CN116119690A - Method for selectively recycling lithium from waste lithium battery - Google Patents
Method for selectively recycling lithium from waste lithium battery Download PDFInfo
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- CN116119690A CN116119690A CN202211621980.8A CN202211621980A CN116119690A CN 116119690 A CN116119690 A CN 116119690A CN 202211621980 A CN202211621980 A CN 202211621980A CN 116119690 A CN116119690 A CN 116119690A
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- lithium
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- leaching
- waste
- waste lithium
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 96
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 42
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 238000004064 recycling Methods 0.000 title claims abstract description 16
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 52
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 43
- 238000001914 filtration Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 18
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001263 FEMA 3042 Substances 0.000 claims abstract description 13
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims abstract description 13
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims abstract description 13
- 229940033123 tannic acid Drugs 0.000 claims abstract description 13
- 235000015523 tannic acid Nutrition 0.000 claims abstract description 13
- 229920002258 tannic acid Polymers 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 10
- 238000000605 extraction Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 101
- 238000002386 leaching Methods 0.000 claims description 91
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 44
- 238000006243 chemical reaction Methods 0.000 claims description 44
- 239000002244 precipitate Substances 0.000 claims description 36
- 238000005406 washing Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 18
- 239000012670 alkaline solution Substances 0.000 claims description 17
- 238000000967 suction filtration Methods 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 16
- 239000002893 slag Substances 0.000 claims description 16
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000706 filtrate Substances 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000012958 reprocessing Methods 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000011084 recovery Methods 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 5
- 150000002739 metals Chemical class 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 150000007524 organic acids Chemical class 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 229910017052 cobalt Inorganic materials 0.000 description 21
- 239000010941 cobalt Substances 0.000 description 21
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 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 6
- 239000000463 material Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002002 slurry 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
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- -1 polyphenol compound Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004289 sodium hydrogen sulphite Substances 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a method for selectively recycling lithium from waste lithium batteries, and belongs to the field of lithium battery recycling treatment. The method has the advantages that the operation steps are simple, the battery-grade lithium carbonate product is obtained through the procedures of adding green tannic acid with strong reducing capability and organic acid to cooperatively leach out, evaporating and concentrating, filtering and adsorbing to remove impurities, thermally decomposing and the like, the impurities can be effectively removed, an industrialization mode can be formed, the use amount of acid and alkali liquid is small, the cost is low, the flow is short, the efficient recovery of valuable metals of the waste lithium battery is facilitated, the pressure is reduced on the requirements of the recovery and extraction of valuable metals from the battery on the environmental protection and resources of China, and the method has great industrial potential.
Description
Technical Field
The invention relates to the field of lithium battery recovery treatment, in particular to a method for selectively recovering lithium from waste lithium batteries.
Background
The lithium ion battery has the advantages of high energy density, high discharge voltage, long cycle life and the like, and is widely applied to the fields of portable appliances, new energy automobiles and the like. The electrochemical performance and cost of the lithium ion battery are determined by the anode material to a great extent, however, cobalt metal in the raw material is expensive and depends on import seriously, and meanwhile, the cobalt element easily causes heavy metal pollution; the country is the country of lithium ion battery production and consumption. The trend towards continued increases is expected to remain for some time in the future. New energy automobiles are increasingly huge in sales volume, and the coming of power batteries is a peak of retirement in the next few years. Therefore, there must be a large amount of battery retirement in the near future. At present, how to effectively recycle and resource-utilize waste lithium batteries has become a social concern. Electrolyte in the waste lithium battery has toxicity and corrosiveness; carbonates (e.g., EC, EMC, DMC, DEC, etc.) as organic electrolytic agents are harmful to human bodies and can cause serious environmental pollution problems if discarded directly without proper treatment. Meanwhile, the waste lithium battery also contains abundant metal resources such as iron, lithium, aluminum and the like, wherein the lithium content is about 1 percent, which is higher than that of common lithium ores, and has higher recovery value.
The leachate for recovering Co and Li includes inorganic and organic leachate. Inorganic leaches such as sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid are typically combined with a reducing agent such as hydrogen peroxide to dissolve Co and Li in the cathode of the lithium battery. Because of the corrosiveness of acids, some studies have focused on safer organic extracts such as malic acid, lactic acid, citric acid, and oxalic acid. The reducing agent is critical in the leaching process to increase the insoluble Co in the cathode of a used lithium battery by reduction 3+ Conversion to soluble Co 2+ . So far, the suggested inorganic reducing agents include sodium bisulphite, sodium sulphite and ferrous iron, whereas the suggested organic reducing agents are glucose, ascorbic acid and ethanol. Although organic reducing agents are less hazardous, leaching is inefficient and costly.
