CN115141933A - Method for purifying ternary lithium battery recycling leaching solution - Google Patents
Method for purifying ternary lithium battery recycling leaching solution Download PDFInfo
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- CN115141933A CN115141933A CN202210740118.2A CN202210740118A CN115141933A CN 115141933 A CN115141933 A CN 115141933A CN 202210740118 A CN202210740118 A CN 202210740118A CN 115141933 A CN115141933 A CN 115141933A
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- lithium
- lithium battery
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- leachate
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000002386 leaching Methods 0.000 title claims abstract description 15
- 238000004064 recycling Methods 0.000 title claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 239000002699 waste material Substances 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 26
- 229910052802 copper Inorganic materials 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 20
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- XCPQSHFJZZSKLG-UHFFFAOYSA-N [Li].[Mg].[Ca] Chemical group [Li].[Mg].[Ca] XCPQSHFJZZSKLG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000012074 organic phase Substances 0.000 claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000010452 phosphate Substances 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- 239000002893 slag Substances 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001804 chlorine Chemical class 0.000 claims description 6
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- 229910000377 hydrazine sulfate Inorganic materials 0.000 claims description 5
- 239000012493 hydrazine sulfate Substances 0.000 claims description 5
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 4
- 238000011084 recovery Methods 0.000 abstract description 17
- 239000012535 impurity Substances 0.000 abstract description 11
- 239000011575 calcium Substances 0.000 abstract description 10
- 239000011777 magnesium Substances 0.000 abstract description 8
- 229910052749 magnesium Inorganic materials 0.000 abstract description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052791 calcium Inorganic materials 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 230000001276 controlling effect Effects 0.000 description 16
- 239000002351 wastewater Substances 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 10
- 239000003513 alkali Substances 0.000 description 9
- -1 sulfide ions Chemical class 0.000 description 8
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000001376 precipitating effect Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 description 5
- 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 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 235000013024 sodium fluoride Nutrition 0.000 description 4
- 239000001488 sodium phosphate Substances 0.000 description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 4
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229940073644 nickel Drugs 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 description 3
- 235000011009 potassium phosphates Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 150000003841 chloride salts Chemical class 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000010926 waste battery Substances 0.000 description 2
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 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
- 230000003446 memory effect Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
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- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Removal Of Specific Substances (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for purifying a ternary lithium battery recycling leachate, which comprises the following steps: (1) Heating a leachate recovered from a ternary lithium battery for the first time, adjusting the pH value to 5.0-6.5, filtering for the first time to remove iron and aluminum residues, adding a reducing agent, controlling the pH value to be acidic, heating for the second time, filtering for the second time to remove copper residues, adding a precipitator, filtering for the third time to obtain calcium-magnesium-lithium residues, adding an extractant into a filtrate obtained after filtering for the third time to extract, standing, separating to obtain an extracted organic phase and a raffinate, and adding a back-extractant into the extracted organic phase to perform back extraction to obtain a solution containing nickel, cobalt and manganese; (2) Adding soluble phosphate into the raffinate, and then carrying out solid-liquid separation to obtain lithium-containing waste residue; (3) And mixing the lithium-containing waste residue and the calcium-magnesium-lithium residue, and adding the mixture into a soluble chloride solution for reaction to obtain a lithium chloride solution. The purification method can improve the copper removal efficiency of the leaching solution, effectively remove calcium and magnesium impurities and improve the recovery rate of lithium.
Description
Technical Field
The invention belongs to the technical field of battery recovery, and particularly relates to a method for purifying a ternary lithium battery recovery leachate.
Background
The lithium ion battery has the advantages of high voltage, good cyclicity, large energy density, small self-discharge, no memory effect and the like, is widely applied to the electronic and wireless communication industries, and is also the preferred power supply of the light high-capacity battery of the electric automobile in the future. As various electronic products have been gradually popularized and kept at a high updating speed, the demand of lithium ion batteries is increasing day by day, the quantity of waste lithium ion batteries and waste materials produced by the lithium ion batteries is increasing day by day, the wastes containing valuable metals belong to dangerous wastes and can cause serious ecological environment pollution, and resource recycling is the best way for solving the problem.
