CN114892005A - Comprehensive recovery method of waste lithium battery - Google Patents
Comprehensive recovery method of waste lithium battery Download PDFInfo
- Publication number
- CN114892005A CN114892005A CN202210521159.2A CN202210521159A CN114892005A CN 114892005 A CN114892005 A CN 114892005A CN 202210521159 A CN202210521159 A CN 202210521159A CN 114892005 A CN114892005 A CN 114892005A
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- manganese
- gear
- powder
- solution
- copper
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Links
- 238000000034 method Methods 0.000 title claims abstract description 77
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 57
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000002699 waste material Substances 0.000 title claims abstract description 26
- 238000011084 recovery Methods 0.000 title claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000001914 filtration Methods 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 26
- 238000000605 extraction Methods 0.000 claims abstract description 25
- 239000002893 slag Substances 0.000 claims abstract description 24
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 22
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 22
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 22
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 21
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 229910052742 iron Inorganic materials 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 17
- 230000008025 crystallization Effects 0.000 claims abstract description 17
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 238000007873 sieving Methods 0.000 claims abstract description 16
- 238000004064 recycling Methods 0.000 claims abstract description 14
- 238000002386 leaching Methods 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims abstract description 11
- 230000001376 precipitating effect Effects 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 69
- 239000000243 solution Substances 0.000 claims description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 42
- 239000000706 filtrate Substances 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 34
- 229910052748 manganese Inorganic materials 0.000 claims description 31
- 239000011572 manganese Substances 0.000 claims description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 25
- 239000010941 cobalt Substances 0.000 claims description 24
- 229910017052 cobalt Inorganic materials 0.000 claims description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 24
- 230000035484 reaction time Effects 0.000 claims description 21
- 229910000831 Steel Inorganic materials 0.000 claims description 19
- 239000010959 steel Substances 0.000 claims description 19
- 238000004090 dissolution Methods 0.000 claims description 17
- 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 claims description 16
- 241000270295 Serpentes Species 0.000 claims description 15
- 210000000988 bone and bone Anatomy 0.000 claims description 15
- 238000005868 electrolysis reaction Methods 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 12
- 239000013081 microcrystal Substances 0.000 claims description 12
- 239000010413 mother solution Substances 0.000 claims description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- 239000012452 mother liquor Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 8
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 8
- 239000011343 solid material Substances 0.000 claims description 8
- 229910052793 cadmium Inorganic materials 0.000 claims description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000007789 sealing Methods 0.000 claims description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 229910001431 copper ion Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 5
- 230000005484 gravity Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 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 4
- 238000007599 discharging Methods 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 238000007885 magnetic separation Methods 0.000 claims description 4
- 229910001437 manganese ion Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 3
- 229940073644 nickel Drugs 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000001276 controlling effect Effects 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 6
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical group [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 2
- 235000010262 sodium metabisulphite Nutrition 0.000 description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 235000010269 sulphur dioxide Nutrition 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- BLOJZEAYCINVPY-UHFFFAOYSA-L S(=O)(=O)([O-])[O-].[Ni+2].[Co+2].[Mn+2].[Li+] Chemical compound S(=O)(=O)([O-])[O-].[Ni+2].[Co+2].[Mn+2].[Li+] BLOJZEAYCINVPY-UHFFFAOYSA-L 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 iron ions Chemical class 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
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 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 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229940001584 sodium metabisulfite Drugs 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/06—Sulfates; Sulfites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/005—Preliminary treatment of scrap
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
- C22B23/0469—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods by chemical substitution, e.g. by cementation
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3842—Phosphinic acid, e.g. H2P(O)(OH)
-
- 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
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a comprehensive recovery method of waste lithium batteries, which comprises the following steps: a. crushing; b. electrolyzing slurry; c. sieving; d. filtering; e. removing oil; f. copper removal; g. removing iron; h. removing impurities; i. replacement; j. extracting; k. adjusting acid; l, precipitating; MVR + crystallization; n, fine grinding; o. back extraction; leaching; and q, removing iron from the replacement slag leachate. The invention has the beneficial effects that: according to the method for comprehensively recycling the waste lithium batteries, on one hand, the traditional treatment method is combined, purer copper powder, aluminum powder and carbon powder can be obtained, the method can be used for producing manganese sulfate and nickel cobalt manganese sulfate crystals for producing the lithium battery anode precursor, the process flow is shorter than that of the traditional method, the cost is lower, the method improves the direct yield from the batteries to the final products, simplifies the battery disassembling and acid dissolving processes, and reduces the process loss; the process flow is simplified and shortened, the amount of generated slag is less, and the process loss is reduced.
Description
Technical Field
The invention relates to the technical field of waste lithium battery recovery, in particular to a comprehensive waste lithium battery recovery method.
Background
The lithium battery is a battery using lithium metal or lithium alloy as a negative electrode material and using a nonaqueous electrolyte solution, and therefore, the battery is also called a lithium metal battery, and the waste lithium battery is directly discarded to affect the environment, so that the waste lithium battery needs to be recycled.
The traditional recovery method firstly needs complicated discharging and crushing processes to generate a large amount of dust in the process of waste batteries; the battery powder after the second disassembly is subjected to wet smelting after being calcined and transported, the process is complicated, and the dust loss in the transporting process is large; the third traditional lithium battery has long recovery process, large occupied area, low direct recovery rate of valuable metals in the process and high production cost.
Therefore, a method for comprehensively recycling the waste lithium batteries is needed to be designed for the above problems.
Disclosure of Invention
The invention aims to provide a method for comprehensively recycling waste lithium batteries, which aims to solve the problems in the background technology.
In order to achieve the purpose, the invention provides the following technical scheme: a method for comprehensively recycling waste lithium batteries comprises the following steps: a. crushing; b. electrolyzing slurry; c. sieving; d. filtering; e. removing oil; f. copper removal; g. removing iron; h. removing impurities; i. replacement; j. extracting; k. adjusting acid; l, precipitating; MVR + crystallization; n, fine grinding; o. back extraction; leaching; q. removing iron from the replacement slag leachate, wherein a: crushing the battery and water together at normal temperature, wherein the mass ratio of the water to the battery is 1: 1-2.5, and b: and putting the crushed water and the battery material into a special slurry electrolytic tank for electrolytic dissolution.
Further, sieving, namely sieving the solid materials generated by the cathode and anode electrolytic cell, wherein the sieve aperture is 60-100 meshes; and d, filtering: filtering the cathode electrolysis overflow liquid to respectively obtain filtrate and filter residues, wherein the filtrate is a sulfate solution of nickel, cobalt, manganese and lithium, and the filter residues are black powder and carbon powder which are not completely dissolved out; and e, deoiling: and (3) removing oil from the filtrate by using activated carbon at normal temperature, and mainly adsorbing and removing organic matters in the battery.