The prior art CN108550939A discloses a method for selectively recovering lithium from waste lithium batteries and preparing lithium carbonate, which has the defects of high energy consumption, high pollution, higher nitric acid use cost, low resource utilization rate and the like because the positive electrode powder of the waste batteries and a nitrating agent are mixed, subjected to nitration reaction and subjected to roasting.
Therefore, how to treat the waste lithium batteries in a harmless, low-cost and high-recovery way and realize the green and environment-friendly recycling of the waste lithium batteries has become a problem which needs to be faced by human beings. Due to the characteristics of relatively low content of valuable metals in the lithium battery, if the traditional waste lithium ion battery treatment method is adopted, the problems of longer recovery flow, secondary pollution and the like exist, and the dilemma of poor economic benefit due to relatively low product purity or performance exists. Therefore, reasonable approaches and process conditions are sought to recycle the waste lithium batteries, the influence of harmful substances in the waste lithium batteries on the environment and human health is reduced to the maximum extent, certain economic benefits are generated, and the method has important significance for environmental protection and economic and social development in China.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for selectively recycling lithium from waste lithium batteries, which comprises the following specific scheme:
a method for selectively recovering lithium from waste lithium batteries, comprising the steps of:
step one, mixing mixed black powder containing positive and negative electrodes of waste lithium batteries with a leaching agent, and placing the mixed black powder and the leaching agent into a reactor for reaction; the leaching agent is tannic acid-acetic acid mixture;
step two, carrying out suction filtration on the solution obtained in the step one to obtain primary leaching solution and primary leaching slag, adding alkaline solution into the primary leaching solution to adjust the pH value of the solution to 10-10.1, and carrying out suction filtration to obtain secondary leaching solution and secondary leaching slag containing Co;
evaporating and concentrating the secondary leaching solution obtained in the step II until the mass concentration of lithium reaches 18-20g/L, and conveying the secondary leaching residue obtained in the step II into an extraction workshop for reprocessing;
step four, carrying out ion exchange on the concentrated solution obtained in the step three by using resin to remove soluble impurities, thereby obtaining a purified solution;
and fifthly, adding the purified solution obtained in the step four into carbonate solution with the theoretical amount of 1.1-1.2 times by adopting an electromagnetic heating stirrer to carry out thermal decomposition to form lithium carbonate precipitate, heating and stirring at 80-95 ℃ to react for 1-5 h, filtering, returning filtrate and washing solution generated by thermal decomposition to the step two for recycling, washing the lithium carbonate precipitate for 2-3 times, and then drying in a 95 ℃ drying box to obtain the battery grade lithium carbonate product.
In the first step, the waste lithium battery black powder comprises one or two of lithium cobaltate anode and cathode mixture and lithium cobaltate anode material.
In the first step, the liquid-solid ratio of the black powder of the waste lithium battery to acetic acid is 3-10 mL:1g.
In the first step, the concentration of acetic acid is 1-3 mol/L, and the concentration of tannic acid is 10-20 g/L.
The first reaction condition is that the stirring reaction rate is 400-600 r/min, the stirring time is 2-4 h, and the reaction temperature is 50-80 ℃.
And step two, the alkaline solution is at least one or a combination of a plurality of liquid alkali, ammonia water and potassium hydroxide.
The method for adding alkaline solution into the primary leaching solution to adjust the pH value of the solution in the second step is a parallel flow precipitation method: adding primary leaching solution and alkaline solution into a reaction kettle at the same time, wherein the feeding rate of the primary leaching solution is 5 mL/min, the feeding rate of the alkaline solution is 0.2-0.3 mL/min, the reaction temperature is 50 ℃, and the reaction time is 8 h.
And step four, the resin is D860 chelate resin.
In the fifth step, the carbonate solution is at least one or a combination of a plurality of sodium carbonate solution with the concentration of 2mol/L, potassium carbonate solution with the concentration of 2mol/L and ammonium carbonate solution with the concentration of 2 mol/L.
The washing process of the lithium carbonate precipitate in the fifth step is as follows: washing with deionized water at 80deg.C 1.5-2 times the wet weight of the filtered lithium carbonate precipitate for 15-20 min, filtering again, and washing the precipitate with saturated lithium carbonate solution at 80deg.C for 2-3 times.
