CN114892005B - Comprehensive recovery method of waste lithium battery - Google Patents
Comprehensive recovery method of waste lithium battery Download PDFInfo
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- CN114892005B CN114892005B CN202210521159.2A CN202210521159A CN114892005B CN 114892005 B CN114892005 B CN 114892005B CN 202210521159 A CN202210521159 A CN 202210521159A CN 114892005 B CN114892005 B CN 114892005B
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- manganese
- gear
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- lithium
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- 238000000034 method Methods 0.000 title claims abstract description 68
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 53
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000002699 waste material Substances 0.000 title claims abstract description 20
- 238000011084 recovery Methods 0.000 title claims description 11
- 239000012535 impurity Substances 0.000 claims abstract description 42
- 238000001914 filtration Methods 0.000 claims abstract description 33
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 23
- 239000002893 slag Substances 0.000 claims abstract description 23
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- 238000002386 leaching Methods 0.000 claims abstract description 20
- 238000007873 sieving Methods 0.000 claims abstract description 19
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 18
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 18
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 18
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 16
- 238000006073 displacement reaction Methods 0.000 claims abstract description 14
- 238000000227 grinding Methods 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 238000001556 precipitation Methods 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 64
- 238000003756 stirring Methods 0.000 claims description 55
- 239000000463 material Substances 0.000 claims description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 239000000706 filtrate Substances 0.000 claims description 34
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 28
- 229910052748 manganese Inorganic materials 0.000 claims description 27
- 239000011572 manganese Substances 0.000 claims description 27
- 238000004090 dissolution Methods 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 25
- 230000035484 reaction time Effects 0.000 claims description 21
- 238000000605 extraction Methods 0.000 claims description 20
- 229910017052 cobalt Inorganic materials 0.000 claims description 19
- 239000010941 cobalt Substances 0.000 claims description 19
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 19
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 239000012452 mother liquor Substances 0.000 claims description 18
- 238000010438 heat treatment 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
- 229910000831 Steel Inorganic materials 0.000 claims description 15
- 239000013081 microcrystal Substances 0.000 claims description 15
- 239000010959 steel Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 241000270295 Serpentes Species 0.000 claims description 13
- 210000000988 bone and bone Anatomy 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
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 230000001276 controlling effect Effects 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
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 230000001105 regulatory effect Effects 0.000 claims description 12
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 11
- 239000007800 oxidant agent Substances 0.000 claims description 10
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- 238000007789 sealing Methods 0.000 claims description 9
- 239000012074 organic phase Substances 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
- 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
- 230000001376 precipitating effect Effects 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
- 238000007599 discharging Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000000926 separation method 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
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 229910001448 ferrous ion Inorganic materials 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
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000012467 final product Substances 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 10
- 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
- 230000000694 effects Effects 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
- 238000010586 diagram Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [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
- 229940001584 sodium metabisulfite Drugs 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
- 235000010269 sulphur dioxide Nutrition 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 230000003245 working effect Effects 0.000 description 2
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229940044175 cobalt sulfate Drugs 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
- 238000005187 foaming Methods 0.000 description 1
- 230000005484 gravity Effects 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
- 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
- 229940073644 nickel Drugs 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to a method for comprehensively recovering waste lithium batteries, which comprises the following steps: a. crushing; b. electrolyzing the slurry; c. sieving; d. filtering; e. removing oil; f. copper removal; g. iron removal; h. removing impurities; i. replacement; j. extracting; k. acid regulation; i, precipitation; mvr+ crystallization; n, fine grinding; back-extracting; leaching; and q, removing iron from the displacement slag leaching solution. The beneficial effects of the invention are as follows: according to the method for comprehensively recycling the waste lithium batteries, on one hand, the traditional treatment method is combined, so that 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 direct yield of the batteries to the final product is improved, the battery disassembling and acid dissolving processes are simplified, and the process loss is reduced; the technological process is simplified and shortened, the amount of slag generated is small, and the process loss is reduced.
Description
Technical Field
The invention relates to the technical field of waste lithium batteries, in particular to a comprehensive recovery method of waste lithium batteries.
Background
The lithium battery is a battery using lithium metal or lithium alloy as a negative electrode material and using a nonaqueous electrolyte solution, so that the battery is also called a lithium metal battery, and the waste lithium battery has an influence on the environment if the waste lithium battery is directly discarded, so that the waste lithium battery needs to be recycled.
The traditional recovery method firstly generates a large amount of dust in the process that the waste batteries need to undergo complicated discharging and crushing processes; the second disassembled battery powder is subjected to wet smelting after being calcined and transported, the process is complicated, and the dust loss in the transportation process is large; the third traditional lithium battery has long recovery flow, 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 aiming at the problems.
Disclosure of Invention
The invention aims to provide a comprehensive recovery method of waste lithium batteries, which aims to solve the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions: the comprehensive recovery method of the waste lithium battery comprises the following steps: a. crushing; b. electrolyzing the slurry; c. sieving; d. filtering; e. removing oil; f. copper removal; g. iron removal; h. removing impurities; i. replacement; j. extracting; k. acid regulation; i, precipitation; mvr+ crystallization; n, fine grinding; back-extracting; leaching; removing iron from the displacement slag leachate, wherein a is crushed: crushing the battery and water at normal temperature, wherein the mass ratio of the water to the battery is 1:1-2.5, and b. electrolyzing the slurry: and (3) putting the crushed water and the crushed battery material into a special slurry electrolytic tank for electrolytic dissolution.