The commonly used lithium ion battery anode materials in the market at present mainly comprise lithium cobaltate, lithium nickelate, lithium manganate, ternary anode materials of nickel cobalt manganese, lithium iron phosphate and the like. In the recovery treatment of these waste batteries, acids such as sulfuric acid, nitric acid, and hydrochloric acid are generally used to leach valuable metals from electrode materials. In the nickel cobalt lithium manganate, cobalt and manganese are in high valence state, so that the metal can be completely leached by adding reducing agents such as hydrogen peroxide, sodium sulfite and the like. Research shows that under the condition of reducing agent, hydrochloric acid or sulfuric acid is 1-3mol/L, the temperature is 60-90 ℃, and the leaching rate of metal can reach more than 90%. The waste battery leachate contains a large amount of valuable metals of Ni, co, mn and Li, and also contains impurity ions of Cu, fe, al, zn, ca, mg and the like, and the mixed metal ions in the leachate can be recycled by adopting a proper purification method.
In the existing leachate purification process, iron powder is mostly adopted for displacement copper removal, then iron and aluminum are removed through oxidation and pH adjustment, and then P204 (di (2-ethylhexyl) phosphate) is adopted for extracting Ni, co, mn and impurity ionsFinally, carbonate or phosphate is added to the raffinate to precipitate lithium for the purpose of lithium recovery. However, the above process has the following problems: (1) the replacement copper removal efficiency of iron powder is low, the copper ion residue is still high, most manufacturers choose to add sodium sulfide to completely remove copper, and the addition of sulfide ions inevitably precipitates valuable metal nickel and cobalt together, so that valuable metal loss is caused; (2) the separation coefficient in the extraction process is not high, impurity ions of Ca and Mg are not easy to remove; (3) the raffinate contains a large amount of lithium and needs to be removed separately, and the lithium is precipitated by sodium carbonate in general, because the solubility product constant of lithium carbonate is 8.15 multiplied by 10 -4 In order to improve the precipitation rate of lithium, excessive sodium carbonate is generally added, but lithium in the lithium precipitation mother liquor is still as high as about 1.5g/L, and lithium precipitation by adopting phosphate causes difficulty in later lithium enrichment and difficulty in improving the recovery rate of lithium.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a method for purifying the recovered leachate of a ternary lithium battery, which can improve the copper removal efficiency of the leachate, further remove calcium and magnesium impurities and improve the recovery rate of lithium, so that the recovery rate of lithium is not lower than 99%.
The technical purpose of the invention is realized by the following technical scheme:
a method for purifying a ternary lithium battery recycling leachate comprises the following steps:
(1) Heating a recovered leachate of a ternary lithium battery for the first time, adjusting the pH value to 5.0-6.5, filtering for the first time to remove iron and aluminum slag, adding a reducing agent, controlling the pH value to be acidic, heating for the second time, filtering for the second time to remove copper slag, adding a precipitator, filtering for the third time to obtain calcium magnesium lithium slag, adding an extractant into the filtrate obtained after filtering for the third time for extraction, standing, separating to obtain an extracted organic phase and a raffinate, adding a back extractant into the extracted organic phase for back extraction to obtain a solution containing nickel, cobalt and manganese, wherein the recovered leachate of the ternary lithium battery is a leachate obtained by using sulfuric acid and hydrogen peroxide in a leaching process;
(2) Adding soluble phosphate into the raffinate, and then carrying out solid-liquid separation to obtain lithium-containing waste residue;
(3) And mixing the lithium-containing waste residue and the calcium-magnesium-lithium residue, and adding the mixture into a soluble chloride solution for reaction to obtain a lithium chloride solution.
Preferably, after the leachate recovered from the ternary lithium battery is heated for the first time in the step (1), the pH value is adjusted to 5.5-6.0.
Preferably, the temperature after the primary heating in the step (1) is 60 to 100 ℃.
Further preferably, the temperature after the primary heating in the step (1) is 75 to 90 ℃.
Preferably, the reducing agent in step (1) is at least one of hydroxylamine, hydroxylamine sulfate and hydrazine sulfate.
Preferably, the addition amount of the reducing agent in the step (1) is 0.2 to 5 times of the molar amount of copper in the filtrate after the primary filtration.
