium salts such as at least one selected from the group consisting of sodium chloride and potassium chloride, dissolved in water, and at least one selected from the group consisting of sodium and potassium
- a first electrolysis step (STEP 7a), which will be described later, is performed in which two salt solutions are electrolyzed using an ion-exchange membrane.
- the lithium salt aqueous solution from which at least one selected from the group consisting of sodium salts and potassium salts has been separated is preferably subjected to the pH adjustment step (STEP 5a) described later, similarly to the lithium salt aqueous solution obtained by the lithium phosphate method. and then subjected to a carbonation step (STEP 6a).
- aqueous salt solution selected from the group consisting of sodium and potassium produced in the carbonation step is an aqueous solution in which at least one selected from the group consisting of sodium chloride and potassium chloride is dissolved as described above
- the aqueous solution may be concentrated in (STEP 9) in the concentration step described later.
- the lithium, at least one aqueous mixed salt solution selected from the group consisting of sodium and potassium, and the homogeneous mixture of the organic solvent for extracting lithium have a pH of at least one selected from the group consisting of sodium hydroxide and potassium hydroxide. It is preferably adjusted to a range of 5 to 9 by the addition of an alkali such as 1, and a lithium-containing organic phase and at least one aqueous salt solution selected from the group consisting of sodium and potassium as extraction residue are obtained.
- organic solvents for extracting lithium include bis(2-ethylhexyl) hydrogen phosphate. Mineral acid scrubbing is performed on the lithium-containing organic phase to recover an aqueous lithium salt solution.
- the aqueous lithium salt solution is preferably subjected to a pH adjustment step (STEP 5a) described later and further subjected to a carbonation step (STEP 6a) in the same manner as the aqueous lithium salt solution obtained by the lithium phosphate method.
- aqueous salt solution selected from the group consisting of sodium and potassium produced in the carbonation step is an aqueous solution in which at least one selected from the group consisting of sodium chloride and potassium chloride is dissolved as described above.
- the aqueous solution may be concentrated in (STEP 9) in the concentration step described later.
- a first electrolysis step (STEP 7a), which will be described later, is carried out in which at least one selected aqueous salt solution is electrolyzed using an ion-exchange membrane. At least one aqueous salt solution selected from the group consisting of sodium and potassium is preferably concentrated in a concentration step (STEP 9) using a reverse osmosis membrane (RO membrane) or the like, which will be described later.
- RO membrane reverse osmosis membrane
- At least one selected from the group consisting of sodium hydroxide and potassium hydroxide is added to the lithium salt aqueous solution obtained in the separation step, and the pH of the lithium salt aqueous solution is adjusted.
- An adjustment step (STEP 5a) may be included.
- the pH of the aqueous lithium salt solution is preferably adjusted to 8-14, more preferably 10-11.
- the recovery method of the second embodiment includes a carbonation step (STEP 6a) of carbonating the lithium salt aqueous solution obtained in the separation step to obtain lithium carbonate.
- carbonation step carbon dioxide is absorbed in an aqueous solution 5 in which at least one selected from the group consisting of sodium hydroxide and potassium hydroxide obtained in the first electrolysis step (STEP 7a) described later is dissolved.
- At least one alkali metal carbonate (excluding lithium carbonate) selected from the group consisting of sodium carbonate and potassium carbonate obtained in the carbon absorption step (STEP 8) may be added to the lithium salt aqueous solution.
- the alkali metal of the alkali metal carbonate is at least one selected from the group consisting of sodium, potassium, rubidium, cesium, and francium.
- the alkali metal is preferably at least one selected from the group consisting of sodium and potassium, more preferably sodium.
- At least one selected from the group consisting of sodium chloride and potassium chloride obtained from the separation step is dissolved, and at least one selected from the group consisting of sodium and potassium It includes a first electrolysis step (STEP 7a) of electrolyzing an aqueous salt solution using an ion-exchange membrane to obtain an aqueous alkali metal hydroxide solution.
- the first electrolysis step can be performed using, for example, an electrolytic bath 11 shown in FIG.
- the electrolytic cell 11 has an anode plate 12 on one inner surface and a cathode plate 13 on the inner surface facing the anode plate 12, the anode plate 12 is connected to the anode 14 of the power source, and the cathode plate 13 is the cathode of the power source. 15 is connected.
- the electrolytic cell 11 is partitioned by an ion exchange membrane 16 into an anode chamber 17 having an anode plate 12 and a cathode chamber 18 having a cathode plate 13 .
- chloride ions generate chlorine gas (Cl 2 ) on the anode plate 12.
- alkali metal ion selected from the group consisting of sodium ions and potassium ions moves through the ion exchange membrane 16 to the cathode chamber 18 .
- aqueous alkali metal hydroxide solution 5 in which at least one selected from the group consisting of sodium hydroxide and potassium hydroxide, which is selected from the group consisting of hydroxide ions and sodium ions and potassium ions, is dissolved. Generate.
- renewable energy preferably at least one selected from the group consisting of solar power generation and wind power generation is used.
- the hydrogen gas (H 2 ) and chlorine gas (Cl 2 ) generated in the first electrolysis step are reacted to form hydrochloric acid.
- hydrochloric acid can be obtained.
- Sulfuric acid can be obtained in the anode chamber 17 when the at least one aqueous salt solution selected from the group consisting of sodium and potassium contains sulfate ions.