Further, the f. copper removal: removing copper from the filtrate by using sodium thiosulfate after removing oil by using activated carbon, wherein the aim is to remove copper ions, and other impurity ions except sodium are not added; g, iron removal: after copper is removed, the temperature of the filtrate is raised to 85-95 ℃, and an oxidant is added to oxidize ferrous iron into ferric iron.
Further, h, impurity removal: after copper is removed, the temperature of the filtrate is raised to 85-95 ℃, manganese powder is added, the dosage of the manganese powder is 0.2-1kg per cubic meter, and the reaction time is 30-60 minutes, so that impurities such as cadmium in the solution can be removed; the i. substitution: controlling the temperature of the solution after impurity removal at 50-75 ℃, adding manganese powder, wherein the adding speed of the manganese powder is 0.05-0.2kg per minute, the adding amount of the manganese powder is 1.05-1.15 times of the theoretical amount of nickel cobalt replacement, the reaction time is 30-60 minutes, and the replacement slag is mixed slag containing nickel, cobalt and manganese.
Further, the j extraction: extracting manganese from the solution after impurity removal by adopting Cyanex272, controlling the content of the Cyanex272 at 15-20%, comparing with 1:2-4, mixing for 2-5 minutes, extracting manganese from the solution after impurity removal into an organic phase according to the extraction characteristics of the Cyanex272, and keeping lithium in raffinate to achieve the separation of manganese and lithium; k, acid adjustment: controlling the temperature of raffinate at 45-60 ℃, adjusting the pH value to 10-11.5 by using alkali, and reacting for 30-60 minutes, wherein the acid is used for adjusting and controlling the pH value of the solution so as to facilitate subsequent operation, and on the other hand, nickel, cobalt and manganese in the raffinate are completely precipitated, and the nickel, cobalt and manganese are precipitated in the acid adjusting process; the l. precipitation: adjusting the acid of the filtered solution, controlling the temperature to be 60-80 ℃, adding sodium carbonate, wherein the adding amount is 1.25-1.3 times of the theoretical amount of the precipitated lithium content, reacting for 60-120 minutes, and precipitating the lithium into lithium carbonate, wherein the lithium in the precipitated solution is still about 2g/L due to the solubility problem of the lithium carbonate.
Further, the m.mvr + crystals: the filtered precipitation mother liquor was concentrated using MVR, the degree of concentration being based on the occurrence of visible crystals. Cooling to obtain the lithium carbonate. The mother liquor can be returned to remove iron and regulate acid or returned to be continuously concentrated and crystallized; n, fine grinding: sieving solid materials after the first electrolytic dissolution to obtain oversize materials, grinding the materials to 60-100 meshes by a fine grinding machine, sieving the materials again after the fine grinding, and respectively carrying out magnetic separation and gravity separation on the oversize materials to obtain a steel shell, a diaphragm, copper-aluminum powder and carbon powder; the undersize products are dissolved out through one time of electrolysis, the undersize products are filtered after the dissolution is finished, the filtrate is merged into the first electrolysis dissolved liquid to remove oil, and the copper-aluminum powder and carbon powder are obtained after the filter residues are reselected; and combining the copper and aluminum powder, and carrying out color sorting to obtain copper powder and aluminum powder.
Further, the o. stripping: performing back extraction on the Cyanex272 organic phase extracted with manganese ions by using 4.5-5.5mol/L dilute sulfuric acid, controlling the pH value of a back extraction solution to be 3.5-4.5, wherein the obtained back extraction solution is a manganese sulfate solution, concentrating and thermally filtering manganese sulfate by MVR to obtain manganese sulfate crystals and a mother solution, returning the mother solution to a replacement process, and reducing impurities in the solution; and p leaching: after washing the replacement slag, leaching the replacement slag by adding hydrogen peroxide into sulfuric acid, wherein the hydrogen peroxide is used as a reducing agent to reduce high-valence cobalt, nickel and manganese without adding new impurity ions; q, removing iron from the replacement slag leachate: filtering the leachate, controlling the temperature to be 85-95 ℃, adding hydrogen peroxide as an oxidant, wherein the adding amount is 0.85-1.05 times of the theoretical oxidation amount of ferrous ions, the reaction time is 30-60 minutes, adding manganese powder to adjust the pH value to 2.5-3.5, and the reaction time is 60-120 minutes, after filtering, concentrating the filtrate, firstly carrying out primary thermal filtration, filtering to generate manganese sulfate microcrystals, wherein the purpose is to control crystal grains during cooling crystallization after removing the microcrystals, returning the microcrystals to the replacement process for dissolution, cooling crystallization after thermal filtration to obtain mixed crystals of nickel, cobalt and manganese sulfate, and returning the mother liquor to the concentration crystallization or deironing to remove enriched impurities.
Further, i, the replacement includes the outer box and gets the material subassembly, the inside lower extreme right side of outer box is provided with the hydrologic cycle subassembly, and the hydrologic cycle subassembly includes water pump, circulating pipe, water discharge pipe and solenoid valve, the upper end of water pump is connected with circulating pipe, and circulating pipe's right-hand member is connected with water discharge pipe, water discharge pipe's externally mounted has the solenoid valve, it is located the inside lower extreme left side of outer box to get the material subassembly.
Further, get the material subassembly and include flitch, shock dynamo, the case that gathers materials, sealed back plate and directional pole down, the lower extreme mid-mounting of flitch has shock dynamo down, and the lower extreme left side of flitch is provided with the case that gathers materials, the right-hand member of the case that gathers materials is connected with sealed back plate, and the lower extreme of sealed back plate runs through there is directional pole, the left side of outer box is installed and is connect the liquid case, and installs the stirring subassembly in the inside upper end of outer box, the stirring subassembly includes puddler, heating plate, pulling force elastic rope, shutoff balancing weight and directional guide arm, and the inside heating plate that is provided with in left side of puddler, the right-hand member of puddler is connected with the pulling force elastic rope, and the right side of pulling force elastic rope is connected with the shutoff balancing weight, the upper and lower both ends of shutoff balancing weight are connected with directional guide arm.