Further preferably, the addition amount of the reducing agent in the step (1) is 0.5 to 3 times of the molar amount of copper in the filtrate after the primary filtration.
Preferably, the pH control in step (1) is acidic by controlling the pH to 4.0 to 6.5.
Further preferably, the pH control in step (1) is acidic by controlling the pH to 5.0 to 6.0.
Preferably, the temperature after the secondary heating in the step (1) is 80 to 100 ℃.
It is further preferred that the first and second liquid crystal compositions, the temperature after the secondary heating in the step (1) is 90-100 ℃, reacting for 1-2h after secondary heating, and then carrying out secondary filtration.
Preferably, in the step (1), after the filtrate obtained after the secondary filtration is cooled to room temperature, a precipitating agent is added.
Preferably, the precipitant in step (1) is a soluble fluoride salt, and the fluoride ion concentration in the filtrate after the third filtration is 3-10g/L. .
Further preferably, the precipitating agent in the step (1) is soluble villiaumite, and the concentration of the fluorine ions in the filtrate after the third filtration is 4-8g/L.
Preferably, the precipitating agent in step (1) is at least one of sodium fluoride and potassium fluoride.
Preferably, the extractant in step (1) is at least one of P204 (di (2-ethylhexyl) phosphate) and P507 (2-ethylhexyl phosphate).
Preferably, the stripping agent in step (1) is at least one of hydrochloric acid or sulfuric acid.
Further preferably, the stripping agent in step (1) is sulfuric acid.
Preferably, the concentration of the stripping agent is 2-6mol/L.
Further preferably, the concentration of the stripping agent is 3-5mol/L.
Preferably, in step (2), soluble phosphate is added to the raffinate in a molar ratio of lithium to phosphorus of 3 (1.0-1.2).
It is further preferred that in step (2) soluble phosphate is added to the raffinate in a molar ratio of lithium to phosphorus of 3 (1.0 to 1.05).
Preferably, the soluble phosphate in step (2) is at least one of sodium phosphate and potassium phosphate.
Preferably, waste water is obtained after solid-liquid separation in the step (2), and the waste water is treated by a waste water treatment system.
Preferably, in the step (3), the lithium-containing waste residue and the calcium-magnesium-lithium residue are mixed and then added into the soluble chlorine salt solution according to the solid-to-liquid ratio of 10-180g/L, wherein the concentration of the soluble chlorine salt solution is 1.0-7.0mol/L.
Further preferably, in the step (3), the lithium-containing waste residue and the calcium-magnesium-lithium residue are mixed and then added into the soluble chlorine salt solution according to the solid-to-liquid ratio of 20-150g/L, wherein the concentration of the soluble chlorine salt solution is 1.0-6.0mol/L.
Preferably, the soluble chloride salt solution in step (3) is a calcium chloride solution.
Preferably, the reaction temperature is controlled to be 60-95 ℃ during the reaction process in the step (3), and the reaction time is 3-7h.
Further preferably, the reaction temperature is controlled to be 70-90 ℃ in the reaction process in the step (3), and the reaction time is 4-6h.