- Nitric acid can be obtained in the anode chamber 17 when the at least one aqueous salt solution selected from the group consisting of sodium and potassium contains nitrate ions. That is, the mineral acid 4 can be obtained in the first electrolysis step, and the mineral acid 4 is used for at least one selected from the group consisting of dissolving the active material powder 1 in STEP 1 and pH adjustment in STEP C. .
- carbon dioxide is added to the alkali metal hydroxide aqueous solution 5 in which at least one selected from the group consisting of sodium hydroxide and potassium hydroxide obtained in the first electrolysis step is dissolved.
- the alkali metal hydroxide aqueous solution 5 generated in the first electrolysis step is obtained from the alkali metal hydroxide addition step, the extraction step, the separation step by the lithium phosphate method, and the separation step by the solvent extraction method. It is reused in at least one step selected from the group consisting of:
- At least one aqueous salt solution selected from the group consisting of potassium is produced. Therefore, in the recovery method of the second embodiment, at least one aqueous salt solution selected from the group consisting of dilute sodium and potassium is concentrated, and at least one salt solution selected from the group consisting of sodium and potassium obtained in the separation step is It may include a concentration step (STEP 9) in which it is added to one aqueous salt solution.
- the concentration step can be performed using, for example, a reverse osmosis membrane (RO membrane).
- a separation step (STEP 4a) is included for separating each of the lithium salt and at least one salt selected from the group consisting of sodium and potassium from the aqueous alkali metal mixed salt solution.
- the third embodiment is a separation step ( Including STEP 4a).
- the separation step is not limited to a specific method, but is preferably carried out by at least one selected from the group consisting of a lithium phosphate method, an evaporative concentration method, and a solvent extraction method.
- Lithium phosphate method in the third embodiment A lithium phosphate method according to the third embodiment will be described with reference to FIG.
- aluminum phosphate and at least one alkali metal hydroxide (MOH) aqueous solution selected from the group consisting of sodium hydroxide and potassium hydroxide are added to the alkali metal mixed salt aqueous solution, and phosphoric acid It includes a phosphorylation step (STEP A) that produces solids containing lithium and aluminum hydroxide.
- Alkali metal chloride (MCl) is dissolved in the aqueous liquid from which the solids are produced.
- the alkali metal hydroxide is preferably sodium hydroxide.
- FIG. 7 shows the case where only sodium hydroxide is used as the alkali metal hydroxide.
- the lithium phosphate method includes a first solid-liquid separation (STEP B) for solid-liquid separation of the solid produced in the phosphorylation step. Filtration is mentioned as the said 1st solid-liquid-separation process, for example.
- the solid matter separated in the first solid-liquid separation step may be washed.
- a pH adjustment step (STEP C) is included in which a mineral acid is added to a suspension obtained by suspending the solid matter in water to adjust the pH of the suspension to 2-3.
- the mineral acid is not limited to a specific mineral acid.
- the mineral acid contains at least one selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid.
- the mineral acid is preferably at least one selected from the group consisting of hydrochloric acid, sulfuric acid, and nitric acid, more preferably hydrochloric acid, sulfuric acid, or nitric acid, and still more preferably hydrochloric acid.
- the lithium salt is lithium chloride and FIG. 7 describes this case.
- the lithium phosphate method includes a second solid-liquid separation step (STEP D) for solid-liquid separation of the aluminum phosphate and lithium salt aqueous solution obtained in the pH adjustment step. Filtration is mentioned as the said 2nd solid-liquid-separation process, for example.
- the aluminum phosphate obtained in the second solid-liquid separation step can be solid-liquid separated in a short time, and the solid-liquid separated aluminum phosphate is reused in the phosphorylation step.
- the pH of the lithium salt aqueous solution obtained in the second solid-liquid separation step is preferably adjusted in the pH adjustment step (STEP 5a) described later. Since the pH of the suspension is adjusted to 2 to 3 in the pH adjustment step (STEP C), the pH of the lithium salt aqueous solution is 2 to 3, and the pH is adjusted to the pH adjustment step (STEP 5a ), preferably 6 to 14, more preferably 6 to 8. In this case, unreacted aluminum and phosphorus precipitate and the purity of the lithium salt aqueous solution becomes higher.
- the lithium salt aqueous solution whose pH has been adjusted in the pH adjustment step (STEP 5a) is electrolyzed using an ion-exchange membrane to obtain an aqueous lithium hydroxide solution (STEP 6b), which will be described later. do.
- the lithium salt aqueous solution may be concentrated in a first concentration step (STEP E) before being subjected to the second electrolysis step.
- the first concentration step can be performed using, for example, a reverse osmosis membrane (RO membrane).
- the filtrate in which the alkali metal chloride is dissolved and separated in the first solid-liquid separation step may be concentrated in the second concentration step (STEP 9) described later.
- the alkali metal mixed salt aqueous solution containing lithium and at least one selected from the group consisting of sodium and potassium is evaporated and concentrated to obtain sodium salts and potassium salts such as at least one selected from the group consisting of sodium chloride and potassium chloride. At least one selected from the group consisting of is sequentially crystallized and separated from the alkali metal mixed salt aqueous solution.