Further, sieving, namely sieving solid materials generated by the cathode and anode electrolytic tank, wherein the sieving aperture is 60-100 meshes; filtering: filtering the cathode electrolysis overflow liquid to obtain filtrate and filter residue respectively, wherein the filtrate is sulfate solution of nickel, cobalt, manganese and lithium, and the filter residue is black powder and carbon powder which are not completely dissolved; deoiling: the filtrate is deoiled by active carbon at normal temperature, and organic matters in the battery are mainly removed by adsorption.
Further, the f. copper removal: removing copper from the filtrate by using sodium thiosulfate after removing oil by using active carbon, wherein other impurity ions are not added except sodium in order to remove copper ions; iron removal: heating the filtrate to 85-95 ℃ after copper removal, and adding an oxidant to oxidize ferrous iron into ferric iron.
Further, the h. removing impurities: heating the filtrate to 85-95 ℃ after copper removal, adding manganese powder with the dosage of 0.2-1kg per cubic meter, and reacting for 30-60 minutes, wherein the purpose is to remove impurities such as cadmium and the like in the solution; substitution: the temperature of the solution after impurity removal is controlled at 50-75 ℃, manganese powder is added, 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 using Cyanex272, wherein the content of Cyanex272 is controlled to be 15-20%, compared with 1:2-4, the mixing time is 2-5 minutes, extracting manganese in the solution after impurity removal into an organic phase according to the extraction characteristic of Cyanex272, and retaining lithium in raffinate to separate manganese from lithium; acid regulation: controlling the temperature of the raffinate to be 45-60 ℃, regulating the pH value to be 10-11.5 by using alkali, and reacting for 30-60 minutes, wherein the acid regulation is used for regulating the pH value of the solution so as to facilitate the subsequent operation, and on the other hand, completely precipitating nickel, cobalt and manganese in the solution, wherein the acid regulation process can generate nickel, cobalt and manganese precipitation; precipitation: adjusting the temperature of the filtered solution to 60-80 ℃, adding sodium carbonate with the addition amount being 1.25-1.3 times of the theoretical amount of precipitated lithium content, reacting for 60-120 minutes, precipitating lithium into lithium carbonate, and still keeping the content of lithium in the precipitated solution to be 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 to a degree that produced visible crystallization. And cooling to obtain lithium carbonate. The mother liquor can be returned to remove iron and adjust acid or returned to continue concentrating crystallization; the n. fine grinding: grinding the materials to 60-100 meshes by a fine grinder after the oversize materials obtained by sieving the solid materials after the first electrolytic dissolution, sieving the materials again after the fine grinding, and respectively carrying out magnetic separation and reselection on the oversize materials to obtain steel shells, diaphragms, copper-aluminum powder and carbon powder; the undersize material is dissolved out again through electrolysis, after dissolution is finished, the undersize material is filtered, the filtrate is merged into the first electrolytic dissolution solution to remove oil, and the filter residue is reselected to obtain copper aluminum powder and carbon powder; and combining the copper powder and the aluminum powder, and separating copper powder and aluminum powder by color separation.
Further, the o. back extraction: carrying out back extraction on the Cyanex272 organic phase extracted with manganese ions by adopting 4.5-5.5mol/L dilute sulfuric acid, controlling the PH value of the back extraction liquid to be 3.5-4.5, obtaining the back extraction liquid which is manganese sulfate solution, concentrating manganese sulfate through MVR and hot filtering to obtain manganese sulfate crystals and mother liquor, returning the mother liquor to a replacement process, and reducing impurities in the solution; the p leaching: leaching the displacement slag by adding sulfuric acid and hydrogen peroxide after washing, wherein the hydrogen peroxide is used as a reducing agent, and the aim is to reduce high-valence cobalt nickel manganese without adding new impurity ions; the substitution slag leaching solution is deironized: filtering the leaching solution, controlling the temperature to be 85-95 ℃, adding hydrogen peroxide as an oxidant, adding 0.85-1.05 times of the theoretical amount of ferrous ion oxidation, reacting for 30-60 minutes, adding manganese powder to adjust the PH value to 2.5-3.5, reacting for 60-120 minutes, filtering, concentrating the filtrate, performing primary thermal filtration, and filtering to obtain manganese sulfate microcrystals, wherein the purpose is to remove the microcrystals, wherein crystal grains are controllable when the microcrystals are cooled and crystallized after cooling, the microcrystals are returned to a replacement procedure for dissolution, cooling and crystallizing are performed after thermal filtration, thus obtaining mixed crystal of nickel cobalt manganese sulfate, and mother liquor is returned to concentrated crystallization or deironing to remove enriched impurities.
Further, the replacement includes outer box and gets material subassembly, the inside lower extreme right side of outer box is provided with hydrologic cycle subassembly, and hydrologic cycle subassembly includes water pump, circulating pipe, drainage 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 the drainage pipe, the externally mounted of drainage pipe has the solenoid valve, it is left that the material subassembly is located the inside lower extreme of outer box.