Preferably, the method for purifying the ternary lithium battery recycling leachate comprises the following steps:
(1) Collecting the leachate from the cell recovery leaching process, and heating to 75-90 deg.C to remove residual hydrogen peroxide;
(2) Adding alkali liquor to adjust the pH to 5.5-6.0, and performing solid-liquid separation to obtain iron-aluminum slag and a first filtrate;
(3) Adding a reducing agent into the obtained first filtrate, and controlling the pH value to be 5.0-6.0 by using alkali liquor, wherein the temperature is controlled to be 90-100 ℃ in the reaction process, and the reaction time is 1-2h; the reducing agent is at least one of hydroxylamine, hydroxylamine sulfate and hydrazine sulfate, and the adding amount is 0.5-3 times of the molar amount of copper in the filtrate (the hydroxylamine group is 2-3 times, and the hydrazine sulfate is 0.5-1 time);
(4) After the reaction in the step (3) is finished, carrying out solid-liquid separation to obtain copper slag and a second filtrate;
(5) After the second filtrate is cooled to room temperature, adding a precipitating agent into the second filtrate, wherein the precipitating agent is at least one of sodium fluoride and potassium fluoride, and the concentration of fluorine ions in the precipitated filtrate is controlled to be 4-8g/L;
(6) After the reaction in the step (5) is finished, carrying out solid-liquid separation to obtain calcium-magnesium-lithium slag and a third filtrate;
(7) Extracting the third filtrate by using an extractant, standing, separating to obtain an extracted organic phase and raffinate, and back-extracting the extracted organic phase and the raffinate from the nickel-containing extracted organic phase by using a 3-5mol/L sulfuric acid solution to obtain a nickel-cobalt-manganese sulfate solution, wherein the extractant is at least one of P204 and P507;
(8) According to the molar ratio of lithium to phosphorus of 3 (1.0-1.05), adding phosphate into the raffinate, wherein the phosphate is at least one of sodium phosphate and potassium phosphate, carrying out solid-liquid separation to obtain lithium-containing waste residue and wastewater, and enabling the wastewater to enter a wastewater treatment system;
(9) And (3) mixing the lithium-containing waste residue with the calcium-magnesium-lithium residue obtained in the step (6), adding the mixture into 1.0-6.0mol/L calcium chloride solution according to the solid-to-liquid ratio of 20-150g/L, replacing lithium in the waste residue, wherein the temperature is controlled to be 70-90 ℃ in the replacement process, and the replacement time is 4-6h, so as to obtain the lithium chloride solution.
The invention has the beneficial effects that:
1. on one hand, ferric iron ions and aluminum ions in the solution are removed by hydrolyzing the ferric aluminum through regulating the pH value of the leaching solution of the ternary lithium battery, and a reducing agent is further added to reduce copper ions at high temperature (cuprous hydroxide is generated at low temperature, and incomplete precipitation) to generate cuprous oxide to remove the cupric oxide, so that the problems of low reaction efficiency caused by adding iron powder and iron removal by adding an oxidizing agent again are avoided; on the other hand, the precipitation rate of lithium is improved by secondary lithium precipitation, and the obtained calcium-magnesium-lithium slag is further enriched to extract lithium to obtain a lithium chloride solution.
Reduction and copper removal:
2Cu 2+ +2NH 2 OH→Cu 2 O+N 2 +4H + +H 2 O。
first-stage lithium precipitation:
Ca 2+ +2F - →CaF 2
Mg 2+ +2F - →MgF 2
Li + +F - →LiF。
secondary lithium deposition:
3Li + +PO 4 3- →Li 3 PO 4
replacement of lithium by calcium chloride:
2LiF+Ca 2+ →CaF 2 +2Li +
2Li 3 PO 4 +3Ca 2+ →Ca 3 (PO 4 ) 2 +6Li + 。
2. the invention adopts the reducing agent to reduce the copper ions into cuprous copper, which not only shortens the reaction time of copper removal, but also reduces the residual copper in the solution. Soluble villiaumite is used as a precipitator for precipitating lithium, calcium and magnesium ions are further removed, and the problems that during subsequent extraction, the lithium content in the raffinate is further reduced by mixing calcium and magnesium ions and precipitating lithium through further phosphate; and finally, enriching and extracting lithium by adopting soluble chloride salt to obtain a lithium chloride solution, recovering the lithium element again, and remaining calcium and magnesium impurities in the waste residue to ensure that the final recovery rate of the lithium is not less than 99 percent.
Drawings
FIG. 1 is a schematic process flow diagram of example 1 of the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples.