- At least one selected from the group consisting of sodium and potassium salts such as at least one selected from the group consisting of sodium chloride and potassium chloride, dissolved in water, and at least one selected from the group consisting of sodium and potassium
- a first electrolysis step (STEP 7a), which will be described later, is performed in which two salt solutions are electrolyzed using an ion-exchange membrane.
- the aqueous lithium salt solution from which at least one selected from the group consisting of sodium salts and potassium salts has been separated is preferably subjected to the pH adjustment step (STEP 5a) described later and the 1 concentration step (STEP E) and the second electrolysis step (STEP 6b) to be described later.
- the pH of the homogeneous mixed solution of the alkali metal mixed salt aqueous solution containing lithium, at least one selected from the group consisting of sodium and potassium, and the organic solvent for extracting lithium is from the group consisting of sodium hydroxide and potassium hydroxide.
- the organic solvent for extracting lithium include bis(2-ethylhexyl) hydrogen phosphate.
- Mineral acid scrubbing is performed on the lithium-containing organic phase to recover an aqueous lithium salt solution.
- the lithium salt aqueous solution is preferably subjected to a pH adjustment step (STEP 5a) and a first concentration step (STEP E) described later in the same manner as the lithium salt aqueous solution obtained by the lithium phosphate method. is subjected to the electrolysis process (STEP 6b).
- the first electrolysis step (STEP 7a) of electrolyzing at least one selected aqueous salt solution using an ion exchange membrane is performed.
- the at least one aqueous salt solution selected from the group consisting of sodium and potassium is preferably concentrated in the second concentration step (STEP 9) using a reverse osmosis membrane (RO membrane) or the like.
- ⁇ pH adjustment step of lithium salt aqueous solution In the recovery method of the third embodiment, at least one selected from the group consisting of lithium hydroxide and an aqueous lithium hydroxide solution is added to the aqueous lithium salt solution obtained in the separation step, and the pH of the aqueous lithium salt solution is adjusted.
- a pH adjustment step (STEP 5a) may be included.
- the pH of the lithium salt aqueous solution is preferably adjusted to 6-14, more preferably 6-8.
- the recovery method of the third embodiment includes a first concentration step (STEP E) for concentrating the lithium salt aqueous solution obtained in the separation step and optionally subjected to the pH adjustment step (STEP 5a).
- the first concentration step can be performed using, for example, a reverse osmosis membrane (RO membrane).
- ⁇ Second electrolysis step> The recovery method of the third embodiment is obtained in the separation step, and optionally in at least one selected from the group consisting of the pH adjustment step (STEP 5a) and the first concentration step (STEP E).
- a second electrolysis step (STEP 6b) is included in which the applied lithium salt aqueous solution is electrolyzed using an ion exchange membrane to obtain a lithium hydroxide aqueous solution.
- the second electrolysis step can be performed using, for example, the electrolytic bath 11 shown in FIG.
- the second electrolysis step is performed in the same manner as the first electrolysis step.
- sulfuric acid can be obtained in the anode chamber 17 when the lithium chloride aqueous solution contains sulfate ions.
- nitric acid can be obtained in the anode chamber 17 .
- the mineral acid 4 can be obtained in the second electrolysis step, and the mineral acid 4 may be used for at least one of dissolving the active material powder 1 in STEP 1 and pH adjustment in STEP C.
- the electric power required for the second electrolysis step for example, renewable energy, preferably at least one selected from the group consisting of solar power generation and wind power generation, is used.
- the recovery method of the third embodiment includes a crystallization step (STEP F) of crystallizing lithium hydroxide monohydrate 8 by evaporating and concentrating the lithium hydroxide aqueous solution obtained in the second electrolysis step. may contain.
- the recovery method of the third embodiment may include a carbonation step (STEP G) of blowing carbon dioxide into the lithium hydroxide aqueous solution obtained in the second electrolysis step to generate lithium carbonate 6.
- a carbonation step STP G
- An aqueous solution in which a lithium salt such as lithium chloride is dissolved and obtained by solid-liquid separation by filtration or the like of the slurry obtained in the carbonation step may be concentrated in the first concentration step (STEP E). 6 and 7 show the case where the lithium salt is lithium chloride.
- ⁇ First electrolysis step> In the recovery method of the third embodiment, at least one selected from the group consisting of sodium chloride and potassium chloride obtained from the separation step is dissolved, and at least one selected from the group consisting of sodium and potassium It includes a first electrolysis step (STEP 7a) of electrolyzing an aqueous salt solution using an ion-exchange membrane to obtain an aqueous alkali metal hydroxide solution.
- the first electrolysis step can be performed in the same manner as the first electrolysis step of the second embodiment using, for example, the electrolytic bath 11 shown in FIG.
- the hydrogen gas (H 2 ) and chlorine gas (Cl 2 ) generated in the first electrolysis step are reacted to form hydrochloric acid.
- hydrochloric acid can be obtained.
- sulfuric acid can be obtained in the anode chamber 27 when the at least one aqueous salt solution selected from the group consisting of sodium and potassium contains sulfate ions.
- Nitric acid can be obtained in the anode chamber 27 when the at least one aqueous salt solution selected from the group consisting of sodium and potassium contains nitrate ions. That is, the mineral acid 4 can be obtained in the first electrolysis step, and the mineral acid 4 is used for at least one selected from the group consisting of dissolving the active material powder 1 in STEP 1 and pH adjustment in STEP C. .
