CN115141933B - Method for purifying ternary lithium battery recovery leaching liquid - Google Patents
Method for purifying ternary lithium battery recovery leaching liquid Download PDFInfo
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- CN115141933B CN115141933B CN202210740118.2A CN202210740118A CN115141933B CN 115141933 B CN115141933 B CN 115141933B CN 202210740118 A CN202210740118 A CN 202210740118A CN 115141933 B CN115141933 B CN 115141933B
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- lithium
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- residues
- filtrate
- lithium battery
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 84
- 238000002386 leaching Methods 0.000 title claims abstract description 47
- 239000007788 liquid Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000011084 recovery Methods 0.000 title claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 58
- 239000000706 filtrate Substances 0.000 claims abstract description 48
- 239000002699 waste material Substances 0.000 claims abstract description 29
- 239000010949 copper Substances 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229910052802 copper Inorganic materials 0.000 claims abstract description 22
- 230000001276 controlling effect Effects 0.000 claims abstract description 21
- 238000001914 filtration Methods 0.000 claims abstract description 21
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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 18
- 239000012074 organic phase Substances 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 12
- 150000003841 chloride salts Chemical class 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
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000012266 salt solution Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 230000001376 precipitating effect Effects 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 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 24
- -1 fluoride ions Chemical class 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 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
- 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
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 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
- 150000004673 fluoride salts Chemical class 0.000 claims description 4
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 4
- 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
- 239000002893 slag Substances 0.000 description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 16
- 239000002351 wastewater Substances 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 12
- 239000003513 alkali Substances 0.000 description 9
- 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 8
- 150000002500 ions Chemical class 0.000 description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 8
- 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
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 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
- 230000035484 reaction time Effects 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
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 150000002739 metals Chemical class 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-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
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 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
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000001514 detection method Methods 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
- 238000000605 extraction Methods 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 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
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910018119 Li 3 PO 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 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
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-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
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 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
- 239000007772 electrode material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 229910000625 lithium cobalt oxide 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
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification 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
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000004064 recycling Methods 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
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 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
- 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
Abstract
The invention discloses a method for purifying a ternary lithium battery recovery leaching solution, which comprises the following steps: (1) Heating the ternary lithium battery recovery leaching solution once, regulating the pH value to 5.0-6.5, filtering once to remove iron and aluminum residues, adding a reducing agent, controlling the pH value to be acidic, heating twice, filtering twice to remove copper residues, adding a precipitating agent, filtering for three times to obtain calcium magnesium lithium residues, adding an extracting agent into the filtrate after filtering for three times to extract, standing, separating to obtain an extracted organic phase and raffinate, and adding a stripping agent into the extracted organic phase to carry out stripping to obtain a nickel-cobalt-manganese-containing solution; (2) Adding soluble phosphate into the raffinate, and then carrying out solid-liquid separation to obtain lithium-containing waste residues; (3) Mixing lithium-containing waste residue and calcium magnesium lithium residue, and then adding the mixture into a soluble chloride salt 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 leaching solution.
Background
The lithium ion battery has the advantages of high voltage, good circularity, high energy density, small self-discharge, no memory effect and the like, is widely applied to the electronic and wireless communication industry, and is also a 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 faster updating speed, the demands of lithium ion batteries are increasing, the number of waste lithium ion batteries and lithium ion battery production waste is increasing, and the valuable metal-containing waste belongs to dangerous waste, so that serious ecological environment pollution problem can be generated, and recycling is the best way for solving the problem.
The lithium ion battery anode materials commonly used in the market at present mainly comprise lithium cobalt oxide, lithium nickel oxide, lithium manganate, nickel cobalt manganese ternary anode materials, lithium iron phosphate and the like. When the waste batteries are recycled, sulfuric acid, nitric acid, hydrochloric acid and other acids are generally adopted to leach valuable metals in the electrode materials. In nickel cobalt lithium manganate, cobalt and manganese are in high valence state, so that reducing agents such as hydrogen peroxide and sodium sulfite are added to completely leach metals. Researches show that under the condition of reducing agent, the leaching rate of the metal can reach more than 90% at the temperature of 60-90 ℃ with 1-3mol/L hydrochloric acid or sulfuric acid. The waste battery leaching solution contains a large amount of Ni, co, mn, li valuable metals and Cu, fe, al, zn, ca, mg and other impurity ions, and the mixed metal ions in the leaching solution can be recycled by adopting a proper purification method.