The ternary lithium battery recovery leachate used in the embodiment of the invention is obtained by using sulfuric acid and hydrogen peroxide in a leaching process, and the metal ions of the leachate mainly comprise the following components:
| composition of metal ions | Li | Ni | Co | Mn | Cu | Al | Fe | Ca | Mg |
| g/L | 9.67 | 36.06 | 14.38 | 21.02 | 4.63 | 5.13 | 0.11 | 0.16 | 0.09 |
Example 1:
as shown in fig. 1, a method for purifying leachate recovered from a ternary lithium battery comprises the following steps:
(1) Collecting the leachate from the cell recovery leaching process, heating to 75 ℃, and removing residual hydrogen peroxide;
(2) Adding alkali liquor to adjust the pH to 5.8, and performing solid-liquid separation to obtain iron-aluminum slag and a first filtrate;
(3) Adding hydroxylamine into the obtained first filtrate, wherein the addition amount of the hydroxylamine is 3 times of the molar amount of copper in the filtrate, controlling the pH value to be 5.5 by using alkali liquor, controlling the temperature to be 95 ℃ in the reaction process, and controlling the reaction time to be 2 hours;
(4) After the reaction in the step (3) is finished, carrying out solid-liquid separation to obtain copper slag and a second filtrate;
(5) After the second filtrate is cooled to room temperature, adding sodium fluoride into the second filtrate, and controlling the concentration of fluorine ions in the filtrate after precipitation to be 8g/L;
(6) After the reaction in the step (5) is finished, carrying out solid-liquid separation to obtain calcium-magnesium-lithium slag and a third filtrate;
(7) Extracting the third filtrate by using an extractant P204, standing, separating to obtain an extracted organic phase and raffinate, and back-extracting the extracted organic phase by using a 5mol/L sulfuric acid solution to obtain a nickel-cobalt-manganese sulfate solution;
(8) Adding sodium phosphate into raffinate according to the molar ratio of lithium to phosphorus of 3.05, carrying out solid-liquid separation to obtain lithium-containing waste residue and wastewater, and enabling the wastewater to enter a wastewater treatment system;
(9) And (4) mixing the lithium-containing waste residue with the calcium-magnesium-lithium residue obtained in the step (6), adding the mixture into a 1.0mol/L calcium chloride solution according to the solid-to-liquid ratio of 20g/L, and replacing lithium in the waste residue, wherein the temperature is controlled to be 90 ℃ in the replacement process, and the replacement time is 6 hours, so as to obtain the lithium chloride solution.
Example 2:
a method for purifying a ternary lithium battery recycling leachate comprises the following steps:
(1) Collecting leachate from the cell recovery leaching process, heating to 80 deg.C, and removing residual hydrogen peroxide;
(2) Adding alkali liquor to adjust the pH value to 5.5, and performing solid-liquid separation to obtain iron-aluminum slag and a first filtrate;
(3) Adding hydroxylamine sulfate into the obtained first filtrate, wherein the addition amount is 1 time of the molar amount of copper in the filtrate, controlling the pH value to be 6.0 by using alkali liquor, controlling the temperature to be 100 ℃ in the reaction process, and controlling the reaction time to be 1.5h;
(4) After the reaction in the step (3) is finished, carrying out solid-liquid separation to obtain copper slag and a second filtrate;
(5) After the second filtrate is cooled to room temperature, adding sodium fluoride into the second filtrate, and controlling the concentration of fluorine ions in the filtrate after precipitation to be 6g/L;
(6) After the reaction in the step (5) is finished, carrying out solid-liquid separation to obtain calcium-magnesium-lithium slag and a third filtrate;
(7) Extracting the third filtrate by using an extracting agent P507, standing, separating to obtain an extracted organic phase and raffinate, and back-extracting the extracted organic phase by using a 4mol/L sulfuric acid solution to obtain a nickel-cobalt-manganese sulfate solution;
(8) Adding sodium phosphate into raffinate according to the molar ratio of lithium to phosphorus of 3.03, carrying out solid-liquid separation to obtain lithium-containing waste residue and wastewater, and enabling the wastewater to enter a wastewater treatment system;
(9) And (4) mixing the lithium-containing waste residue with the calcium-magnesium-lithium residue obtained in the step (6), adding the mixture into a 4.0mol/L calcium chloride solution according to the solid-to-liquid ratio of 100g/L, and replacing lithium in the waste residue, wherein the temperature is controlled to be 80 ℃ in the replacement process, and the replacement time is 5 hours, so as to obtain the lithium chloride solution.