The method provided by the invention has the advantages of wide applicability, short process flow, simple operation, high metal recovery rate and high product purity. The method for efficiently recycling valuable metals in the waste lithium batteries has important significance in the field. Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the black powder of the waste lithium battery is combined with a new green reducing agent tannic acid as a leaching agent by introducing green organic acid acetic acid, so that the leaching rate of lithium and cobalt is improved; specifically, tannic acid is a polyphenol compound having a strong reducing ability by dissolving insoluble Co 3+ Reduction to soluble Co 2+ To promote the dissolution of cobalt, and the tannic acid is combined with acetic acid to be used as a pH regulator, so that the acidic condition favorable for keeping Co in the leaching solution is created, and the leaching rate of cobalt is greatly improved. In addition, acetic acid is chosen to meet the green and sustainable guidelines in the recovery process.
(2) According to the invention, the primary leaching solution is subjected to alkali addition and pH value adjustment to 10-10.1 by a parallel flow precipitation method, so that the purpose of removing impurity elements such as heavy metal cobalt and the like is achieved, the loss rate of lithium is extremely low, the formed slurry is easy to separate solid from liquid, the dispersibility is good, suction filtration is easier, and the cost is saved.
(3) The invention adopts deionized water at 80 ℃ for slurry washing and saturated lithium carbonate solution at 80 ℃ for washing and precipitating for 2-3 times in the washing procedure to obtain the battery grade lithium carbonate product, and the washing liquid can be returned to the front-end step for recycling, thereby being more beneficial to resources and economy.
(4) The battery-grade lithium carbonate product obtained by the procedures of adding green tannic acid with strong reducing capability and organic acid for collaborative leaching, evaporating concentration, filtering, adsorbing, removing impurities, thermally decomposing and the like can form an industrialized mode, has lower cost and shorter flow, and has great industrial potential. The pressure is reduced on the environmental protection and resource requirements by battery recovery for lithium extraction. Drawings
FIG. 1 is a process flow diagram of the invention for preparing lithium carbonate from waste lithium battery material;
FIG. 2 shows purity profiles of lithium carbonate products prepared in comparative examples, examples 1-5.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to examples. The scope of protection is not limited to the description made.
Comparative example
Step one, mixing black powder containing positive and negative electrodes of lithium cobaltate with 3 mol/L acetic acid according to 1g:10 The ratio of the mL is respectively added into the reactor, the reaction is carried out under the conditions of stirring reaction rate of 400 r/min and reaction temperature of 80 ℃ for 4 h, and the leaching rates of lithium and cobalt are respectively 60 percent and 42 percent.
And step two, carrying out suction filtration on the solution obtained in the step one to obtain primary leaching solution and primary leaching slag, simultaneously adding the primary leaching solution and alkaline solution into a reaction kettle, wherein the feeding rate of the primary leaching solution is 5. 5 mL/min, the feeding rate of the NaOH solution with the mass concentration of 30% is 0.2-0.3 mL/min, the reaction temperature is 50 ℃, the reaction time is 8 h, and the reaction pH value is controlled to be 10-10.1. Carrying out suction filtration to obtain secondary leaching liquid and secondary leaching slag containing Ni, mn and Co;
evaporating and concentrating the secondary leaching solution obtained in the step II until the mass concentration of lithium reaches 18-20g/L, and conveying the secondary leaching residue obtained in the step II into an extraction workshop for reprocessing;
and fourthly, flowing the concentrated solution obtained in the third step into D860 type chelating ion exchange resin filled with 1.5L at the flow rate of 1 mL/min for ion exchange impurity removal. The impurities of nickel, cobalt, manganese, copper, aluminum, iron, calcium and magnesium are all less than 0.0006/g/L, so as to obtain a purifying liquid;
and fifthly, adding the purified solution obtained in the step four into a sodium carbonate solution with the concentration of 2mol/L which is 1.2 times of the theoretical amount by adopting an electromagnetic heating stirrer to carry out thermal decomposition to form lithium carbonate precipitate, heating and stirring at 80 ℃ to react for 4 h, filtering, washing with deionized water with the wet weight of the filtered lithium carbonate precipitate being 2 times of the wet weight of the filtered lithium carbonate precipitate for 20 min at 80 ℃, filtering again, and washing the precipitate with a saturated lithium carbonate solution with the temperature of 80 ℃ for 3 times. And (3) returning filtrate and washing liquid generated by thermal decomposition after filtration to the second step for recycling, and finally drying the washed lithium carbonate precipitate in a drying box at the temperature of 95 ℃ to obtain a lithium carbonate product with the purity of 99.95%.