- the alkali metal hydroxide aqueous solution produced in the first electrolysis step comprises the alkali metal hydroxide addition step, the extraction step, the separation step by the lithium phosphate method, and the separation step by the solvent extraction method. It is reused in at least one step selected from the group.
- the recovery method of the third embodiment at least one aqueous salt solution selected from the group consisting of dilute sodium and potassium is concentrated, and at least one salt solution selected from the group consisting of sodium and potassium obtained in the separation step is It may include a second concentration step (STEP 9) in which it is added to one aqueous salt solution.
- the second concentration step can be performed using, for example, a reverse osmosis membrane (RO membrane).
- RO membrane reverse osmosis membrane
- Example 1 A used lithium-ion battery whose life as a battery product has been exhausted was subjected to a discharge treatment to discharge all remaining electric charges. Next, the waste lithium ion battery was heat-treated (roasted), pulverized with a hammer mill, and the housing, current collector, etc. constituting the waste lithium ion battery were sieved to obtain active material powder. 500 g of the active material powder was dissolved in 3 L of 6 mol/L hydrochloric acid, and 2.8 L of 2 mol/L aqueous sodium hydroxide solution was added to the resulting solution to neutralize the solution.
- nickel was extracted from the first extraction residue to obtain a lithium and sodium mixed salt aqueous solution as the extraction residue. 3.5 g/L lithium and 38.2 g/L sodium were contained in the aqueous solution.
- the white slurry B was filtered and washed to obtain 467 g of white cake B with a moisture content of 60% and a total of 1060 mL of filtrate and washing water.
- Sodium hydroxide was added to the above 1060 mL of the filtrate and washing water to adjust the pH to 7, and the filtered solution was added with 680 g of a 35% by mass sodium carbonate aqueous solution, heated to 60° C., and reacted for 1 hour. .
- the resulting solid matter was filtered and washed to obtain hydrous lithium carbonate.
- the hydrated lithium carbonate was dried at 500° C. for 4 hours to obtain 129 g of lithium carbonate.
- the recovery of lithium was 83.5%.
- the content of sodium in the lithium carbonate was less than 200 ppm, the content of aluminum was less than 10 ppm, the content of phosphorus was less than 10 ppm, and the content of water was less than 0.1% by mass.
- the filtrate obtained by filtering and washing the white slurry A and 10.5 L of washing water were concentrated using the RO membrane to obtain an aqueous sodium chloride solution (sodium chloride concentration: 300 g/L) is electrolyzed using an ion-exchange membrane (Nafion N324 manufactured by Chemours) under the conditions of a current density of 40 A/dm 2 , an electrode area of 1.75 dm 2 , and an energization time of 4 hours (first electrolysis step). to obtain 1.6 kg of 21.2% by mass sodium hydroxide. Further, the reaction product of chlorine gas and hydrogen gas produced was absorbed in water to obtain 1.04 kg of 30% by mass hydrochloric acid.
- the sodium hydroxide generated in the first electrolysis step was reusable in the sodium hydroxide addition step (STEP 2), extraction step (STEP 3), and separation step (STEP 4). Furthermore, the hydrochloric acid synthesized in the first electrolysis step was reusable in the dissolution step (STEP 1). The current efficiency in the first electrolysis step was 81.5%.
- Example 1 it was found that the mineral acids and alkalis used could be regenerated and reused. Furthermore, it was also found that the purity of lithium carbonate obtained in the final stage of recovering lithium from waste lithium ion batteries and the recovery rate of lithium are very high.
- Example 2 A used lithium-ion battery whose life as a battery product has been exhausted was subjected to a discharge treatment to discharge all remaining electric charges. Next, the waste lithium ion battery was heat-treated (roasted), pulverized with a hammer mill, and the housing, current collector, etc. constituting the waste lithium ion battery were sieved to obtain active material powder. 500 g of the active material powder was dissolved in 3 L of 6 mol/L hydrochloric acid, and 2.8 L of 2 mol/L aqueous sodium hydroxide solution was added to the resulting solution to neutralize the solution.
- nickel was extracted from the first extraction residue to obtain a lithium and sodium mixed salt aqueous solution as the extraction residue. 3.5 g/L lithium and 38.2 g/L sodium were contained in the aqueous solution.
- the white slurry B was filtered and washed to obtain 467 g of white cake B with a moisture content of 60% and a total of 1060 mL of filtrate and washing water.
- Lithium hydroxide was added to the 1060 mL filtrate and washing water to adjust the pH to 7, and the filtrate (filtrate 1) 1060 mL (lithium chloride concentration 92 g/L) was concentrated using the RO membrane.
- the obtained lithium chloride aqueous solution (lithium chloride concentration: 200 g/L) was electrolyzed using an ion-exchange membrane (Nafion N324 manufactured by Chemours) under the conditions of a current density of 40 A/dm 2 and an electrode area of 0.7 dm 2 .
- second electrolysis step to obtain 1100 g of a 6.2% by mass lithium hydroxide aqueous solution. Furthermore, the reaction product of chlorine gas and hydrogen gas produced was absorbed in water to obtain 350 g of 30% by mass hydrochloric acid. The lithium recovery rate in the second electrolysis step was 70.3%.