Example 3:
a method for purifying a ternary lithium battery recycling leachate comprises the following steps:
(1) Collecting leachate from the cell recovery leaching process, heating to 90 ℃, and removing residual hydrogen peroxide;
(2) Adding alkali liquor to adjust the pH to 6.0, and performing solid-liquid separation to obtain iron-aluminum slag and a first filtrate;
(3) Adding hydrazine sulfate into the obtained first filtrate, wherein the addition amount is 1 time of the molar amount of copper in the filtrate, controlling the pH value to be 5.0 by using alkali liquor, controlling the temperature to be 90 ℃ in the reaction process, and controlling the reaction time to be 1h;
(4) After the reaction in the step (3) is finished, carrying out solid-liquid separation to obtain copper slag and a second filtrate;
(5) After the second filtrate is cooled to room temperature, adding potassium fluoride into the second filtrate, and controlling the concentration of fluorine ions in the filtrate after precipitation to be 4g/L;
(6) After the reaction in the step (5) is finished, carrying out solid-liquid separation to obtain calcium-magnesium-lithium slag and a third filtrate;
(7) Extracting the third filtrate by using an extracting agent P507, standing, separating to obtain an extracted organic phase and raffinate, and back-extracting the extracted organic phase by using a 3mol/L sulfuric acid solution to obtain a nickel-cobalt-manganese sulfate solution;
(8) Adding potassium phosphate into the raffinate according to the molar ratio of lithium to phosphorus of 3.0, carrying out solid-liquid separation to obtain lithium-containing waste residue and wastewater, and enabling the wastewater to enter a wastewater treatment system;
(9) And (4) mixing the lithium-containing waste residue with the calcium-magnesium-lithium residue obtained in the step (6), adding the mixture into a 6.0mol/L calcium chloride solution according to the solid-to-liquid ratio of 150g/L, and replacing lithium in the waste residue, wherein the temperature is controlled to be 70 ℃ in the replacement process, and the replacement time is 4 hours, so as to obtain the lithium chloride solution.
Comparative example 1:
a method for purifying a ternary lithium battery recycling leachate comprises the following steps:
(1) Collecting leachate from a battery recovery leaching process, adding iron powder into the leachate, wherein the molar ratio of the adding amount of the iron powder to copper ions is 1.1;
(2) Adding hydrogen peroxide with the same molar weight as the iron element, adding alkali liquor to adjust the pH to 5.5, and performing solid-liquid separation to obtain iron-aluminum slag and filtrate;
(3) Extracting the filtrate by using an extractant P204, standing, separating to obtain an extracted organic phase and raffinate, and back-extracting the extracted organic phase by using a 5mol/L sulfuric acid solution to obtain a nickel, cobalt and manganese sulfate solution;
(4) Adding sodium carbonate with the molar weight of 0.6 time of lithium element into the raffinate, and carrying out solid-liquid separation to obtain lithium-containing waste residue and wastewater;
(5) Adding the lithium-containing waste residue into 1.0mol/L calcium chloride solution according to the solid-to-liquid ratio of 20g/L, replacing lithium in the waste residue, wherein the temperature in the replacement process is controlled to be 90 ℃, and the replacement time is 6 hours, so as to obtain the lithium chloride solution.
Test example:
the contents of impurity metal ions in the nickel cobalt manganese sulfate solutions obtained in examples 1 to 3 and comparative example 1 were measured, and the results are shown in table 1.
Table 1: the detection result of the content of impurity metal ions in the nickel, cobalt and manganese sulfate solution is as follows:
| metal ion content g/L | Cu | Ca | Mg |
| Example 1 | Not detected out | 0.0001 | 0.0001 |
| Example 2 | Not detected out | 0.0001 | 0.0001 |
| Example 3 | Not detected out | 0.0001 | 0.0001 |
| Comparative example 1 | 0.0005 | 0.0027 | 0.0019 |
As can be seen from table 1, the method for purifying the recovered leachate of the ternary lithium battery can effectively remove impurity ions of Cu, ca and Mg in the leachate, the removal rate of Cu ions is close to 100%, and the removal rate of impurity ions of Ca and Mg reaches 99.9%, while the nickel, cobalt and manganese sulfate solution obtained in comparative example 1 by using the existing leachate purification process still has more impurity ions of Cu, ca and Mg.
The lithium content in the waste water obtained in examples 1 to 3 and comparative example 1 was measured, and the results are shown in Table 2.