Furthermore, the upper end of the outer box body is provided with a power assembly, the power assembly comprises a driving motor, a first gear, a second gear, a third gear, a rotating positioning block and a rotating ball, the outside of the driving motor is sequentially provided with the first gear and the second gear from right to left, the lower end of the second gear is connected with the third gear, the lower end of the third gear is sequentially provided with the rotating positioning block and the rotating ball from outside to inside, the upper end of the power assembly is provided with a stirring assembly, the stirring assembly comprises a snake bone steel cable, a fourth gear, a fifth gear and a first bearing, the outside of the snake bone steel cable is sequentially provided with a fourth gear, a fifth gear and a first bearing, the left end of the fifth gear is connected with a lifting assembly, the lifting assembly comprises a lifting plate, a second bearing, a threaded lifting rod, a sixth gear, a threaded sleeve and a telescopic rod, and the second bearing is arranged inside the lifting plate, and a threaded lifting rod penetrates through the inside of the second bearing, a sixth gear is connected to the upper end of the threaded lifting rod, a threaded sleeve is connected to the lower end of the threaded lifting rod, and a telescopic rod is connected to the lower end of the lifting plate.
Compared with the prior art, the invention has the beneficial effects that:
1. on one hand, the method combines the traditional treatment method, purer copper powder, aluminum powder and carbon powder can be obtained, the method can be used for producing manganese sulfate and manganese nickel cobalt sulfate crystals for producing the lithium battery anode precursor, the process flow is shorter than that of the traditional method, the cost is lower, the method improves the direct yield from the battery to the final product, simplifies the battery disassembling and acid dissolving processes, and reduces the process loss; the process flow is simplified and shortened, the amount of generated slag is less, the process loss is reduced, auxiliary materials containing other impurity ions are used as little as possible in the patent process, the introduction of the impurity ions is reduced, and the impurity removal difficulty is reduced.
2. The driving motor drives the third gear to rotate through the second gear, so that the stirring rod is driven to rotate, the plugging counter weight block slides along the directional guide rod under the influence of centrifugal force, the stirring rod is opened by the plugging counter weight block, manganese powder is conveniently and uniformly sprinkled in the rotating process, replacement work of equipment is facilitated, and the working effect of the equipment is improved.
3. According to the invention, the filtered liquid can be conveyed to the upper part of the blanking plate again through the water pump to be continuously replaced, so that the equipment forms a cycle, the replacement effect of the equipment is better, and meanwhile, the vibration motor can continuously vibrate the blanking plate, so that particles replaced on the blanking plate slide down to the collection box along the inclined surface of the blanking plate to be collected.
4. The driving motor drives the fourth gear to rotate through the first gear, so that the snake bone steel rope rotates to stir and scatter manganese powder in the stirring rod, the manganese powder is prevented from being blocked when being sprayed out, meanwhile, the fifth gear drives the sixth gear to rotate, the lifting plate is lifted and lowered by means of threaded connection of the threaded lifting rod and the threaded sleeve, and the snake bone steel rope can scatter the manganese powder in the stirring rod repeatedly.
Drawings
FIG. 1 is a process flow diagram of a comprehensive recovery method of waste lithium batteries according to the present invention;
FIG. 2 is a schematic front view of a replacement device in the method for comprehensively recovering waste lithium batteries according to the present invention;
FIG. 3 is an enlarged structural diagram of a section of a stirring assembly in the method for comprehensively recovering waste lithium batteries according to the present invention;
fig. 4 is an enlarged structural schematic diagram of a dispersing component of the comprehensive waste lithium battery recycling method of the invention.
In the figure: 1. an outer case; 2. a water circulation assembly; 201. a water pump; 202. a circulating water pipe; 203. a water discharge pipe; 204. an electromagnetic valve; 3. a material taking assembly; 301. a blanking plate; 302. vibrating a motor; 303. a material collecting box; 304. sealing the back plate; 305. an orientation bar; 4. a liquid receiving box; 5. a stirring assembly; 501. a stirring rod; 502. a heating plate; 503. pulling the elastic rope; 504. plugging a balancing weight; 505. a directional guide rod; 6. a power assembly; 601. a drive motor; 602. a first gear; 603. a second gear; 604. a third gear; 605. rotating the positioning block; 606. rotating the ball; 7. a dispersing component; 701. a snake bone steel cable; 702. a fourth gear; 703. a fifth gear; 704. a first bearing; 8. a lifting assembly; 801. a lifting plate; 802. a second bearing; 803. a threaded lifting rod; 804. a sixth gear; 805. a threaded sleeve; 806. a telescopic rod.
Detailed Description
As shown in fig. 1 to 4, the present invention provides a technical solution: a comprehensive recovery method of waste lithium batteries comprises the following steps:
a. crushing: crushing the battery and water together under the condition of normal temperature, wherein the mass ratio of the water to the battery (the specific gravity of the water is considered as 1) is 1:1 to 2.5;
b. slurry electrolysis: the crushed water and battery materials are put into a special slurry electrolytic tank (the concrete structure and use of the slurry electrolytic tank are shown in 2. a slurry mixing electrolytic device and a condition description) for electrolytic dissolution, and the temperature: 45-55 ℃, voltage of 1.8-3.0V, current of 2000-3000A, current density of 100-300A/m2, stirring speed of 30-100 r/min for the anode tank and 50-130 r/min for the cathode tank, wherein the reducing agent is sodium metabisulfite, sodium sulfite, sulfur dioxide and sodium thiosulfate, the adding amount is 0.01-0.05 of the mass of the battery, sulfuric acid is added to control the dissolution PH value, the PH value control range is 0.5-2.0, the surfactant is non-ionic, the foaming is mainly controlled in the process to improve the dissolution efficiency, the adding amount is 0.001-0.008 of the mass of the battery,
acid leaching reaction:
2LiCoO2+3H2SO4＝2CoSO4+Li2SO4+3H2O
2LiNiO2+3H2SO4＝2NiSO4+Li2SO4+3H2O
2LiMn2O4+5H2SO4＝4MnSO4+Li2SO4+5H2O
Fe+H2SO4＝FeSO4+H2↑
electrode reduction leaching reaction:
LiCoO2+2e+4H+＝Co2++2H2O
LiNiO2+2e+4H+＝Ni2++2H2O
LiMn2O4+2e+8H+＝2Mn2++4H2O
and (3) cathode reaction:
LiCoO2+2Fe2++4H+＝Co2++2Fe3++2H2O
LiNiO2+2Fe2++4H+＝Ni2++2Fe3++2H2O
LiMn2O4+2Fe2++8H+＝2Mn2++2Fe3++4H2O
and (3) anode reaction:
Mn2++2H2O＝MnO2+4H++2e
H2O＝1/2O2↑+2H++2e
Fe2+＝Fe3++e；
c. sieving: sieving the solid material produced by the cathode and anode electrolytic cell, wherein the sieve aperture is 60-100 meshes;
d. and (3) filtering: filtering the cathode electrolysis overflow liquid to respectively obtain filtrate and filter residues, wherein the filtrate is a sulfate solution of nickel, cobalt, manganese and lithium, and the filter residues are black powder and carbon powder which are not completely dissolved out;