Example 1
Step one, mixing black powder material of positive and negative electrodes of lithium cobaltate, 1 mol/L acetic acid and 10g/L tannic acid of a waste lithium battery according to 1g:10 mL: the 2mL are respectively added into a reactor, and the leaching rates of lithium and cobalt are respectively 99 percent and 94 percent under the conditions of stirring reaction rate of 500 r/min and reaction temperature of 80 ℃ for 3 h.
And step two, carrying out suction filtration on the solution obtained in the step one to obtain primary leaching solution and primary leaching slag, simultaneously adding the primary leaching solution and alkaline solution into a reaction kettle, wherein the feeding rate of the primary leaching solution is 5 mL/min, the feeding rate of the alkaline solution of the NaOH solution with the mass concentration of 30% is 0.2-0.3 mL/min, the reaction temperature is 50 ℃, the reaction time is 8 h, and the reaction pH value is controlled to be 10-10.1. Carrying out suction filtration to obtain secondary leaching liquid and secondary leaching slag containing Ni, mn and Co;
evaporating and concentrating the secondary leaching solution obtained in the step II until the mass concentration of lithium reaches 18-20g/L, and conveying the secondary leaching residue obtained in the step II into an extraction workshop for reprocessing;
and fourthly, flowing the concentrated solution obtained in the third step into D860 type chelating ion exchange resin filled with 1.5L at the flow rate of 1 mL/min for ion exchange impurity removal. The impurities of nickel, cobalt, manganese, copper, aluminum, iron, calcium and magnesium are all less than 0.0006/g/L, so as to obtain a purifying liquid;
and fifthly, adding the purified solution obtained in the step four into a sodium carbonate solution with the concentration of 2mol/L which is 1.2 times of the theoretical amount by adopting an electromagnetic heating stirrer to carry out thermal decomposition to form lithium carbonate precipitate, heating and stirring at 95 ℃ to react for 4 h, filtering, washing with deionized water with the wet weight of the filtered lithium carbonate precipitate being 1.5 times of the wet weight of the filtered lithium carbonate precipitate for 15 min, filtering again, and washing the precipitate with a saturated lithium carbonate solution with the temperature of 80 ℃ for 2 times. And (3) returning filtrate and washing liquid generated by thermal decomposition after filtration to the second step for recycling, and finally drying the washed lithium carbonate precipitate in a drying box at the temperature of 95 ℃ to obtain a lithium carbonate product with the purity of 99.55%.
Example 2
Step one, mixing black powder material of positive and negative electrodes of lithium cobaltate, 2mol/L acetic acid and 15g/L tannic acid of a waste lithium battery according to 1g:5 mL: the 2mL are respectively added into a reactor, and the leaching rates of lithium and cobalt are respectively 96 percent and 92 percent under the conditions of stirring reaction rate of 600 r/min and reaction temperature of 60 ℃ for 2 h.
And step two, carrying out suction filtration on the solution obtained in the step one to obtain primary leaching solution and primary leaching slag, simultaneously adding the primary leaching solution and alkaline solution into a reaction kettle, wherein the feeding rate of the primary leaching solution is 5. 5 mL/min, the feeding rate of 30% KOH solution is 0.2-0.3 mL/min, the reaction temperature is 50 ℃, the reaction time is 8 h, and the reaction pH value is controlled to be 10-10.1. Carrying out suction filtration to obtain secondary leaching liquid and secondary leaching slag containing Ni, mn and Co;
evaporating and concentrating the secondary leaching solution obtained in the step II until the mass concentration of lithium reaches 18-20g/L, and conveying the secondary leaching residue obtained in the step II into an extraction workshop for reprocessing;
and fourthly, flowing the concentrated solution obtained in the third step into D860 type chelating ion exchange resin filled with 1.5L at the flow rate of 1 mL/min for ion exchange impurity removal. The impurities of nickel, cobalt, manganese, copper, aluminum, iron, calcium and magnesium are all less than 0.0006/g/L, so as to obtain a purifying liquid;
and fifthly, adding the purified solution obtained in the step four into a sodium carbonate solution with the concentration of 2mol/L which is 1.1 times of the theoretical amount by adopting an electromagnetic heating stirrer to carry out thermal decomposition to form lithium carbonate precipitate, heating and stirring at 95 ℃ to react for 4 h, filtering, washing with deionized water with the wet weight of the filtered lithium carbonate precipitate being 1.5 times of 80 ℃ for 15 min, filtering again, and washing the precipitate with saturated lithium carbonate solution with the temperature of 80 ℃ for 2 times. And (3) returning filtrate and washing liquid generated by thermal decomposition after filtration to the second step for recycling, and finally drying the washed lithium carbonate precipitate in a drying box at the temperature of 95 ℃ to obtain a lithium carbonate product with the purity of 99.58%.