Further, get material subassembly and include flitch, vibrating motor, collection workbin, sealed back plate and directional pole, the lower extreme mid-mounting of flitch has vibrating motor, and the lower extreme left side of flitch is provided with collection workbin, the right-hand member of collection workbin is connected with sealed back plate, and the lower extreme of sealed back plate runs through there is directional pole, connect the liquid case in the left side of outer box, and the inside upper end of outer box installs the stirring subassembly, the stirring subassembly includes puddler, heating plate, pulling force bullet 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 pulling force bullet rope, and the right-hand member of pulling force bullet rope is connected with the shutoff balancing weight, the upper and lower both ends of shutoff balancing weight are connected with directional guide arm.
Further, the power component is installed to the upper end of outer box, and power component includes driving motor, first gear, second gear, third gear, rotation locating piece and spin ball, driving motor's outside has set gradually first gear and second gear from the right side to the left side, and the lower extreme of second gear is connected with the third gear, the lower extreme of third gear has set gradually rotation locating piece and spin ball from the outside to interior, power component's upper end is provided with stirs the subassembly, and stirs the subassembly and include snake bone cable, fourth gear, fifth gear and first bearing, the outside of snake bone cable has set gradually fourth gear, fifth gear and first bearing, the left end of fifth gear is connected with the lifting component, and the lifting component includes lifter plate, second bearing, screw thread lifter, sixth gear, thread bush and telescopic link, the internally mounted of lifter plate has the second bearing, and the inside run through screw thread lifter, the upper end of screw thread lifter is connected with sixth gear, and the lower extreme connection of screw thread lifter has the lower extreme of thread lifter.
Compared with the prior art, the invention has the beneficial effects that:
1. on one hand, the method combines the traditional treatment method, so that 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 direct yield of the battery to the final product is improved, the battery disassembly and acid dissolution processes are simplified, and the process loss is reduced; the process flow is simplified and shortened, the slag amount is small, the process loss is reduced, auxiliary materials containing other impurity ions are used as little as possible in the process of the patent, the carrying-in of the impurity ions is reduced, and the impurity removal difficulty is reduced.
2. According to the invention, the driving motor drives the third gear to rotate through the second gear, so that the stirring rod is driven to rotate, the plugging balancing weight is enabled to slide along the directional guide rod under the influence of centrifugal force, so that the plugging balancing weight is opened for the stirring rod, manganese powder is conveniently and uniformly sprayed out in the rotation process, replacement work of equipment is facilitated, and the working effect of the equipment is increased.
3. According to the invention, the filtered liquid can be conveyed to the upper part of the blanking plate again through the water pump for continuous replacement, 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 material collecting box along the inclined plane of the blanking plate for collection.
4. According to the invention, the driving motor drives the fourth gear to rotate through the first gear, so that the snake bone steel cable rotates to stir and break up manganese powder in the stirring rod, the blocking of the stirring rod during manganese powder sprinkling is prevented, and meanwhile, the fifth gear drives the sixth gear to rotate, so that the lifting plate is lifted by means of threaded connection of the threaded lifting rod and the threaded sleeve, and the snake bone steel cable can more repeatedly break up manganese powder in the stirring rod.
Drawings
FIG. 1 is a process flow diagram of a method for the integrated recovery of spent lithium batteries of the present invention;
FIG. 2 is a schematic diagram showing the front view structure of a replacement device of the method for comprehensively recovering waste lithium batteries;
FIG. 3 is an enlarged schematic cross-sectional view of a stirring assembly according to the method for comprehensively recovering waste lithium batteries of the present invention;
fig. 4 is an enlarged schematic view of a stirring assembly of the method for comprehensively recovering waste lithium batteries.
In the figure: 1. an outer case; 2. a water circulation assembly; 201. a water pump; 202. a circulating water pipe; 203. a drain pipe; 204. an electromagnetic valve; 3. a material taking assembly; 301. a blanking plate; 302. a vibration motor; 303. a material collecting box; 304. sealing the rear plate; 305. a directional rod; 4. a liquid receiving box; 5. a stirring assembly; 501. a stirring rod; 502. a heating sheet; 503. pulling force elastic ropes; 504. plugging the balancing weight; 505. a directional guide rod; 6. a power assembly; 601. a driving motor; 602. a first gear; 603. a second gear; 604. a third gear; 605. rotating the positioning block; 606. a rotating ball; 7. a stirring assembly; 701. snake bone steel rope; 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 thread sleeve; 806. a telescopic rod.