In the existing leaching liquid purification process, iron powder is mostly adopted for replacing and removing copper, then pH is regulated for removing iron and aluminum through oxidization, then P204 (di (2-ethylhexyl) phosphate) is adopted for extracting Ni, co and Mn and separating impurity ions, and finally, carbonate or phosphate is added into raffinate for lithium recovery to precipitate lithium. However, the above process has the following problems: (1) the efficiency of removing copper by iron powder replacement is low, the copper ion residue is still higher, sodium sulfide is selected by most manufacturers to thoroughly remove copper, and valuable metals nickel cobalt are inevitably precipitated together by adding sulfur ions, so that the loss of the valuable metals is caused; (2) the separation coefficient in the extraction process is not high, and impurity ions Ca and Mg are not easy to remove; (3) the raffinate contains a large amount of lithium, which needs to be removed separately, and common sodium carbonate is used for precipitating lithium, because the solubility product constant of the 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 the lithium in the lithium precipitation mother liquor still reaches about 1.5g/L, and the adoption of phosphate for precipitating lithium can lead to difficult enrichment of later-stage lithium, and the recovery rate of lithium is difficult to improve.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the invention provides a method for purifying the ternary lithium battery recovery leaching solution, which can improve the copper removal efficiency of the leaching solution, 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 aim of the invention is realized by the following technical scheme:
a method for purifying a ternary lithium battery recovery leaching solution comprises the following steps:
(1) After primary heating of the ternary lithium battery recovery leaching solution, regulating 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 precipitating agent, filtering for the third time to obtain calcium magnesium lithium residues, adding an extracting agent into the filtrate after the filtering for the third time to extract, standing, separating to obtain an extracted organic phase and raffinate, adding a stripping agent into the extracted organic phase to carry out stripping to obtain a solution containing nickel, cobalt and manganese, wherein the ternary lithium battery recovery leaching solution is a leaching solution 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 residues;
(3) Mixing lithium-containing waste residue and calcium magnesium lithium residue, and then adding the mixture into a soluble chloride salt solution for reaction to obtain a lithium chloride solution.
Preferably, in the step (1), after the leaching solution recovered from the ternary lithium battery is heated for one time, the pH is adjusted to 5.5-6.0.
Preferably, the temperature after the primary heating in the step (1) is 60-100 ℃.
Further preferably, the temperature after the one heating in the step (1) is 75 to 90 ℃.
Preferably, the reducing agent in the step (1) is at least one of hydroxylamine, hydroxylamine sulfate and hydrazine sulfate.
Preferably, the reducing agent is added in step (1) in an amount of 0.2 to 5 times the molar amount of copper in the filtrate after the one filtration.
It is further preferred that the reducing agent is added in step (1) in an amount of 0.5 to 3 times the molar amount of copper in the filtrate after the one filtration.
Preferably, the pH is controlled to be acidic in the step (1) by controlling the pH to be 4.0-6.5.
Further preferably, the controlling the pH to be acidic in the step (1) is controlling the pH to be 5.0 to 6.0.
Preferably, the temperature after the secondary heating in the step (1) is 80-100 ℃.
Further preferably, the temperature after the secondary heating in the step (1) is 90-100 ℃, the reaction is carried out for 1-2 hours after the secondary heating, and then the secondary filtration is carried out.
Preferably, the filtrate after the secondary filtration in the step (1) is cooled to room temperature, and then the precipitant is added.
Preferably, the precipitant in the step (1) is soluble fluoride salt, and the concentration of fluoride ions in the filtrate after the three times of filtration is 3-10g/L. .