Table 2: and (3) detecting the lithium content in the wastewater:
| lithium content g/L | |
| Example 1 | 0.0024 |
| Example 2 | 0.0028 |
| Example 3 | 0.0037 |
| Comparative example 1 | 1.0 |
As can be seen from table 2, the recovery rate of lithium by the method for purifying the leachate recovered from the ternary lithium battery according to the present invention reaches 99.9%, while the recovery rate of lithium in comparative example 1 using the existing leachate purification process is only 89.7%.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for purifying a ternary lithium battery recycling leachate is characterized by comprising the following steps: the method comprises the following steps:
(1) Heating the recovered leachate of the ternary lithium battery for the first time, adjusting the pH value to 5.0-6.5, filtering for the first time to remove iron and aluminum slag, adding a reducing agent, controlling the pH value to be acidic, heating for the second time, filtering for the second time to remove copper slag, adding a precipitator, filtering for the third time to obtain calcium magnesium lithium slag, adding an extractant into the filtrate obtained after the third filtering for extraction, standing, separating to obtain an extraction organic phase and raffinate, and adding a back-extraction agent into the extraction organic phase for back extraction to obtain a solution containing nickel, cobalt and manganese;
(2) Adding soluble phosphate into the raffinate, and then carrying out solid-liquid separation to obtain lithium-containing waste residue;
(3) And mixing the lithium-containing waste residue and the calcium-magnesium-lithium residue, and adding the mixture into a soluble chloride solution for reaction to obtain a lithium chloride solution.
2. The method for purifying the leachate recovered by the ternary lithium battery as claimed in claim 1, wherein the method comprises the following steps: the temperature after the primary heating in the step (1) is 60-100 ℃.
3. The method for purifying the leachate recovered by the ternary lithium battery as claimed in claim 1, wherein the method comprises the following steps: the reducing agent in the step (1) is at least one of hydroxylamine, hydroxylamine sulfate and hydrazine sulfate.
4. The method for purifying the leachate recovered by the ternary lithium battery as claimed in claim 1, wherein the method comprises the following steps: the addition amount of the reducing agent in the step (1) is 0.2-5 times of the molar amount of copper in the filtrate after the primary filtration.
5. The method for purifying the leachate recovered by the ternary lithium battery as claimed in claim 1, wherein the method comprises the following steps: the pH control in the step (1) to be acidic is to control the pH to be 4.0-6.5.
6. The method for purifying the leaching solution recovered by the ternary lithium battery as claimed in claim 1, wherein the method comprises the following steps: the temperature after the secondary heating in the step (1) is 80-100 ℃.
7. The method for purifying the leaching solution recovered by the ternary lithium battery as claimed in claim 1, wherein the method comprises the following steps: the precipitator is soluble villiaumite, and the concentration of the fluorinion in the filtrate after the three times of filtration is 3-10g/L.
8. The method for purifying the leachate recovered by the ternary lithium battery as claimed in claim 1, wherein the method comprises the following steps: the stripping agent is at least one of hydrochloric acid or sulfuric acid.
9. The method for purifying the leaching solution recovered by the ternary lithium battery as claimed in claim 1, wherein the method comprises the following steps: in the step (2), soluble phosphate is added into the raffinate according to the molar ratio of lithium to phosphorus of 3 (1.0-1.2).
10. The method for purifying the leachate recovered by the ternary lithium battery as claimed in claim 1, wherein the method comprises the following steps: and (3) mixing the lithium-containing waste residue and the calcium-magnesium-lithium residue, and adding the mixture into the soluble chlorine salt solution according to the solid-liquid ratio of 10-180g/L, wherein the concentration of the soluble chlorine salt solution is 1.0-7.0mol/L.
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| CN106505272A (en) * | 2016-12-12 | 2017-03-15 | 江西赣锋锂业股份有限公司 | A kind of processing method of anode material of lithium battery waste material |
| CN108767353A (en) * | 2018-05-25 | 2018-11-06 | 北京矿冶科技集团有限公司 | The method for producing rich lithium net liquid from waste lithium ion cell anode active material |
| CN110092398A (en) * | 2019-04-23 | 2019-08-06 | 北京科技大学 | A kind of method of waste and old lithium ion battery baking tail gases resource utilization |
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