e. oil removal: the filtrate is deoiled by using active carbon at normal temperature, organic matters (electrolyte and adhesive) in the battery are mainly removed by adsorption, the dosage of the active carbon is adjusted according to the TOC content in the filtrate, the dosage is 1:50-200 of the TOC value, namely 1g/LTOC is added into the active carbon with the dosage of 50-200g/L, and the reaction time is 30-120 minutes;
f. copper removal: removing copper from the filtrate by using sodium thiosulfate after removing oil by using activated carbon, aiming at removing copper ions without adding other impurity ions except sodium, wherein the reaction temperature is 80-95 ℃, and the using amount of the sodium thiosulfate is as follows: the ratio of copper ions is 1:1.05-1.25, and the reaction time is 30-90 minutes;
g. iron removal: after copper is removed, heating the filtrate to 85-95 ℃, adding an oxidant (sodium chlorate, sodium hypochlorite, sodium persulfate and the like) to oxidize ferrous iron into ferric iron, wherein the dosage of the oxidant is 1.05-1.2 times of the theoretical quantity of the oxidized ferrous iron, the reaction time is 30-70 minutes, and then adding alkali (sodium carbonate and sodium hydroxide) to adjust the pH value to 2.5-4.5, and the reaction time is 60-120 minutes;
h. removing impurities: after copper is removed, the temperature of the filtrate is raised to 85-95 ℃, manganese powder is added, the dosage of the manganese powder is 0.2-1kg per cubic meter, the reaction time is 30-60 minutes, and the aim is to remove impurities such as cadmium in the solution, and the standard potential of the cadmium: cd2+ +2e → Cd-0.783
Standard potential of manganese: mn2+ +2e → Mn-1.185
Performing a displacement reaction on the metal manganese powder and cadmium in the solution, and removing impurities in the solution by using the displacement reaction;
i. and (3) replacement: controlling the temperature of the solution after impurity removal at 50-75 ℃, adding manganese powder at the speed of 0.05-0.2kg per minute, wherein the addition of the manganese powder is 1.05-1.15 times of the theoretical amount of nickel cobalt replacement, reacting for 30-60 minutes, and replacing slag is mixed slag containing nickel, cobalt and manganese,
standard potential of nickel: ni2+ +2e → Ni-0.257
Standard potential of cobalt: co2+ +2e → Co-0.28
Standard potential of manganese: mn2+ +2e → Mn-1.185
The metal manganese powder and nickel and cobalt in the solution are subjected to a replacement reaction, only manganese and lithium are left in the replaced solution, and cobalt and nickel enter the replacement slag;
j. and (3) extraction: extracting manganese from the impurity-removed liquid by adopting Cyanex272 (organic extraction), controlling the content of the Cyanex272 to be 15-20%, comparing with 1:2-4, mixing for 2-5 minutes, extracting manganese from the impurity-removed liquid into an organic phase according to the extraction characteristics of the Cyanex272, and keeping lithium in raffinate to achieve the separation of manganese and lithium;
k. acid adjustment: controlling the temperature of raffinate at 45-60 ℃, adjusting the pH value to 10-11.5 by using alkali, and reacting for 30-60 minutes, wherein the acid is used for adjusting and controlling the pH value of the solution so as to facilitate subsequent operation, and on the other hand, nickel, cobalt and manganese in the raffinate are completely precipitated, and the nickel, cobalt and manganese are precipitated in the acid adjusting process;
l, precipitation: adjusting the acid of the filtered solution, controlling the temperature to be 60-80 ℃, adding sodium carbonate, wherein the adding amount is 1.25-1.3 times of the theoretical amount of the precipitated lithium content, reacting for 60-120 minutes, and precipitating lithium into lithium carbonate, wherein the lithium in the solution after precipitation is still about 2g/L due to the solubility problem of lithium carbonate;
mvr + crystallization: concentrating the filtered precipitation mother liquor by adopting MVR, wherein the concentration degree takes the generation of visible crystals as a standard, cooling to obtain lithium carbonate, and returning the mother liquor to remove iron and regulate acid or returning to continue to concentrate and crystallize;
n, fine grinding: sieving solid materials after the first electrolytic dissolution to obtain oversize materials, grinding the materials to 60-100 meshes by a fine grinding machine, sieving the materials again after the fine grinding, and respectively carrying out magnetic separation and gravity separation on the oversize materials to obtain a steel shell, a diaphragm, copper-aluminum powder and carbon powder; the undersize products are dissolved out through one time of electrolysis, the undersize products are filtered after the dissolution is finished, the filtrate is merged into the first electrolysis dissolved liquid to remove oil, and the copper-aluminum powder and carbon powder are obtained after the filter residues are reselected; combining copper and aluminum powder, and performing color sorting to separate copper powder and aluminum powder;
o. back extraction: performing back extraction on the Cyanex272 organic phase extracted with manganese ions by using 4.5-5.5mol/L dilute sulfuric acid, controlling the pH value of a back extraction solution to be 3.5-4.5, wherein the obtained back extraction solution is a manganese sulfate solution, concentrating and thermally filtering manganese sulfate by MVR to obtain manganese sulfate crystals and a mother solution, returning the mother solution to a replacement process, and reducing impurities in the solution;
p leaching: after the replacement slag is washed, sulfuric acid and hydrogen peroxide are used for leaching, the hydrogen peroxide is used as a reducing agent, the purpose is to reduce high-valence cobalt, nickel and manganese without adding new impurity ions, the use amount of the hydrogen peroxide is 0.1-0.25 of the weight of the replacement slag, the pH value is regulated by the sulfuric acid, the end point pH value is controlled at 0.5-2.0, the reaction temperature is controlled at 75-85 ℃, and the reaction time is 120-180 minutes;
q, replacing the slag leachate to remove iron: filtering the leachate, controlling the temperature to be 85-95 ℃, adding hydrogen peroxide as an oxidant, wherein the addition amount is 0.85-1.05 times of the oxidation theoretical amount of divalent iron ions, reacting for 30-60 minutes, adding manganese powder to adjust the pH value to 2.5-3.5, and reacting for 60-120 minutes, after filtering, concentrating the filtrate, performing primary thermal filtration, filtering to generate manganese sulfate microcrystals, wherein the purpose is to remove microcrystals, control crystal grains during cooling crystallization, returning the microcrystals to a replacement process for dissolution, performing cooling crystallization after thermal filtration to obtain mixed crystals of nickel, cobalt and manganese sulfate, and returning the mother liquor to concentration crystallization or deironing to remove enriched impurities;
on one hand, the method combines the traditional treatment method, purer copper powder, aluminum powder and carbon powder can be obtained, the method can be used for producing manganese sulfate and manganese nickel cobalt sulfate crystals for producing the lithium battery anode precursor, the process flow is shorter than that of the traditional method, the cost is lower, the method improves the direct yield from the battery to the final product, simplifies the battery disassembling and acid dissolving processes, and reduces the process loss; the process flow is simplified and shortened, the amount of generated slag is less, the process loss is reduced, auxiliary materials containing other impurity ions are used as little as possible in the patent process, the introduction of the impurity ions is reduced, and the impurity removal difficulty is reduced.