Further preferably, the precipitant in the step (1) is a soluble fluoride salt, and the concentration of fluoride ions in the filtrate after the three times of filtration is 4-8g/L.
Preferably, the precipitating agent in the step (1) is at least one of sodium fluoride and potassium fluoride.
Preferably, the extractant in the step (1) is at least one of P204 (di (2-ethylhexyl) phosphate) and P507 (2-ethylhexyl phosphate).
Preferably, the stripping agent in the 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 (1.0-1.05).
Preferably, the soluble phosphate in the step (2) is at least one of sodium phosphate and potassium phosphate.
Preferably, the step (2) is performed with solid-liquid separation to obtain wastewater, and the wastewater is treated by a wastewater treatment system.
Preferably, in the step (3), after the lithium-containing waste residue and the calcium magnesium lithium residue are mixed, the mixture is added into the soluble chloride salt solution according to the solid-to-liquid ratio of 10-180g/L, and the concentration of the soluble chloride salt solution is 1.0-7.0mol/L.
Further preferably, in the step (3), after the lithium-containing waste residue and the calcium-magnesium-lithium residue are mixed, the mixture is added into the soluble chloride salt solution according to a solid-to-liquid ratio of 20-150g/L, and the concentration of the soluble chloride 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 ℃ and the reaction time is controlled to be 3-7h in the reaction process in the step (3).
It is further preferable that the reaction temperature is controlled to be 70-90 ℃ and the reaction time is controlled to be 4-6h in the reaction process in the step (3).
Preferably, the method for purifying the reclaimed leaching solution of the ternary lithium battery comprises the following steps:
(1) Collecting leaching liquid from the battery recovery leaching process, heating to 75-90 ℃ and removing residual hydrogen peroxide;
(2) Adding alkali liquor to adjust the pH value to 5.5-6.0, and carrying out solid-liquid separation to obtain iron-aluminum slag and a first filtrate;
(3) Adding a reducing agent into the obtained first filtrate, controlling the pH value to be 5.0-6.0 by using alkali liquor, controlling the temperature to be 90-100 ℃ in the reaction process, and controlling the reaction time to be 1-2h; the reducing agent is at least one of hydroxylamine, hydroxylamine sulfate and hydrazine sulfate, and the addition amount is 0.5-3 times of the molar amount of copper in the filtrate (2-3 times of hydroxylamine group and 0.5-1 time of hydrazine sulfate);
(4) After the reaction of the step (3), carrying out solid-liquid separation to obtain copper slag and second filtrate;
(5) After the second filtrate is cooled to room temperature, adding a precipitant into the second filtrate, wherein the precipitant is at least one of sodium fluoride and potassium fluoride, and controlling the concentration of fluoride ions in the filtrate after precipitation to be 4-8g/L;
(6) After the reaction of the step (5), 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 by using a sulfuric acid solution with the concentration of 3-5mol/L to obtain a nickel cobalt manganese sulfate solution, wherein the extractant is at least one of P204 and P507;
(8) Adding phosphate into raffinate according to the mole ratio of lithium to phosphorus of 3 (1.0-1.05), wherein the phosphate is at least one of sodium phosphate and potassium phosphate, and performing solid-liquid separation to obtain lithium-containing waste residue and wastewater, and enabling the wastewater to enter a wastewater treatment system;
(9) Mixing the lithium-containing waste residue with the calcium-magnesium-lithium residue obtained in the step (6), adding the mixture into a calcium chloride solution with the solid-to-liquid ratio of 20-150g/L and the concentration of 1.0-6.0mol/L, and replacing lithium in the waste residue, wherein the temperature is controlled to be 70-90 ℃ in the replacement process, and the replacement time is controlled to be 4-6h, so as to obtain the lithium chloride solution.