Detailed Description
As shown in fig. 1 to 4, the present invention provides a technical solution: the comprehensive recovery method of the waste lithium battery comprises the following steps:
a. crushing: crushing the battery and water together under normal temperature, wherein the mass ratio of the water to the battery is (the specific gravity of the water is considered as 1) 1:1 to 2.5;
b. and (3) slurry electrolysis: the crushed water and the battery material are put into a special slurry electrolytic tank (the concrete structure and the 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 is as follows: 45-55 ℃, 1.8-3.0V of voltage, 2000-3000A of current, 100-300A/m2 of current density, 30-100 r/min of stirring rotation speed of an anode tank, 50-130 r/min of stirring rotation speed of a cathode tank, sodium metabisulfite, sodium sulfite, sulfur dioxide and sodium thiosulfate as reducing agents, the adding amount is 0.01-0.05 of the mass of a battery, sulfuric acid is added to control the pH value of dissolution, the pH value is controlled within the range of 0.5-2.0, the surfactant is nonionic, the foaming is mainly controlled in the process, the dissolution efficiency is improved, 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
cathode reaction:
LiCoO2+2Fe2++4H+＝Co2++2Fe3++2H2O
LiNiO2+2Fe2++4H+＝Ni2++2Fe3++2H2O
LiMn2O4+2Fe2++8H+＝2Mn2++2Fe3++4H2O
anode reaction:
Mn2++2H2O＝MnO2+4H++2e
H2O＝1/2O2↑+2H++2e
Fe2+＝Fe3++e；
c. sieving: sieving solid materials generated by the cathode and anode electrolytic tank, wherein the sieving aperture is 60-100 meshes;
d. and (3) filtering: filtering the cathode electrolysis overflow liquid to obtain filtrate and filter residue respectively, wherein the filtrate is sulfate solution of nickel, cobalt, manganese and lithium, and the filter residue is black powder and carbon powder which are not completely dissolved;
e. deoiling: removing oil from the filtrate by adopting active carbon under normal temperature, mainly removing organic matters (electrolyte and adhesive) in the battery by adsorption, wherein the dosage of the active carbon is adjusted according to the TOC content in the filtrate, the dosage is 1:50-200 of TOC value, namely the dosage of 1g/LTOC added active carbon is 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 active carbon, wherein in order to remove copper ions, other impurity ions are not added except sodium, the reaction temperature is 80-95 ℃, and the dosage of the sodium thiosulfate is as follows: copper ions are 1:1.05-1.25, and the reaction time is 30-90 minutes;
g. iron removal: heating the filtrate to 85-95 ℃ after copper removal, adding an oxidant (sodium chlorate, sodium hypochlorite, sodium persulfate and the like), oxidizing ferrous iron into ferric iron, wherein the dosage of the oxidant is 1.05-1.2 times of the theoretical amount of ferrous iron oxide, reacting for 30-70 minutes, adding alkali (sodium carbonate and sodium hydroxide) to adjust the PH to 2.5-4.5, and reacting for 60-120 minutes;
h. removing impurities: heating the filtrate to 85-95 ℃ after copper removal, adding manganese powder, wherein the dosage of the manganese powder is 0.2-1kg per cubic meter, and the reaction time is 30-60 minutes, so as 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
The metal manganese powder and cadmium in the solution undergo a displacement reaction, and impurities in the solution are removed by the displacement reaction;
i. replacement: the temperature of the liquid after impurity removal is controlled at 50-75 ℃, manganese powder is added, 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, the replacement 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 undergo a displacement reaction, only manganese and lithium are left in the displaced solution, and cobalt and nickel enter displacement slag;
j. extraction: extracting manganese from the solution after impurity removal by using Cyanex272 (extracted organic), wherein the content of Cyanex272 is controlled to be 15-20%, compared with 1:2-4, the mixing time is 2-5 minutes, and extracting manganese in the solution after impurity removal into an organic phase according to the extraction characteristic of Cyanex272, and lithium is left in raffinate to achieve separation of manganese and lithium;
k. acid regulation: controlling the temperature of the raffinate to be 45-60 ℃, regulating the pH value to be 10-11.5 by using alkali, and reacting for 30-60 minutes, wherein the acid regulation is used for regulating the pH value of the solution so as to facilitate the subsequent operation, and on the other hand, completely precipitating nickel, cobalt and manganese in the solution, wherein the acid regulation process can generate nickel, cobalt and manganese precipitation;
precipitation: regulating the temperature of the filtered solution to 60-80 ℃, adding sodium carbonate, wherein the adding amount is 1.25-1.3 times of the theoretical amount of precipitated lithium content, reacting for 60-120 minutes, precipitating lithium into lithium carbonate, and still keeping the content of lithium in the precipitated solution to be about 2g/L due to the solubility problem of the lithium carbonate;
mvr+ crystallization: concentrating the filtered precipitation mother liquor by MVR (mechanical vapor recompression) to the extent that visible crystallization is generated as a standard, cooling to obtain lithium carbonate, and returning the mother liquor to remove iron and adjust acid or to continue concentrating crystallization;
and n, fine grinding: grinding the materials to 60-100 meshes by a fine grinder after the oversize materials obtained by sieving the solid materials after the first electrolytic dissolution, sieving the materials again after the fine grinding, and respectively carrying out magnetic separation and reselection on the oversize materials to obtain steel shells, diaphragms, copper-aluminum powder and carbon powder; the undersize material is dissolved out again through electrolysis, after dissolution is finished, the undersize material is filtered, the filtrate is merged into the first electrolytic dissolution solution to remove oil, and the filter residue is reselected to obtain copper aluminum powder and carbon powder; combining copper and aluminum powder, and separating copper powder and aluminum powder by color separation;
back extraction: carrying out back extraction on the Cyanex272 organic phase extracted with manganese ions by adopting 4.5-5.5mol/L dilute sulfuric acid, controlling the PH value of the back extraction liquid to be 3.5-4.5, obtaining the back extraction liquid which is manganese sulfate solution, concentrating manganese sulfate through MVR and hot filtering to obtain manganese sulfate crystals and mother liquor, returning the mother liquor to a replacement process, and reducing impurities in the solution;