As shown in fig. 2-3, i. the replacement comprises an outer box 1 and a material taking assembly 3, the right side of the inner lower end of the outer box 1 is provided with a water circulation assembly 2, the water circulation assembly 2 comprises a water pump 201, a circulating water pipe 202, a water discharge pipe 203 and an electromagnetic valve 204, the upper end of the water pump 201 is connected with the circulating water pipe 202, the right end of the circulating water pipe 202 is connected with the water discharge pipe 203, the electromagnetic valve 204 is installed outside the water discharge pipe 203, the material taking assembly 3 is positioned on the left side of the inner lower end of the outer box 1, the material taking assembly 3 comprises a blanking plate 301, a vibration motor 302, a material collecting box 303, a sealing rear plate 304 and a directional rod 305, the middle part of the lower end of the blanking plate 301 is provided with the vibration motor 302, the left side of the lower end of the blanking plate 301 is provided with the material collecting box 303, the right end of the material collecting box 303 is connected with the sealing rear plate 304, the lower end of the sealing rear plate 304 is penetrated by the directional rod 305, the left side of the outer box 1 is provided with a liquid receiving box 4, the stirring assembly 5 is installed at the upper end of the inner part of the outer box body 1, the stirring assembly 5 comprises a stirring rod 501, a heating plate 502, a pulling force elastic rope 503, a plugging balancing weight 504 and a directional guide rod 505, the heating plate 502 is arranged inside the left side of the stirring rod 501, the pulling force elastic rope 503 is connected to the right end of the stirring rod 501, the plugging balancing weight 504 is connected to the right side of the pulling force elastic rope 503, and the directional guide rod 505 is connected to the upper end and the lower end of the plugging balancing weight 504;
the driving motor 601 of the present invention drives the third gear 604 to rotate through the second gear 603, thereby driving the stirring rod 501 to rotate, causing the blocking clump weight 504 to slide along the directional guide rod 505 under the influence of centrifugal force, thereby opening the plugging balancing weight 504 to the stirring rod 501, facilitating the manganese powder to be uniformly sprinkled in the rotating process, facilitating the replacement work of the equipment, increasing the working effect of the equipment, the filtered liquid can be conveyed to the upper part of the blanking plate 301 again through the water pump 201 to be continuously replaced, so that the equipment forms a cycle, the replacement effect of the equipment can be better, meanwhile, the vibration motor 302 can continuously vibrate the blanking plate 301, so that the particles displaced on the blanking plate 301 slide down to the collecting box 303 along the inclined surface of the blanking plate 301 for collection, the electromagnetic valve 204 can control the opening and closing of the water discharge pipe 203, thereby controlling the liquid discharge, the pulling force elastic rope 503 can be convenient for plugging the balancing weight 504 to reset.
As shown in fig. 4, a power assembly 6 is mounted at the upper end of the outer box 1, the power assembly 6 includes a driving motor 601, a first gear 602, a second gear 603, a third gear 604, a rotational positioning block 605 and a rotational ball 606, the first gear 602 and the second gear 603 are sequentially disposed outside the driving motor 601 from right to left, the lower end of the second gear 603 is connected with the third gear 604, the rotational positioning block 605 and the rotational ball 606 are sequentially disposed at the lower end of the third gear 604 from outside to inside, the dispersing assembly 7 is disposed at the upper end of the power assembly 6, the dispersing assembly 7 includes a snake bone steel cable 701, a fourth gear 702, a fifth gear 703 and a first bearing 704, the fourth gear 702, the fifth gear 703 and the first bearing are sequentially disposed outside the snake bone steel cable 701, the lifting assembly 8 is connected to the left end of the fifth gear 703, and the lifting assembly 8 includes a lifting plate 801, a second bearing 802, a lifting assembly 8, The lifting plate 801 comprises a threaded lifting rod 803, a sixth gear 804, a threaded sleeve 805 and a telescopic rod 806, wherein a second bearing 802 is installed inside the lifting plate 801, the threaded lifting rod 803 penetrates through the inside of the second bearing 802, the upper end of the threaded lifting rod 803 is connected with the sixth gear 804, the lower end of the threaded lifting rod 803 is connected with the threaded sleeve 805, and the lower end of the lifting plate 801 is connected with the telescopic rod 806;
according to the invention, the driving motor 601 drives the fourth gear 702 to rotate through the first gear 602, so that the snake bone steel cable 701 rotates to stir and scatter manganese powder in the stirring rod 501, the blockage caused by the scattering of the manganese powder is prevented, meanwhile, the fifth gear 703 drives the sixth gear 804 to rotate, the lifting plate 801 is lifted and lowered through the threaded connection of the threaded lifting rod 803 and the threaded sleeve 805, the snake bone steel cable 701 can more repeatedly scatter the manganese powder in the stirring rod 501, the telescopic rod 806 can play a role in positioning and supporting the lifting plate 801, the driving motor 601 drives the third gear 604 to rotate through the second gear 603, the positioning block 605 can be rotated to position the rotation of the third gear 604, and the rotating ball 606 can reduce the friction force generated by the rotation of the third gear 604.