- lithium hydroxide monohydrate crystals 380 g of the 6.2% by mass lithium hydroxide aqueous solution was separated, and 80% by mass of the aqueous solution was crystallized to obtain 19.3 g (mass after drying) of lithium hydroxide monohydrate crystals.
- the sodium content in the lithium hydroxide monohydrate was less than 50 ppm, the aluminum content was less than 10 ppm, and the phosphorus content was less than 10 ppm.
- the filtrate obtained by filtering and washing the white slurry A and 10.5 L of washing water were concentrated using the RO membrane to obtain an aqueous sodium chloride solution (sodium chloride concentration: 300 g/L) is electrolyzed using an ion-exchange membrane (Nafion N324 manufactured by Chemours) under the conditions of a current density of 40 A/dm 2 , an electrode area of 1.75 dm 2 , and an energization time of 4 hours (first electrolysis step). to obtain 1.6 kg of 21.2% by mass sodium hydroxide. Further, the reaction product of chlorine gas and hydrogen gas produced was absorbed in water to obtain 1.04 kg of 30% by mass hydrochloric acid.
- the sodium hydroxide generated in the first electrolysis step was reusable in the sodium hydroxide addition step (STEP 2), extraction step (STEP 3), and separation step (STEP 4). Furthermore, the hydrochloric acid synthesized in the first electrolysis step was reusable in the dissolution step (STEP 1). The current efficiency in the first electrolysis step was 81.5%.
- Example 2 it was found that the mineral acids and alkalis used could be regenerated and reused. Furthermore, it was found that the purity of lithium hydroxide monohydrate obtained in the final stage of recovering lithium from waste lithium-ion batteries and the recovery rate of lithium were very high.
- the alkali metal hydroxide can be directly obtained in the first and second electrolysis steps using the ion exchange membrane of the alkali metal salt aqueous solution. Since the mineral acids and alkalis generated in these electrolysis steps can be recycled for the recovery method of the present invention, a closed-loop recycling process can be realized. Furthermore, since the recovery method of the present invention cyclically utilizes mineral acids and alkalis, compared to the case where mineral acids and alkalis are purchased from the outside as in the past, emissions of carbon dioxide generated in the distribution process of mineral acids and alkalis are reduced. can be reduced.
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Abstract