The beneficial effects of the invention are as follows:
1. according to the invention, on one hand, the pH value of the ternary lithium battery leaching solution is adjusted to hydrolyze ferric iron and aluminum ions in the solution, and a reducing agent is further added to reduce copper ions to generate cuprous oxide at high temperature (cuprous hydroxide is generated at low temperature and precipitation is incomplete), so that the cuprous oxide is removed, the problems that the reaction efficiency is low due to the addition of iron powder, and iron is removed due to the need of adding an oxidizing agent again are avoided; on the other hand, through secondary lithium precipitation, the precipitation rate of lithium is improved, and the obtained calcium magnesium lithium slag is further enriched and extracted to obtain lithium chloride solution.
Reduction copper removal:
2Cu 2+ +2NH 2 OH→Cu 2 O+N 2 +4H + +H 2 O。
and (3) a section of lithium precipitation:
Ca 2+ +2F - →CaF 2
Mg 2+ +2F - →MgF 2
Li + +F - →LiF。
second-stage lithium precipitation:
3Li + +PO 4 3- →Li 3 PO 4
extracting lithium by replacing calcium chloride:
2LiF+Ca 2+ →CaF 2 +2Li +
2Li 3 PO 4 +3Ca 2+ →Ca 3 (PO 4 ) 2 +6Li + 。
2. the method adopts the reducing agent to reduce copper ions into cuprous ions, so that the copper removal reaction time is shortened, and the residual copper in the solution is less. The soluble fluoride salt is used as a precipitator for precipitating lithium, meanwhile, calcium and magnesium ions are further removed, the mixing of the calcium and magnesium ions in the subsequent extraction is avoided, and the lithium content in the raffinate is further reduced through further precipitation of lithium by phosphate; and finally, enriching and extracting lithium by adopting soluble chloride salt to obtain lithium chloride solution, recovering lithium element again, and keeping calcium and magnesium impurities in waste residues, so that the recovery rate of the final lithium is not lower than 99%.
Drawings
Fig. 1 is a schematic process flow diagram of embodiment 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to specific examples.
The ternary lithium battery recovery leaching solution used in the specific embodiment of the invention is leaching solution obtained by using sulfuric acid and hydrogen peroxide in a leaching process, and the main components of metal ions are as follows:
| 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 a ternary lithium battery recovery leaching solution comprises the following steps:
(1) Collecting leaching liquid from the battery recovery leaching process, heating to 75 ℃, and removing residual hydrogen peroxide;
(2) Adding alkali liquor to adjust the pH value to 5.8, and carrying out solid-liquid separation to obtain iron-aluminum slag and first filtrate;
(3) Adding hydroxylamine into the obtained first filtrate, wherein the adding amount 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 of the step (3), carrying out solid-liquid separation to obtain copper slag and second filtrate;
(5) After the second filtrate is cooled to room temperature, adding sodium fluoride into the second filtrate, and controlling the concentration of fluoride ions in the filtrate after precipitation to be 8g/L;
(6) After the reaction of the step (5), 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 sulfuric acid solution with the concentration of 5mol/L to obtain a nickel cobalt manganese sulfate solution;
(8) Adding sodium phosphate into the raffinate according to the molar ratio of lithium to phosphorus of 3:1.05, and carrying out solid-liquid separation to obtain lithium-containing waste residue and wastewater, wherein the wastewater enters a wastewater treatment system;
(9) Mixing lithium-containing waste residue and calcium magnesium lithium slag obtained in the step (6), adding the mixture into a calcium chloride solution of 1.0mol/L according to a 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 recovery leaching solution comprises the following steps:
(1) Collecting leaching liquid from the battery recovery leaching process, heating to 80 ℃, and removing residual hydrogen peroxide;
(2) Adding alkali liquor to adjust the pH value to 5.5, and carrying out solid-liquid separation to obtain iron-aluminum slag and 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 1.5 hours;
(4) After the reaction of the step (3), carrying out solid-liquid separation to obtain copper slag and second filtrate;
(5) After the second filtrate is cooled to room temperature, adding sodium fluoride into the second filtrate, and controlling the concentration of fluoride ions in the filtrate after precipitation to be 6g/L;
(6) After the reaction of the step (5), carrying out solid-liquid separation to obtain calcium magnesium lithium slag and a third filtrate;