The working principle is as follows: crushing the battery and water together at normal temperature, wherein the mass ratio of the water to the battery is 1: 1-2.5, putting the crushed water and the battery material into a special slurry electrolytic tank for electrolytic dissolution, and the temperature is as follows: 45-55 ℃, voltage of 1.8-3.0V, current of 2000-3000A, current density of 100-300A/m2, stirring speed of 30-100 r/min of an anode tank, stirring speed of 50-130 r/min of a cathode tank, adopting sodium pyrosulfite, sodium sulfite, sulfur dioxide and sodium thiosulfate as a reducing agent, adding sulfuric acid to control the dissolved PH value, controlling the PH value within the range of 0.5-2.0, adopting a nonionic surfactant to control foaming in the process and improve the dissolving efficiency, wherein the adding amount is 0.001-0.008 of the mass of the battery, sieving solid materials generated by a cathode and anode electrolytic tank, the sieve aperture is 60-100 meshes, filtering the cathode electrolytic overflow liquid to respectively obtain filtrate and filter residue, the filtrate is a nickel-cobalt-manganese-lithium sulfate solution, filter residues are black powder and carbon powder which are not completely dissolved out, active carbon is used for removing oil from filtrate at normal temperature, organic matters in a battery are mainly removed by adsorption, the using amount of the active carbon is adjusted according to the TOC content in the filtrate, the using amount is 1:50-200 of the TOC value, namely the adding amount of the active carbon is 50-200g/L per 1g/LTOC, the reaction time is 30-120 minutes, the filtrate is subjected to oil removal by the active carbon and then is subjected to copper removal by sodium thiosulfate, the aim is to remove copper ions, other impurity ions except sodium are not added, the reaction temperature is 80-95 ℃, and the using amount of the sodium thiosulfate: copper ions are 1:1.05-1.25, the reaction time is 30-90 minutes, the filtrate after copper removal is heated to 85-95 ℃, oxidants (sodium chlorate, sodium hypochlorite, sodium persulfate and the like) are added to oxidize ferrous iron into ferric iron, the dosage of the oxidants is 1.05-1.2 times of the theoretical amount of the oxidized ferrous iron, the reaction time is 30-70 minutes, alkali (sodium carbonate and sodium hydroxide) is added to adjust the pH to 2.5-4.5, the reaction time is 60-120 minutes, the filtrate after copper removal is heated to 85-95 ℃, manganese powder is added, the dosage of the manganese powder is 0.2-1kg per cubic meter, the reaction time is 30-60 minutes, the aim is to remove impurities such as cadmium in the solution, the metal manganese powder and cadmium in the solution are subjected to displacement reaction, the impurities in the solution are removed by the displacement reaction, the temperature of the liquid in the external box body 1 is controlled to be 50-75 ℃ by a heating plate 502, then the driving motor 601 is turned on, the stirring rod 501 is driven to rotate by the second gear 603 and the third gear 604, the liquid is uniformly heated by the heating plate 502, meanwhile, the plugging counter weight block 504 slides outwards along the directional guide rod 505 by the centrifugal force generated by the rotation of the stirring rod 501, so that the manganese powder in the stirring rod 501 is thrown out and uniformly added into the liquid, the rotation speed of the stirring rod 501 is controlled, the manganese powder adding speed is 0.05-0.2kg per minute, the manganese powder adding amount is 1.05-1.15 times of the theoretical amount of nickel and cobalt replacement, the driving motor 601 drives the snake bone steel cable 701 to rotate by the first gear 602 and the fourth gear 702 while the manganese powder is added, the manganese powder in the stirring rod 501 is scattered to be conveniently spilled out, meanwhile, the fifth gear 703 can drive the sixth gear 804 to rotate, and further the threaded lifting rod 803 which forms a rotating structure between the second bearing 802 and the lifting plate 801 is rotated, the snake bone steel cable 701 is lifted through threaded connection between the threaded lifting rod 803 and the threaded sleeve 805, so that manganese powder in the stirring rod 501 is scattered better, the reaction time of the manganese powder is 30-60 minutes, liquid can be conveyed to the upper part of the blanking plate 301 from the position of the circulating water pipe 202 through the water pump 201, the liquid is circulated, the reaction is convenient to complete, particles generated in the reaction can shake the blanking plate 301 through the vibration motor 302 and fall into the collecting box 303 to be collected, liquid after impurity removal is used for extracting manganese by using Cyanex272 (organic extraction), the content of the Cyanex272 is controlled to be 15-20%, compared with 1:2-4, the mixing time is 2-5 minutes, manganese in the liquid after impurity removal is extracted into an organic phase according to the extraction characteristic of the Cyanex272, lithium is left in raffinate to achieve the separation of the manganese and the lithium, the temperature of the raffinate is controlled to be 45-60 ℃, and the pH value is adjusted to 10-11.5 by alkali, the reaction time is 30-60 minutes, the acid adjustment is to adjust and control the PH value of the solution to be convenient for the subsequent operation, on the other hand, the nickel, cobalt and manganese in the solution are completely precipitated, the precipitation of the nickel, cobalt and manganese can be generated in the acid adjustment process, the temperature of the solution after the acid adjustment and filtration is controlled to be 60-80 ℃, sodium carbonate is added, the addition amount is 1.25-1.3 times of the theoretical amount of the precipitated lithium content, the reaction time is 60-120 minutes, lithium is precipitated into lithium carbonate, because of the solubility problem of the lithium carbonate, the solution after the precipitation still contains lithium about 2g/L, the filtered precipitation mother solution is concentrated by MVR, the concentration degree is based on the generation of visible crystallization, lithium carbonate is obtained after cooling, the mother solution can be returned to remove the iron and adjust the acid or returned to be continuously concentrated and crystallized, the oversize obtained after the first electrolysis and the solid material is sieved by a fine grinding machine to 60-100 meshes, and then is sieved once, respectively carrying out magnetic separation and gravity separation on oversize products to obtain a steel shell, a diaphragm, copper-aluminum powder and carbon powder; the undersize products are dissolved out through one time of electrolysis, the undersize products are filtered after the dissolution is finished, the filtrate is merged into the first electrolysis dissolved liquid to remove oil, and the copper-aluminum powder and carbon powder are obtained after the filter residues are reselected; combining copper and aluminum powder, performing color sorting to separate copper powder and aluminum powder, performing back extraction on a Cyanex272 organic phase extracted with manganese ions by using dilute sulfuric acid of 4.5-5.5mol/L, controlling the pH value of the back extraction solution to be 3.5-4.5, obtaining a back extraction solution which is a manganese sulfate solution, concentrating and thermally filtering manganese sulfate by MVR to obtain manganese sulfate crystals and a mother solution, returning the mother solution to a replacement process, reducing impurities in the solution, washing the replacement slag by water, leaching by using sulfuric acid and hydrogen peroxide, wherein the hydrogen peroxide is used as a reducing agent for reducing high-valence cobalt-nickel manganese without adding new impurity ions, the usage of the hydrogen peroxide is 0.1-0.25 of the weight of the replacement slag, regulating the pH value by using the sulfuric acid, controlling the end point pH value to be 0.5-2.0, controlling the reaction temperature to be 75-85 ℃, reacting for 180 minutes, controlling the temperature of the leachate after filtering to be 85-95 ℃, adding the hydrogen peroxide as an oxidizing agent, adding the manganese powder into the solution in an amount which is 0.85 to 1.05 times of the theoretical amount of oxidation of ferrous ions, reacting for 30 to 60 minutes, adding the manganese powder to adjust the pH value to 2.5 to 3.5, reacting for 60 to 120 minutes, filtering, concentrating the filtrate, performing primary heat filtration, filtering manganese sulfate microcrystals generated by the material, removing the microcrystals, performing cooling crystallization, returning the microcrystals to a replacement process for dissolution, performing cooling crystallization after the heat filtration to obtain a nickel-cobalt-manganese sulfate mixed crystal, and returning the mother solution to the concentration crystallization or removing iron to remove enriched impurities.