p leaching: leaching the displacement slag by adding sulfuric acid and hydrogen peroxide after washing, wherein the hydrogen peroxide is used as a reducing agent, the aim is to reduce high-valence cobalt nickel manganese without adding new impurity ions, the consumption of the hydrogen peroxide is 0.1-0.25 of the weight of the displacement slag, the PH value is regulated and controlled by adopting sulfuric acid, the end PH value is controlled to be 0.5-2.0, the reaction temperature is controlled to be 75-85 ℃, and the reaction time is 120-180 minutes;
and q, removing iron from the displacement slag leaching solution: filtering the leaching solution, controlling the temperature to be 85-95 ℃, adding hydrogen peroxide serving as an oxidant, wherein the addition amount of the hydrogen peroxide is 0.85-1.05 times of the theoretical amount of ferrous ion oxidation, the reaction time is 30-60 minutes, adding manganese powder to adjust the PH value to 2.5-3.5, the reaction time is 60-120 minutes, filtering, concentrating the filtrate, performing primary hot filtration, and filtering to obtain manganese sulfate microcrystals, wherein the purpose is that crystal grains are controllable when the microcrystals are cooled and crystallized after removal, the microcrystals return to a replacement procedure for dissolution, cooling and crystallization are performed after hot filtration, thus obtaining mixed crystals of nickel, cobalt and manganese sulfate, and mother liquor returns to concentrated crystallization or deironing to remove enriched impurities;
on one hand, the method combines the traditional treatment method, so that 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 direct yield of the battery to the final product is improved, the battery disassembly and acid dissolution processes are simplified, and the process loss is reduced; the process flow is simplified and shortened, the slag amount is small, the process loss is reduced, auxiliary materials containing other impurity ions are used as little as possible in the process of the patent, the carrying-in 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, wherein a water circulation assembly 2 is arranged on the right side of the lower end of the inner part of the outer box 1, 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 arranged on the outer part of the water discharge pipe 203, the material taking assembly 3 is positioned on the left side of the lower end of the inner part of the outer box 1, the material taking assembly 3 comprises a blanking plate 301, a vibrating motor 302, an aggregate box 303, a sealing rear plate 304 and a directional rod 305, the lower end middle part of the blanking plate 301 is provided with the vibrating motor 302, the lower end left side of the blanking plate 301 is provided with the aggregate box 303, the right end of the aggregate box 303 is connected with the sealing rear plate 304, the lower end of the sealing rear plate 304 penetrates through the directional rod 305, the left side of the outer box 1 is provided with a liquid receiving box 4, the upper end of the water discharge pipe 203 is provided with the electromagnetic valve 204, the inner part of the water discharge pipe 203 is provided with the electromagnetic valve, the material taking assembly 5, the material taking assembly 3 is positioned on the left side of the inner part of the outer box 1, the lower end of the material taking assembly comprises a stirring assembly 504, the stirring assembly 5, the stirring assembly comprises a stirring rod, the stirring rod 502, the stirring rod 501, the heating rods and the stirring rod 502 are connected with the stirring rods and the stirring rods are connected to the stirring rods, the stirring rods are arranged in a sealing rods, and the heating rods are connected to the stirring rods, and the stirring rods are connected to the stirring rods and the stirring rods are respectively, and the heating rods and the one;
according to the invention, the driving motor 601 drives the third gear 604 to rotate through the second gear 603, so that the stirring rod 501 is driven to rotate, the plugging counter weight 504 is enabled to slide along the directional guide rod 505 under the influence of centrifugal force, so that the plugging counter weight 504 is opened for the stirring rod 501, manganese powder is convenient to uniformly spill out in the rotation process, replacement work of equipment is convenient, the working effect of the equipment is improved, filtered liquid can be conveyed to the upper side of the blanking plate 301 again through the water pump 201 to continue replacement, the equipment forms a circulation, the replacement effect of the equipment is better, meanwhile, the vibration motor 302 can continuously vibrate the blanking plate 301, particles replaced on the blanking plate 301 slide down into the collecting box 303 along the inclined plane of the blanking plate 301 to be collected, the electromagnetic valve 204 can control the switch of the drainage pipe 203, liquid discharging is controlled, and the pulling force elastic rope 503 can be convenient for resetting the plugging counter weight 504.
As shown in fig. 4, a power assembly 6 is installed 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 rotating positioning block 605 and a rotating ball 606, the first gear 602 and the second gear 603 are sequentially arranged at the left end of the driving motor 601 from right, the lower end of the second gear 603 is connected with a third gear 604, the rotating positioning block 605 and the rotating ball 606 are sequentially arranged at the lower end of the third gear 604 from outside to inside, a stirring assembly 7 is arranged at the upper end of the power assembly 6, the stirring assembly 7 comprises 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 704 are sequentially arranged at the outer end of the snake bone steel cable 701, a lifting assembly 8 is connected at the left end of the fifth gear 703, 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 a telescopic rod, the lifting plate 801 is internally installed at the lifting assembly 801, the second bearing 802 is internally provided with a lifting rod 803, and a threaded rod 803 is connected at the lower end of the lifting assembly 803 through the lifting rod 803, and a threaded rod 803 is threaded at the lifting assembly 803;
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 break up manganese powder in the stirring rod 501, the blocking is prevented when manganese powder is sprayed out, meanwhile, the fifth gear 703 drives the sixth gear 804 to rotate, the lifting plate 801 is lifted by means of threaded connection of the threaded lifting rod 803 and the threaded sleeve 805, the snake bone steel cable 701 can conveniently and repeatedly break up 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 rotating positioning block 605 can play a role in positioning the rotation of the third gear 604, and the rotating ball 606 can reduce the friction force of the rotation of the third gear 604.