(7) Extracting the third filtrate by using an extractant P507, standing, separating to obtain an extracted organic phase and raffinate, and back-extracting the extracted organic phase by using a sulfuric acid solution with the concentration of 4mol/L to obtain a nickel cobalt manganese sulfate solution;
(8) Adding sodium phosphate into the raffinate according to the molar ratio of lithium to phosphorus of 3:1.03, and carrying out solid-liquid separation to obtain lithium-containing waste residue and wastewater, wherein the wastewater enters a wastewater treatment system;
(9) Mixing lithium-containing waste residue and calcium magnesium lithium slag obtained in the step (6), adding the mixture into a calcium chloride solution of 4.0mol/L according to a solid-to-liquid ratio of 100g/L, and replacing lithium in the waste residue, wherein the temperature is controlled at 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 recovery leaching solution comprises the following steps:
(1) Collecting leaching liquid from the battery recovery leaching process, heating to 90 ℃, and removing residual hydrogen peroxide;
(2) Adding alkali liquor to adjust the pH value to 6.0, and carrying out solid-liquid separation to obtain iron-aluminum slag and first filtrate;
(3) Adding hydrazine sulfate into the obtained first filtrate, wherein the adding 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 reacting for 1h;
(4) After the reaction of the step (3), carrying out solid-liquid separation to obtain copper slag and second filtrate;
(5) After the second filtrate is cooled to room temperature, adding potassium fluoride into the second filtrate, and controlling the concentration of fluoride ions in the filtrate after precipitation to be 4g/L;
(6) After the reaction of the step (5), carrying out solid-liquid separation to obtain calcium magnesium lithium slag and a third filtrate;
(7) Extracting the third filtrate by using an extractant P507, standing, separating to obtain an extracted organic phase and raffinate, and back-extracting the extracted organic phase by using a sulfuric acid solution with the concentration of 3mol/L 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 3:1.0, and carrying out solid-liquid separation to obtain lithium-containing waste residue and wastewater, wherein the wastewater enters a wastewater treatment system;
(9) Mixing lithium-containing waste residue and calcium magnesium lithium slag obtained in the step (6), adding the mixture into a calcium chloride solution of 6.0mol/L according to a 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 controlled to be 4 hours, so as to obtain the lithium chloride solution.
Comparative example 1:
a method for purifying a ternary lithium battery recovery leaching solution comprises the following steps:
(1) Collecting leaching liquid from a battery recovery leaching process, adding iron powder into the leaching liquid, wherein the molar ratio of the added amount of the iron powder to copper ions is 1.1:1, and performing solid-liquid separation after reacting for 4 hours to remove iron and copper residues;
(2) Adding hydrogen peroxide with the same molar weight as the iron element, adding alkali liquor to adjust the pH value to 5.5, and carrying out 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 sulfuric acid solution with the concentration of 5mol/L to obtain a nickel cobalt manganese sulfate solution;
(4) Adding sodium carbonate with the molar weight of lithium element being 0.6 times into the raffinate, and carrying out solid-liquid separation to obtain lithium-containing waste residue and waste water;
(5) Adding lithium-containing waste residue into 1.0mol/L calcium chloride solution according to a 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.
Test example:
the impurity metal ion content in the nickel cobalt manganese sulfate solutions obtained in examples 1 to 3 and comparative example 1 was measured, and the results are shown in table 1.
Table 1: the detection result of the impurity metal ion content in the nickel cobalt manganese sulfate solution comprises the following steps:
| metal ion content g/L | Cu | Ca | Mg |
| Example 1 | Not detected | 0.0001 | 0.0001 |
| Example 2 | Not detected | 0.0001 | 0.0001 |
| Example 3 | Not detected | 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 ternary lithium battery recovery leaching solution of the invention can effectively remove Cu, ca and Mg impurity ions in the leaching solution, the removal rate of Cu ions is close to 100%, and the removal rate of Ca and Mg impurity ions reaches 99.9%, while the nickel cobalt manganese sulfate solution obtained in comparative example 1 using the existing leaching solution purification process still has more Cu, ca and Mg impurity ions remained.