Claims (10)
1. A comprehensive recovery method of waste lithium batteries is characterized by comprising the following steps: a. crushing; b. electrolyzing slurry; c. sieving; d. filtering; e. removing oil; f. copper removal; g. removing iron; h. removing impurities; i. replacement; j. extracting; k. adjusting acid; l, precipitating; MVR + crystallization; n, fine grinding; o. back extraction; leaching; q. removing iron from the replacement slag leachate, wherein a: crushing the battery and water together at normal temperature, wherein the mass ratio of the water to the battery is 1: 1-2.5, and b, slurry electrolysis: and putting the crushed water and the battery material into a special slurry electrolytic tank for electrolytic dissolution.
2. The method for comprehensively recycling the waste lithium batteries according to claim 1, wherein the step c is sieving, namely sieving the solid materials generated by the cathode and anode electrolytic cells, wherein the sieve aperture is 60-100 meshes; and d, filtering: filtering the cathode electrolysis overflow liquid to respectively obtain filtrate and filter residues, wherein the filtrate is a sulfate solution of nickel, cobalt, manganese and lithium, and the filter residues are black powder and carbon powder which are not completely dissolved out; and e, deoiling: and (3) removing oil from the filtrate at normal temperature by using activated carbon, and mainly adsorbing and removing organic matters in the battery.
3. The method for comprehensively recycling waste lithium batteries according to claim 1, wherein the f-decoppering: removing copper from the filtrate by using sodium thiosulfate after removing oil by using activated carbon, wherein the aim is to remove copper ions, and other impurity ions except sodium are not added; g, iron removal: after copper is removed, the temperature of the filtrate is raised to 85-95 ℃, and an oxidant is added to oxidize ferrous iron into ferric iron.
4. The method for comprehensively recycling waste lithium batteries according to claim 1, wherein the h.impurity removal: after copper is removed, the temperature of the filtrate is raised to 85-95 ℃, manganese powder is added, the dosage of the manganese powder is 0.2-1kg per cubic meter, and the reaction time is 30-60 minutes, so that impurities such as cadmium in the solution can be removed; the i, substitution: controlling the temperature of the solution after impurity removal at 50-75 ℃, adding manganese powder at the speed of 0.05-0.2kg per minute, wherein the addition amount of the manganese powder is 1.05-1.15 times of the theoretical amount of nickel cobalt replacement, reacting for 30-60 minutes, and replacing slag is mixed slag containing nickel, cobalt and manganese.
5. The method for comprehensively recycling waste lithium batteries according to claim 1, wherein j is an extraction: extracting manganese from the solution after impurity removal by adopting Cyanex272, controlling the content of the Cyanex272 at 15-20%, comparing with 1:2-4, mixing for 2-5 minutes, extracting manganese from the solution after impurity removal into an organic phase according to the extraction characteristics of the Cyanex272, and keeping lithium in raffinate to achieve the separation of manganese and lithium; k, acid adjustment: controlling the temperature of raffinate at 45-60 ℃, adjusting the pH value to 10-11.5 by using alkali, and reacting for 30-60 minutes, wherein the acid is used for adjusting and controlling the pH value of the solution so as to facilitate subsequent operation, and on the other hand, nickel, cobalt and manganese in the raffinate are completely precipitated, and the nickel, cobalt and manganese are precipitated in the acid adjusting process; the l. precipitation: adjusting the acid of the filtered solution, controlling the temperature to be 60-80 ℃, adding sodium carbonate, wherein the adding amount is 1.25-1.3 times of the theoretical amount of the precipitated lithium content, reacting for 60-120 minutes, and precipitating the lithium into lithium carbonate, wherein the lithium contained in the precipitated solution is still about 2g/L due to the solubility problem of the lithium carbonate.
6. The method for comprehensively recycling waste lithium batteries according to claim 1, wherein the m.mvr + crystal: the filtered precipitation mother liquor was concentrated using MVR, the degree of concentration being based on the occurrence of visible crystals. Cooling to obtain the lithium carbonate. The mother liquor can be returned to remove iron and regulate acid or returned to be continuously concentrated and crystallized; n, fine grinding: sieving solid materials after the first electrolytic dissolution to obtain oversize materials, grinding the materials to 60-100 meshes by a fine grinding machine, sieving the materials again after the fine grinding, and respectively carrying out magnetic separation and gravity separation on the oversize materials to obtain a steel shell, a diaphragm, copper-aluminum powder and carbon powder; the undersize products are dissolved out through one time of electrolysis, the undersize products are filtered after the dissolution is finished, the filtrate is merged into the first electrolysis dissolved liquid to remove oil, and the copper-aluminum powder and carbon powder are obtained after the filter residues are reselected; and combining the copper and aluminum powder, and carrying out color sorting to obtain copper powder and aluminum powder.