Working principle: under the normal temperature condition, crushing the battery and water together, wherein the mass ratio of the water to the battery is 1:1-2.5, and throwing the crushed water and battery materials into a special slurry electrolytic tank for electrolytic dissolution at the temperature: 45-55 ℃, 1.8-3.0V of voltage, 2000-3000A of current, 100-300A/m < 2 > of current density, 30-100 r/min of stirring rotation speed of an anode tank, 50-130 r/min of stirring rotation speed of a cathode tank, sodium metabisulfite, sodium sulfite, sulfur dioxide and sodium thiosulfate as reducing agents, the adding amount is 0.01-0.05 of the mass of a put-in battery, sulfuric acid is added to control the pH value of dissolution, the pH value is controlled to be between 0.5-2.0, a surfactant is nonionic, bubbles are mainly generated in the control process, the dissolution efficiency is improved, the adding amount is 0.001-0.008 of the mass of the put-in battery, solid materials generated by a cathode-anode electrolytic tank are screened, the screening aperture is 60-100 meshes, filtering the cathode electrolysis overflow liquid to obtain filtrate and filter residue respectively, wherein the filtrate is sulfate solution of nickel, cobalt, manganese and lithium, the filter residue is black powder and carbon powder which are not completely dissolved out, active carbon is adopted to remove oil under the condition of normal temperature of the filtrate, organic matters in a battery are mainly removed by adsorption, the dosage of the active carbon is adjusted according to the content of TOC in the filtrate, namely, the dosage of 1g/LTOC is 1:50-200 g/L of the added active carbon, the reaction time is 30-120 minutes, sodium thiosulfate is adopted to remove copper after the filtrate is removed by the active carbon, the aim is to remove copper ions, other impurity ions are not added except sodium, the reaction temperature is 80-95 ℃, and the dosage of sodium thiosulfate is: copper ions are 1:1.05-1.25, the reaction time is 30-90 minutes, the filtrate is heated to 85-95 ℃ after copper removal, oxidant (sodium chlorate, sodium hypochlorite, sodium persulfate and the like) is added, ferrous iron is oxidized into ferric iron, the dosage of the oxidant is 1.05-1.2 times of the theoretical dosage of ferrous iron oxide, the reaction time is 30-70 minutes, then 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 is heated to 85-95 ℃ after copper removal, manganese powder is added, the dosage of manganese powder is 0.2-1kg per cubic meter, the reaction time is 30-60 minutes, the purpose is that in order to remove impurities such as cadmium in solution, metal manganese powder and cadmium in solution undergo displacement reaction, the impurities in solution are removed by displacement reaction, the temperature of the heating plate 502 is controlled at 50-75 ℃ for liquid inside the outer box body 1, then the driving motor 601 is turned on, the stirring rod 501 is driven to rotate through the second gear 603 and the third gear 604, the heating plate 502 is used for uniformly heating liquid, meanwhile, the blocking balancing weight 504 is enabled to slide outwards along the directional guide rod 505 through the centrifugal force of rotation of the stirring rod 501, so that 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 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 driving motor 601 drives the snake bone steel cable 701 to rotate through 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 and is convenient to be sprinkled, meanwhile, the fifth gear 703 can drive the sixth gear 804 to rotate, further, the threaded lifting rod 803 which forms a rotary 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, the scattering effect of manganese powder in the stirring rod 501 is 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 circulating water pipe 202 through the water pump 201, the liquid is circulated, the reaction is convenient to complete, meanwhile, particles generated by the reaction can shake the blanking plate 301 through the vibrating motor 302 and fall into the collecting box 303 for collection, the impurity-removed liquid adopts Cyanex272 (extracted organic) to extract manganese, the content of Cyanex272 is controlled to be 15-20%, compared with 1:2-4, the mixing time is 2-5 minutes, manganese in the impurity-removed liquid is extracted into an organic phase according to the extraction characteristic of Cyanex272, lithium is remained in the raffinate to separate manganese from lithium, the temperature of the raffinate is controlled to be 45-60 ℃, the pH value of the raffinate is regulated to be 10-11.5 by alkali, the reaction time is 30-60 minutes, the acid regulation is used for regulating the pH value of the solution to facilitate the subsequent operation, on the other hand, the nickel, cobalt and manganese in the solution are completely precipitated, the nickel, cobalt and manganese are precipitated in the acid regulation process, the acid regulation is carried out, the filtered solution is regulated, the temperature is controlled to be 60-80 ℃, sodium carbonate is added, the adding amount is 1.25-1.3 times of the theoretical amount of precipitated lithium, the reaction time is 60-120 minutes, lithium is precipitated into lithium carbonate, the lithium is still contained in the precipitated solution by about 2g/L due to the solubility problem of lithium carbonate, the filtered precipitated mother solution is concentrated by MVR, the concentration degree is used for producing visible crystals as standard, the lithium carbonate is obtained after cooling, the mother solution can be returned to remove the iron and regulate the acid or is returned to continue to concentrate crystallization, grinding the materials to 60-100 meshes by a fine grinder after the oversize materials obtained by sieving the solid materials after the first electrolytic dissolution, sieving the materials again after the fine grinding, and respectively carrying out magnetic separation and reselection on the oversize materials to obtain steel shells, diaphragms, copper-aluminum powder and carbon powder; the undersize material is