Description
さらに水酸化鉄及び水酸化アルミニウムが、前記有価金属の溶解液への水酸化ナトリウム及び水酸化カリウムの少なくとも1つの添加により順次沈殿し、前記有価金属の溶解液から鉄及びアルミニウムが分離される場合がある。
前記分離工程は、特定の方法に限定されないが、好ましくはリン酸リチウム法、蒸発濃縮法、及び溶媒抽出法からなる群から選ばれる少なくとも1つにより行われる。
図4を用いて、リン酸リチウム法について説明する。リン酸リチウム法は、リン酸アルミニウムと、水酸化ナトリウム及び水酸化カリウムの少なくとも1つのアルカリ金属水酸化物(MOH)水溶液を、前記アルカリ金属混合塩水溶液に添加し、リン酸リチウム及び水酸化アルミニウムを含む固形物を生成させるリン酸化工程(STEP A)を含む。塩化アルカリ金属(MCl)が、前記固形物が生成した前記水性液に溶解している。前記アルカリ金属水酸化物は、好ましくは水酸化ナトリウムである。図4では、前記アルカリ金属水酸化物として水酸化ナトリウムのみを使用する場合が示されている。
前記リチウムと、ナトリウム及びカリウムからなる群から選ばれる少なくとも1つのアルカリ金属混合塩水溶液が蒸発濃縮され、塩化ナトリウム及び塩化カリウムからなる群から選ばれる少なくとも1つ等の、ナトリウム塩及びカリウム塩からなる群から選ばれる少なくとも1つが順次晶析され、当該アルカリ金属混合塩水溶液から分離される。分離された塩化ナトリウム及び塩化カリウムからなる群から選ばれる少なくとも1つ等の、ナトリウム塩及びカリウム塩からなる群から選ばれる少なくとも1つが水に溶解され、ナトリウム及びカリウムからなる群から選ばれる少なくとも1つの塩水溶液を、イオン交換膜を用いて電解する、後述する第1の電解工程(STEP 7a)が実施される。ナトリウム塩及びカリウム塩からなる群から選ばれる少なくとも1つが分離されたリチウム塩水溶液は、前記リン酸リチウム法で得られたリチウム塩水溶液と同様に、好ましくは後述するpH調整工程(STEP 5a)に付され、更に炭酸化工程(STEP 6a)に付される。当該炭酸化工程で生成するナトリウム及びカリウムからなる群から選ばれる少なくとも1つの塩水溶液が前記されるように塩化ナトリウム及び塩化カリウムからなる群から選ばれる少なくとも1つが溶解している水溶液となる場合、当該水溶液は、後述する濃縮工程で(STEP 9)で濃縮されてよい。
前記リチウムと、ナトリウム及びカリウムからなる群から選ばれる少なくとも1つの混合塩水溶液、及びリチウム抽出用有機溶媒の均質な混合液のpHが、水酸化ナトリウム及び水酸化カリウムからなる群から選ばれる少なくとも1つ等のアルカリの添加により、好ましくは5~9の範囲に調整され、リチウム含有有機相と、抽出残液としてナトリウム及びカリウムからなる群から選ばれる少なくとも1つの塩水溶液が得られる。リチウム抽出用有機溶媒として、例えばリン酸水素ビス(2-エチルヘキシル)が挙げられる。当該リチウム含有有機相に対し鉱酸によるスクラビングが実施され、リチウム塩水溶液が回収される。当該リチウム塩水溶液は、前記リン酸リチウム法で得られたリチウム塩水溶液と同様に好ましくは後述するpH調整工程(STEP 5a)に付され、更に炭酸化工程(STEP 6a)に付される。当該炭酸化工程で生成するナトリウム及びカリウムからなる群から選ばれる少なくとも1つの塩水溶液が、前記されるように塩化ナトリウム及び塩化カリウムからなる群から選ばれる少なくとも1つが溶解している水溶液となる場合、当該水溶液は、後述する濃縮工程で(STEP 9)で濃縮されてよい。
アルカリ金属混合塩水溶液からリチウム塩と、ナトリウム及びカリウムからなる群から選ばれる少なくとも1つの塩のそれぞれを分離する分離工程(STEP 4a)を含む。
前記分離工程は、特定の方法に限定されないが、好ましくはリン酸リチウム法、蒸発濃縮法、及び溶媒抽出法からなる群から選ばれる少なくとも1つにより行われる。
図7を用いて、第3の実施形態におけるリン酸リチウム法について説明する。リン酸リチウム法は、リン酸アルミニウムと、水酸化ナトリウム及び水酸化カリウムからなる群から選ばれる少なくとも1つのアルカリ金属水酸化物(MOH)水溶液を、前記アルカリ金属混合塩水溶液に添加し、リン酸リチウム及び水酸化アルミニウムを含む固形物を生成させるリン酸化工程(STEP A)を含む。塩化アルカリ金属(MCl)が、前記固形物が生成した前記水性液に溶解している。前記アルカリ金属水酸化物は、好ましくは水酸化ナトリウムである。図7では、前記アルカリ金属水酸化物として水酸化ナトリウムのみを使用する場合が示されている。
リチウムと、ナトリウム及びカリウムからなる群から選ばれる少なくとも1つを含む前記アルカリ金属混合塩水溶液が蒸発濃縮され、塩化ナトリウム及び塩化カリウムからなる群から選ばれる少なくとも1つ等の、ナトリウム塩及びカリウム塩からなる群から選ばれる少なくとも1つが順次晶析され、当該アルカリ金属混合塩水溶液から分離される。分離された塩化ナトリウム及び塩化カリウムからなる群から選ばれる少なくとも1つ等の、ナトリウム塩及びカリウム塩からなる群から選ばれる少なくとも1つが水に溶解され、ナトリウム及びカリウムからなる群から選ばれる少なくとも1つの塩水溶液を、イオン交換膜を用いて電解する、後述する第1の電解工程(STEP 7a)が実施される。ナトリウム塩及びカリウム塩からなる群から選ばれる少なくとも1つが分離されたリチウム塩水溶液は、前記リン酸リチウム法で得られたリチウム塩水溶液と同様に好ましくは後述するpH調整工程(STEP 5a)及び第1の濃縮工程(STEP E)に付され、後述する第2の電解工程(STEP 6b)に付される。