The lithium content in the wastewater obtained in examples 1 to 3 and comparative example 1 was measured, and the results are shown in Table 2.
Table 2: detection result of lithium content in 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 method for purifying the ternary lithium battery recovery leachate of the present invention has a lithium recovery rate of 99.9%, whereas comparative example 1 using the conventional leachate purification process has a lithium recovery rate of only 89.7%.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (5)
1. A method for purifying a ternary lithium battery recovery leaching solution is characterized by comprising the following steps: the method comprises the following steps:
(1) Heating the ternary lithium battery recovery leaching solution once, regulating the pH value to 5.0-6.5, filtering once to remove iron and aluminum residues, adding a reducing agent, controlling the pH value to be acidic, heating twice, filtering twice to remove copper residues, adding a precipitating agent, filtering for three times to obtain calcium magnesium lithium residues, adding an extracting agent into the filtrate after filtering for three times to extract, standing, separating to obtain an extracted organic phase and raffinate, and adding a stripping agent into the extracted organic phase to carry out stripping to obtain a nickel-cobalt-manganese-containing solution;
(2) Adding soluble phosphate into the raffinate, and then carrying out solid-liquid separation to obtain lithium-containing waste residues;
(3) Mixing lithium-containing waste residues and calcium magnesium lithium residues, and then adding the mixture into a soluble chloride salt solution for reaction to obtain a lithium chloride solution; the reducing agent in the step (1) is at least one of hydroxylamine, hydroxylamine sulfate and hydrazine sulfate, the adding amount of the reducing agent is 0.5-3 times of the molar amount of copper in the filtrate after the primary filtration, the pH is controlled to be acidic, the pH is controlled to be 5.0-6.0, the temperature after the secondary heating is 90-100 ℃, the reaction is carried out for 1-2 hours after the secondary heating, the secondary filtration is carried out, the precipitating agent is soluble fluoride salt, and the concentration of fluoride ions in the filtrate after the tertiary filtration is 4-8g/L; the soluble chloride salt solution in the step (3) is a calcium chloride solution.
2. The method for purifying the reclaimed leaching solution of the ternary lithium battery according to claim 1, which is characterized by comprising the following steps: the temperature after the primary heating in the step (1) is 60-100 ℃.
3. The method for purifying the reclaimed leaching solution of the ternary lithium battery according to claim 1, which is characterized by comprising the following steps: the back extractant is at least one of hydrochloric acid or sulfuric acid.
4. The method for purifying the reclaimed leaching solution of the ternary lithium battery according to claim 1, which is characterized by comprising the following steps: in the step (2), soluble phosphate is added into the raffinate according to the mole ratio of 3 (1.0-1.2) of lithium to phosphorus.
5. The method for purifying the reclaimed leaching solution of the ternary lithium battery according to claim 1, which is characterized by comprising the following steps: and (3) mixing the lithium-containing waste residue and the calcium magnesium lithium residue, and then adding the mixture into the soluble chloride salt solution according to a solid-to-liquid ratio of 10-180g/L, wherein the concentration of the soluble chloride 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 |
| CN110396607A (en) * | 2019-09-03 | 2019-11-01 | 中南大学 | A kind of processing method of waste and old ternary lithium ion battery powder |
| CN111180819A (en) * | 2019-12-30 | 2020-05-19 | 荆门市格林美新材料有限公司 | Preparation method of battery-grade Ni-Co-Mn mixed solution and battery-grade Mn solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN110396607A (en) * | 2019-09-03 | 2019-11-01 | 中南大学 | A kind of processing method of waste and old ternary lithium ion battery powder |
| CN111180819A (en) * | 2019-12-30 | 2020-05-19 | 荆门市格林美新材料有限公司 | Preparation method of battery-grade Ni-Co-Mn mixed solution and battery-grade Mn solution |
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