dissolved out again through electrolysis, after dissolution is finished, the undersize material is filtered, the filtrate is merged into the first electrolytic dissolution solution to remove oil, and the filter residue is reselected to obtain copper aluminum powder and carbon powder; combining copper aluminum powder, separating copper powder and aluminum powder by color separation, carrying out back extraction on an organic phase of Cyanex272 extracted with manganese ions by adopting dilute sulfuric acid with the concentration of MVR (mechanical vapor recompression) and the thermal filtration of the concentrated solution to obtain manganese sulfate crystals and mother liquor, returning the mother liquor to a replacement process, reducing impurities in the solution, washing the replacement slag, leaching the replacement slag by adopting sulfuric acid and hydrogen peroxide, taking hydrogen peroxide as a reducing agent, reducing high-valence cobalt nickel manganese without adding new impurity ions, regulating the pH value by adopting sulfuric acid, controlling the pH value to be 0.1-0.25 of the weight of the replacement slag, controlling the end point pH value to be 0.5-2.0, the reaction temperature is controlled at 75-85 ℃, the reaction time is controlled at 120-180 minutes, the leaching solution is filtered, the temperature is controlled at 85-95 ℃, hydrogen peroxide is added as an oxidant, the addition amount is 0.85-1.05 times of the ferrous ion oxidation theoretical amount, the reaction time is 30-60 minutes, manganese powder is added to adjust the PH value to 2.5-3.5, the reaction time is 60-120 minutes, after filtration, the filtrate is concentrated and then subjected to primary thermal filtration, the manganese sulfate microcrystals generated by the filtering material are removed, the crystal grains are controllable when the microcrystals are cooled and crystallized after the microcrystals are removed, the microcrystals are returned to the replacement process for dissolution, the mixed crystal of nickel cobalt manganese sulfate is obtained after the thermal filtration, and the mother liquor is returned to concentrated crystallization or deironized to remove enriched impurities.
Claims (4)
1. The comprehensive recovery method of the waste lithium battery is characterized by comprising the following steps of: a. crushing; b. electrolyzing the slurry; c. sieving; d. filtering; e. removing oil; f. copper removal; g. iron removal; h. removing impurities; i. replacement; j. extracting; k. acid regulation; i, precipitation; mvr+ crystallization; n, fine grinding; back-extracting; leaching; removing iron from the displacement slag leachate, wherein a. Crushing: crushing the battery and water at normal temperature, wherein the mass ratio of the water to the battery is 1:1-2.5, and b. electrolyzing the slurry: putting the crushed water and battery materials into a special slurry electrolytic tank for electrolytic dissolution, and c. sieving the solid materials generated by the cathode electrolytic tank, wherein the sieving aperture is 60-100 meshes; filtering: filtering the cathode electrolysis overflow liquid to obtain filtrate and filter residue respectively, wherein the filtrate is sulfate solution of nickel, cobalt, manganese and lithium, and the filter residue is black powder and carbon powder which are not completely dissolved; deoiling: removing oil from the filtrate by adopting active carbon at normal temperature, mainly removing organic matters in the battery by adsorption, and removing copper: removing copper from the filtrate by using sodium thiosulfate after removing oil by using active carbon, wherein other impurity ions are not added except sodium in order to remove copper ions; iron removal: heating the filtrate to 85-95 ℃ after copper removal, adding an oxidant, and oxidizing ferrous iron into ferric iron, wherein the steps of: heating the filtrate to 85-95 ℃ after copper removal, adding manganese powder, wherein the dosage of the manganese powder is 0.2-1kg per cubic meter, and the reaction time is 30-60 minutes, so as to remove cadmium impurities in the solution; substitution: controlling the temperature of the solution after impurity removal at 50-75 ℃, adding manganese powder with the addition speed of 0.05-0.2kg per minute, wherein the addition amount of the manganese powder is 1.05-1.15 times of the nickel-cobalt replacement theoretical amount, the reaction time is 30-60 minutes, the replacement slag is mixed slag containing nickel, cobalt and manganese, and the j. extraction: extracting manganese from the solution after impurity removal by using Cyanex272, wherein the content of Cyanex272 is controlled to be 15-20%, compared with 1:2-4, the mixing time is 2-5 minutes, extracting manganese in the solution after impurity removal into an organic phase according to the extraction characteristic of Cyanex272, and retaining lithium in raffinate to separate manganese from lithium; acid regulation: controlling the temperature of the raffinate to be 45-60 ℃, regulating the pH value to be 10-11.5 by using alkali, and reacting for 30-60 minutes, wherein the acid regulation is used for regulating the pH value of the solution so as to facilitate the subsequent operation, and on the other hand, completely precipitating nickel, cobalt and manganese in the solution, wherein the acid regulation process can generate nickel, cobalt and manganese precipitation; precipitation: adjusting the temperature of the filtered solution to 60-80 ℃, adding sodium carbonate with the addition amount being 1.25-1.3 times of the theoretical amount of precipitated lithium content, reacting for 60-120 minutes, precipitating lithium into lithium carbonate, wherein the content of lithium in the precipitated solution is still about 2g/L due to the solubility problem of the lithium carbonate, and the m.MVR+ is crystallized: concentrating the filtered precipitation mother liquor by MVR (mechanical vapor recompression) to the extent that visible crystallization is generated as a standard, cooling to obtain lithium carbonate, and returning the mother liquor to remove iron and adjust acid or to continue concentrating crystallization; the