リチウムと、ナトリウム及びカリウムからなる群から選ばれる少なくとも1つを含む前記アルカリ金属混合塩水溶液、及びリチウム抽出用有機溶媒の均質な混合液のpHが、水酸化ナトリウム及び水酸化カリウムからなる群から選ばれる少なくとも1つ等のアルカリの添加により、好ましくは5~9の範囲に調整され、リチウム含有有機相と、抽出残液としてナトリウム及びカリウムからなる群から選ばれる少なくとも1つの塩水溶液が得られる。リチウム抽出用有機溶媒として、例えばリン酸水素ビス(2-エチルヘキシル)が挙げられる。当該リチウム含有有機相に対し鉱酸によるスクラビングが実施され、リチウム塩水溶液が回収される。当該リチウム塩水溶液は、前記リン酸リチウム法で得られたリチウム塩水溶液と同様に好ましくは後述するpH調整工程(STEP 5a)及び第1の濃縮工程(STEP E)に付され、後述する第2の電解工程(STEP 6b)に付される。
第3の実施形態の回収方法は、前記分離工程で得られるリチウム塩水溶液に水酸化リチウム及び水酸化リチウム水溶液からなる群から選ばれる少なくとも1つを添加し、当該リチウム塩水溶液のpHを調整するpH調整工程(STEP 5a)を含んでいてよい。前記リチウム塩水溶液のpHは、好ましくは6~14、より好ましくは6~8に調整される。
第3の実施形態の回収方法は、前記分離工程で得られ、必要に応じて前記pH調整工程(STEP 5a)に付された前記リチウム塩水溶液を濃縮する第1の濃縮工程(STEP E)を含んでいてよい。当該第1の濃縮工程を、例えば逆浸透膜(RO膜)を用いて行うことができる。
第3の実施形態の回収方法は、前記分離工程で得られ、必要に応じて前記pH調整工程(STEP 5a)及び前記第1の濃縮工程(STEP E)からなる群から選ばれる少なくとも1つに付された前記リチウム塩水溶液を、イオン交換膜を用いて電解し水酸化リチウム水溶液を得る第2の電解工程(STEP 6b)を含む。
前記第2の電解工程に要する電力として、例えば再生可能エネルギー、好ましくは太陽光発電及び風力発電からなる群から選ばれる少なくとも1つが使用される。
第3の実施形態の回収方法は、前記第2の電解工程で得られた前記水酸化リチウム水溶液を蒸発濃縮して水酸化リチウム一水和物8を晶析する晶析工程(STEP F)を含んでいてよい。
第3の実施形態の回収方法は、二酸化炭素を前記第2の電解工程で得られた前記水酸化リチウム水溶液に吹き込み、炭酸リチウム6を生成させる炭酸化工程(STEP G)を含んでいてもよい。当該炭酸化工程で得られるスラリーをろ過等により固液分離して得られる塩化リチウム等のリチウム塩が溶解している水溶液は、前記第1の濃縮工程(STEP E)で濃縮されてよい。なお、図6及び7には、前記リチウム塩が塩化リチウムである場合が示されている。
第3の実施形態の回収方法は、前記分離工程から得られる、塩化ナトリウム及び塩化カリウムからなる群から選ばれる少なくとも1つ等が溶解している、ナトリウム及びカリウムからなる群から選ばれる少なくとも1つの塩水溶液を、イオン交換膜を用いて電解し、アルカリ金属水酸化物水溶液を得る第1の電解工程(STEP 7a)を含む。当該第1の電解工程を、例えば図5に示す電解槽11を用いて、第2の実施形態の第1の電解工程と同様に行うことができる。
前記第1の電解工程に要する電力として、例えば再生可能エネルギー、好ましくは太陽光発電及び風力発電からなる群から選ばれる少なくとも1つが使用される。
<リチウム及びナトリウム混合塩水溶液中の金属の含有量、炭酸リチウム中の不純物の含有量>
PerkinElmer社製Optima8300を使用し、誘導結合プラズマ発光分光分析装置(ICP-OES)によりリチウム及びナトリウム混合塩水溶液中の金属の含有量、炭酸リチウム中の不純物の含有量を測定した。
電池製品としての寿命が消尽した使用済みのリチウムイオン電池を放電処理し、残留している電荷を全て放電させた。次いで当該廃リチウムイオン電池を加熱処理(焙焼)した後、ハンマーミルで粉砕し、当該廃リチウムイオン電池を構成する筐体、集電体等を篩分けし、活物質粉を得た。当該活物質粉500gを6mol/Lの塩酸3Lに溶解し、得られた溶液に2mol/Lの水酸化ナトリウム水溶液2.8Lを添加して、当該溶液を中和した。中和した溶液5.8Lと抽出剤としてビス(2,4,4-トリメチルペンチル)ホスフィン酸(Cyanex272、希釈剤はケロシン)5.8Lを混合し、コバルトを溶媒抽出した。5mol/Lの水酸化ナトリウム水溶液を混合液に添加し、pHを4に調整して、コバルト含有有機相と第1の抽出残液を得た。コバルト含有有機相は、薄硫酸でスクラビングした後、1.5mol/Lの硫酸で逆抽出し、硫酸コバルト溶液を得た。当該コバルト抽出工程で使用された有機溶媒と同一の有機溶媒を使用して、第1の抽出残液からニッケルを抽出し、抽出残液としてリチウム及びナトリウム混合塩水溶液を得た。3.5g/Lのリチウム及び38.2g/Lのナトリウムが当該水溶液に含まれていた。
前記第1の電解工程で生成した水酸化ナトリウムは、水酸化ナトリウム添加工程(STEP 2)、抽出工程(STEP 3)、及び分離工程(STEP 4)で再利用可能であった。さらに前記第1の電解工程で合成された塩酸は溶解工程(STEP 1)で再利用可能であった。前記第1の電解工程における電流効率は81.5%であった。