7. The method for comprehensively recycling waste lithium batteries according to claim 1, characterized in that the o-strip: performing back extraction on the Cyanex272 organic phase extracted with manganese ions by using 4.5-5.5mol/L dilute sulfuric acid, controlling the pH value of a back extraction solution to be 3.5-4.5, wherein the obtained back extraction solution is a manganese sulfate solution, concentrating and thermally filtering manganese sulfate by MVR to obtain manganese sulfate crystals and a mother solution, returning the mother solution to a replacement process, and reducing impurities in the solution; and p leaching: after washing the replacement slag, leaching the replacement slag by adding hydrogen peroxide into sulfuric acid, wherein the hydrogen peroxide is used as a reducing agent to reduce high-valence cobalt, nickel and manganese without adding new impurity ions; q, removing iron from the replacement slag leachate: filtering the leachate, controlling the temperature to be 85-95 ℃, adding hydrogen peroxide as an oxidant, wherein the adding amount is 0.85-1.05 times of the theoretical oxidation amount of ferrous ions, the reaction time is 30-60 minutes, adding manganese powder to adjust the pH value to 2.5-3.5, and the reaction time is 60-120 minutes, after filtering, concentrating the filtrate, firstly carrying out primary thermal filtration, filtering to generate manganese sulfate microcrystals, wherein the purpose is to control crystal grains during cooling crystallization after removing the microcrystals, returning the microcrystals to the replacement process for dissolution, cooling crystallization after thermal filtration to obtain mixed crystals of nickel, cobalt and manganese sulfate, and returning the mother liquor to the concentration crystallization or deironing to remove enriched impurities.
8. The method for comprehensively recycling waste lithium batteries according to claim 4, wherein the i-displacement comprises an outer box body (1) and a material taking assembly (3), the right side of the lower end inside the outer box body (1) is provided with a water circulation assembly (2), the water circulation assembly (2) comprises a water pump (201), a water circulation pipe (202), a water discharge pipe (203) and an electromagnetic valve (204), the upper end of the water pump (201) is connected with the water circulation pipe (202), the right end of the water circulation pipe (202) is connected with the water discharge pipe (203), the electromagnetic valve (204) is installed outside the water discharge pipe (203), and the material taking assembly (3) is located on the left side of the lower end inside the outer box body (1).
9. The method for comprehensively recycling waste lithium batteries according to claim 8, wherein the material taking assembly (3) comprises a material discharging plate (301), a vibration motor (302), a material collecting box (303), a sealing rear plate (304) and a directional rod (305), the vibration motor (302) is installed in the middle of the lower end of the material discharging plate (301), the material collecting box (303) is arranged on the left side of the lower end of the material discharging plate (301), the sealing rear plate (304) is connected to the right end of the material collecting box (303), the directional rod (305) penetrates through the lower end of the sealing rear plate (304), the liquid receiving box (4) is installed on the left side of the outer box (1), the stirring assembly (5) is installed at the upper end inside the outer box (1), the stirring assembly (5) comprises a stirring rod (501), a heating plate (502), a tensile elastic rope (503), a blocking balancing weight (504) and a directional guide rod (505), and the inside heating plate (502) that is provided with in left side of puddler (501), the right-hand member of puddler (501) is connected with pulling force and plays rope (503), and the right side of pulling force play rope (503) is connected with shutoff balancing weight (504), the upper and lower both ends of shutoff balancing weight (504) are connected with directional guide arm (505).
10. The method for comprehensively recycling waste lithium batteries according to claim 8, characterized in that a power assembly (6) is mounted at the upper end of the outer box (1), the power assembly (6) comprises a driving motor (601), a first gear (602), a second gear (603), a third gear (604), a rotary positioning block (605) and a rotary ball (606), the first gear (602) and the second gear (603) are sequentially arranged outside the driving motor (601) from right to left, the third gear (604) is connected to the lower end of the second gear (603), the rotary positioning block (605) and the rotary ball (606) are sequentially arranged at the lower end of the third gear (604) from outside to inside, a dispersing assembly (7) is arranged at the upper end of the power assembly (6), and the dispersing assembly (7) comprises a snake bone steel cable (701), a fourth gear (702) and a snake bone steel cable (606), The snake bone steel cable comprises a fifth gear (703) and a first bearing (704), a fourth gear (702), the fifth gear (703) and the first bearing (704) are sequentially arranged outside the snake bone steel cable (701), the left end of the fifth gear (703) is connected with a lifting assembly (8), the lifting assembly (8) comprises a lifting plate (801), a second bearing (802), a threaded lifting rod (803), a sixth gear (804), a threaded sleeve (805) and an expansion rod (806), the second bearing (802) is installed inside the lifting plate (801), the threaded lifting rod (803) penetrates through the inside of the second bearing (802), the sixth gear (804) is connected to the upper end of the threaded lifting rod (803), the threaded sleeve (805) is connected to the lower end of the threaded lifting rod (803), and the expansion rod (806) is connected to the lower end of the lifting plate (801).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115679117A (en) * | 2022-11-18 | 2023-02-03 | 金川集团股份有限公司 | Method for reducing cobalt content of iron-removing tailings of cobalt raw material leaching solution |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106785174A (en) * | 2017-02-24 | 2017-05-31 | 中南大学 | A kind of method for being leached from lithium ion cell anode waste based on electrochemical process and reclaiming metal |
| CN107385220A (en) * | 2017-08-04 | 2017-11-24 | 俞振元 | A kind of method of the reclaiming high purity nickel from waste nickel catalyst |
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| CN108270045A (en) * | 2018-01-05 | 2018-07-10 | 昆明理工大学 | A kind of electrochemical leaching method of waste lithium cell positive electrode |
| CN109321745A (en) * | 2018-11-06 | 2019-02-12 | 泰州华昊废金属综合利用有限公司 | Utilize the method for Treatment of Metal Surface waste preparation nickel plate |
| CN109518225A (en) * | 2019-01-16 | 2019-03-26 | 北京矿冶科技集团有限公司 | A kind of method of ferrous iron and cobalt nickel in separation solution |
-
2022
- 2022-05-13 CN CN202210521159.2A patent/CN114892005B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106785174A (en) * | 2017-02-24 | 2017-05-31 | 中南大学 | A kind of method for being leached from lithium ion cell anode waste based on electrochemical process and reclaiming metal |
| CN107385220A (en) * | 2017-08-04 | 2017-11-24 | 俞振元 | A kind of method of the reclaiming high purity nickel from waste nickel catalyst |
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| CN108270045A (en) * | 2018-01-05 | 2018-07-10 | 昆明理工大学 | A kind of electrochemical leaching method of waste lithium cell positive electrode |
| CN109321745A (en) * | 2018-11-06 | 2019-02-12 | 泰州华昊废金属综合利用有限公司 | Utilize the method for Treatment of Metal Surface waste preparation nickel plate |
| CN109518225A (en) * | 2019-01-16 | 2019-03-26 | 北京矿冶科技集团有限公司 | A kind of method of ferrous iron and cobalt nickel in separation solution |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115679117A (en) * | 2022-11-18 | 2023-02-03 | 金川集团股份有限公司 | Method for reducing cobalt content of iron-removing tailings of cobalt raw material leaching solution |
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