n. fine grinding: grinding the materials to 60-100 meshes by a fine grinder after the oversize materials obtained by sieving the solid materials after the first electrolytic dissolution, sieving the materials again after the fine grinding, and respectively carrying out magnetic separation and reselection on the oversize materials to obtain steel shells, diaphragms, copper-aluminum powder and carbon powder; the undersize material is dissolved out again through electrolysis, after dissolution is finished, the undersize material is filtered, the filtrate is merged into the first electrolytic dissolution solution to remove oil, and the filter residue is reselected to obtain copper aluminum powder and carbon powder; combining copper and aluminum powder, performing color separation to separate copper powder and aluminum powder, and performing o. back extraction: carrying out back extraction on the Cyanex272 organic phase extracted with manganese ions by adopting 4.5-5.5mol/L dilute sulfuric acid, controlling the PH value of the back extraction liquid to be 3.5-4.5, obtaining the back extraction liquid which is manganese sulfate solution, concentrating manganese sulfate through MVR and hot filtering to obtain manganese sulfate crystals and mother liquor, returning the mother liquor to a replacement process, and reducing impurities in the solution; the p leaching: leaching the displacement slag by adding sulfuric acid and hydrogen peroxide after washing, wherein the hydrogen peroxide is used as a reducing agent, and the aim is to reduce high-valence cobalt nickel manganese without adding new impurity ions; the substitution slag leaching solution is deironized: filtering the leaching solution, controlling the temperature to be 85-95 ℃, adding hydrogen peroxide as an oxidant, adding 0.85-1.05 times of the theoretical amount of ferrous ion oxidation, reacting for 30-60 minutes, adding manganese powder to adjust the PH value to 2.5-3.5, reacting for 60-120 minutes, filtering, concentrating the filtrate, performing primary thermal filtration, and filtering to obtain manganese sulfate microcrystals, wherein the purpose is to remove the microcrystals, wherein crystal grains are controllable when the microcrystals are cooled and crystallized after cooling, the microcrystals are returned to a replacement procedure for dissolution, cooling and crystallizing are performed after thermal filtration, thus obtaining mixed crystal of nickel cobalt manganese sulfate, and mother liquor is returned to concentrated crystallization or deironing to remove enriched impurities.
2. The method for comprehensively recycling waste lithium batteries according to claim 1, wherein the replacement device used in the step i comprises an outer box body (1) and a material taking assembly (3), a water circulation assembly (2) is arranged on the right side of the lower end of the inner part of the outer box body (1), the water circulation assembly (2) comprises a water pump (201), a circulating water pipe (202), a discharging water 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 discharging water pipe (203), the electromagnetic valve (204) is arranged on the outer part of the discharging water pipe (203), and the material taking assembly (3) is positioned on the left side of the lower end of the inner part of the outer box body (1).
3. The method for comprehensively recycling waste lithium batteries according to claim 2, wherein 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 vibration motor (302) is installed in the middle of the lower end of the blanking plate (301), the material collecting box (303) is arranged on the left side of the lower end of the blanking 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 on the upper end of the inner portion of the outer box (1), the stirring assembly (5) comprises a stirring rod (501), a heating plate (502), a tension elastic rope (503), a blocking counter weight (504) and a directional guide rod (505), the heating plate (502) is arranged in the left side of the stirring rod (501), the right end of the stirring rod (501) is connected with the sealing rear plate (304), and the two ends of the stirring rod (503) are connected with the tension elastic rope (503).
4. The method for comprehensively recycling waste lithium batteries according to claim 3, wherein a power assembly (6) is arranged at the upper end of the outer box body (1), the power assembly (6) comprises a driving motor (601), a first gear (602), a second gear (603), a third gear (604), a rotating positioning block (605) and a rotating ball (606), the first gear (602) and the second gear (603) are sequentially arranged outside the driving motor (601) from right to left, the lower end of the second gear (603) is connected with a third gear (604), the rotating positioning block (605) and the rotating ball (606) are sequentially arranged at the lower end of the third gear (604) from outside to inside, a stirring assembly (7) is arranged at the upper end of the power assembly (6), the stirring assembly (7) comprises 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 (704) are sequentially arranged outside the driving motor (601), the fourth gear (702), the fifth gear (703) and the fifth bearing (704) are sequentially arranged outside the snake bone steel cable (701), the lifting assembly (802), the lifting assembly (80) is connected with the lifting assembly (803), and the lifting assembly (80) is connected with the lifting assembly (80) Screw sleeve (805) and telescopic link (806), the internally mounted of lifter plate (801) has second bearing (802), and the inside of second bearing (802) runs through has screw lifter (803), the upper end of screw lifter (803) is connected with sixth gear (804), and the lower extreme of screw lifter (803) is connected with screw sleeve (805), the lower extreme of lifter plate (801) is connected with telescopic link (806).
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| 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 |
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| 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 |
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