電池製品としての寿命が消尽した使用済みのリチウムイオン電池を放電処理し、残留している電荷を全て放電させた。次いで当該廃リチウムイオン電池を加熱処理(焙焼)した後、ハンマーミルで粉砕し、当該廃リチウムイオン電池を構成する筐体、集電体等を篩分けし、活物質粉を得た。当該活物質粉500gを6mol/Lの塩酸3Lに溶解し、得られた溶液に2mol/Lの水酸化ナトリウム水溶液2.8Lを添加して、当該溶液を中和した。中和した溶液5.8Lと抽出剤としてビス(2,4,4-トリメチルペンチル)ホスフィン酸(Cyanex272、希釈剤はケロシン)5.8Lを混合し、コバルトを溶媒抽出した。5mol/Lの水酸化ナトリウム水溶液を混合液に添加し、pHを4に調整して、コバルト含有有機相と第1の抽出残液を得た。コバルト含有有機相は、薄硫酸でスクラビングした後、1.5mol/Lの硫酸で逆抽出し、硫酸コバルト溶液を得た。当該コバルト抽出工程で使用された有機溶媒と同一の有機溶媒を使用して、第1の抽出残液からニッケルを抽出し、抽出残液としてリチウム及びナトリウム混合塩水溶液を得た。3.5g/Lのリチウム及び38.2g/Lのナトリウムが当該水溶液に含まれていた。
前記第1の電解工程で生成した水酸化ナトリウムは、水酸化ナトリウム添加工程(STEP 2)、抽出工程(STEP 3)、及び分離工程(STEP 4)で再利用可能であった。さらに前記第1の電解工程で合成された塩酸は溶解工程(STEP 1)で再利用可能であった。前記第1の電解工程における電流効率は81.5%であった。
5…水酸化ナトリウム水溶液、 6…炭酸リチウム、 7…炭酸ナトリウム、
8…水酸化リチウム一水和物、 11…電解槽、 16…イオン交換膜。
Claims (11)
- 廃リチウムイオン電池からリチウムを回収する方法であって、
廃リチウムイオン電池を前処理して得られた活物質粉を鉱酸にて溶解して少なくともリチウムを含む該活物質の酸溶解液を得る溶解工程と、
該溶解工程で得られた該酸溶解液にアルカリ金属水酸化物を添加するアルカリ金属水酸化物添加工程と、
該アルカリ金属水酸化物添加工程で得られた該酸溶解液から、該活物質粉に含まれる金属のうち、アルカリ金属を除く少なくとも1種の金属を溶媒抽出により分離し、第1のアルカリ金属塩水溶液を得る抽出工程と、
イオン交換膜を用いて該第1のアルカリ金属塩水溶液を電解し、アルカリ金属水酸化物水溶液と、酸と、該第1のアルカリ金属塩水溶液よりも希薄な第2のアルカリ金属塩水溶液とを得る第1の電解工程と、
該第1の電解工程で得られるアルカリ金属水酸化物水溶液を、該アルカリ金属水酸化物添加工程、及び該抽出工程からなる群から選ばれる少なくとも1つで再利用し、
該第1の電解工程で生成する気体を回収して得られる鉱酸、及び該第1の電解工程の陽極室で得られる鉱酸からなる群から選ばれる少なくとも1つを該溶解工程で再利用することを特徴とする廃リチウムイオン電池からリチウムを回収する方法。 - 請求項1に記載の廃リチウムイオン電池からリチウムを回収する方法において、前記アルカリ金属水酸化物は水酸化リチウムであることを特徴とする廃リチウムイオン電池からリチウムを回収する方法。
- 請求項1に記載の廃リチウムイオン電池からリチウムを回収する方法において、前記アルカリ金属水酸化物は、水酸化ナトリウム及び水酸化カリウムからなる群から選ばれる少なくとも1つであり、
前記抽出工程で得られる、溶媒抽出の残液としてのアルカリ混合塩水溶液からリチウム塩と、ナトリウム及びカリウムからなる群から選ばれる少なくとも1つの塩のそれぞれを分離する分離工程を更に含み、
前記第1の電解工程で得られるアルカリ金属水酸化物水溶液を、前記アルカリ金属水酸化物添加工程、前記抽出工程、及び該分離工程からなる群から選ばれる少なくとも1つで再利用することを特徴とする廃リチウムイオン電池からリチウムを回収する方法。 - 請求項3に記載の廃リチウムイオン電池からリチウムを回収する方法において、前記分離工程で得られるリチウム塩水溶液を、イオン交換膜を用いて電解し水酸化リチウム水溶液を得る第2の電解工程、及び該分離工程で得られるリチウム塩水溶液を炭酸化して炭酸リチウムを得る炭酸化工程からなる群から選ばれる少なくとも1つを更に含むことを特徴とする廃リチウムイオン電池からリチウムを回収する方法。
- 請求項3に記載の廃リチウムイオン電池からリチウムを回収する方法において、前記分離工程が、リン酸リチウム法、蒸発濃縮法、及び溶媒抽出法の少なくとも1つにより行われることを特徴とする廃リチウムイオン電池からリチウムを回収する方法。
- 請求項4に記載の廃リチウムイオン電池からリチウムを回収する方法において、前記分離工程が、リン酸リチウム法、蒸発濃縮法、及び溶媒抽出法の少なくとも1つにより行われることを特徴とする廃リチウムイオン電池からリチウムを回収する方法。
- 請求項1に記載の廃リチウムイオン電池からリチウムを回収する方法において、前記第2のアルカリ金属塩水溶液を濃縮し、前記第1のアルカリ金属塩水溶液に添加することを特徴とする廃リチウムイオン電池からリチウムを回収する方法。
- 請求項1に記載の廃リチウムイオン電池からリチウムを回収する方法において、前記鉱酸は、塩酸、硫酸、及び硝酸からなる群から選択される少なくとも1種の酸を含むこと特徴とする廃リチウムイオン電池からリチウムを回収する方法。
- 請求項8に記載の廃リチウムイオン電池からリチウムを回収する方法において、前記鉱酸は塩酸を含むことを特徴とする廃リチウムイオン電池からリチウムを回収する方法。
- 請求項1~9のいずれか1項に記載の廃リチウムイオン電池からリチウムを回収する方法において、前記第1の電解工程、及び第2の電解工程からなる群から選ばれる少なくとも1つに用いる電力は、再生可能エネルギーによって得られた電力を含むこと特徴とする廃リチウムイオン電池からリチウムを回収する方法。
- 請求項10に記載の廃リチウムイオン電池からリチウムを回収する方法において、前記再生可能エネルギーによって得られた電力は、太陽光発電によって得られた電力、及び風力発電によって得られた電力からなる群から選ばれる少なくとも1つを含むこと特徴とする廃リチウムイオン電池からリチウムを回収する方法。
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