Example 3
Step one, mixing black powder material of positive and negative electrodes of lithium cobaltate, 3 mol/L acetic acid and 20g/L tannic acid of a waste lithium battery according to 1g:3 mL: the 2mL are respectively added into a reactor, and the leaching rates of lithium and cobalt are respectively 95% and 91% under the conditions of stirring reaction rate of 400 r/min and reaction temperature of 60 ℃ for 3 h.
And step two, carrying out suction filtration on the solution obtained in the step one to obtain primary leaching solution and primary leaching slag, simultaneously adding the primary leaching solution and alkaline solution into a reaction kettle, wherein the feeding rate of the primary leaching solution is 5. 5 mL/min, the feeding rate of 30% KOH solution is 0.2-0.3 mL/min, the reaction temperature is 50 ℃, the reaction time is 8 h, and the reaction pH value is controlled to be 10-10.1. Carrying out suction filtration to obtain secondary leaching liquid and secondary leaching slag containing Ni, mn and Co;
evaporating and concentrating the secondary leaching solution obtained in the step II until the mass concentration of lithium reaches 18-20g/L, and conveying the secondary leaching residue obtained in the step II into an extraction workshop for reprocessing;
and fourthly, flowing the concentrated solution obtained in the third step into D860 type chelating ion exchange resin filled with 1.5L at the flow rate of 1 mL/min for ion exchange impurity removal. The impurities of nickel, cobalt, manganese, copper, aluminum, iron, calcium and magnesium are all less than 0.0006/g/L, so as to obtain a purifying liquid;
and fifthly, adding the purified solution obtained in the step four into a sodium carbonate solution with the concentration of 2mol/L which is 1.1 times of the theoretical amount by adopting an electromagnetic heating stirrer to carry out thermal decomposition to form lithium carbonate precipitate, heating and stirring at 80 ℃ to react for 4 h, filtering, washing with deionized water with the wet weight of the filtered lithium carbonate precipitate being 2 times of 80 ℃ for 15 min, filtering again, and washing the precipitate with saturated lithium carbonate solution with the temperature of 80 ℃ for 2 times. And (3) returning filtrate and washing liquid generated by thermal decomposition after filtration to the second step for recycling, and finally drying the washed lithium carbonate precipitate in a drying box at the temperature of 95 ℃ to obtain a lithium carbonate product with the purity of 99.78%.
Example 4
Step one, mixing black powder material of positive and negative electrodes of lithium cobaltate, 1 mol/L acetic acid and 10g/L tannic acid of a waste lithium battery according to 1g:5 mL: the 2mL are respectively added into a reactor, and the leaching rates of lithium and cobalt are 97 percent and 94 percent respectively under the conditions of stirring reaction rate of 500 r/min and reaction temperature of 60 ℃ for 4 h.
And step two, carrying out suction filtration on the solution obtained in the step one to obtain primary leaching solution and primary leaching slag, simultaneously adding the primary leaching solution and alkaline solution into a reaction kettle, wherein the feeding rate of the primary leaching solution is 5. 5 mL/min, the feeding rate of the NaOH solution with the mass concentration of 30% is 0.2-0.3 mL/min, the reaction temperature is 50 ℃, the reaction time is 8 h, and the reaction pH value is controlled to be 10-10.1. Carrying out suction filtration to obtain secondary leaching liquid and secondary leaching slag containing Ni, mn and Co;
evaporating and concentrating the secondary leaching solution obtained in the step II until the mass concentration of lithium reaches 18-20g/L, and conveying the secondary leaching residue obtained in the step II into an extraction workshop for reprocessing;
and fourthly, flowing the concentrated solution obtained in the third step into D860 type chelating ion exchange resin filled with 1.5L at the flow rate of 1 mL/min for ion exchange impurity removal. The impurities of nickel, cobalt, manganese, copper, aluminum, iron, calcium and magnesium are all less than 0.0006/g/L, so as to obtain a purifying liquid;
and fifthly, adding the purified solution obtained in the step four into a sodium carbonate solution with the concentration of 2mol/L which is 1.2 times of the theoretical amount by adopting an electromagnetic heating stirrer to carry out thermal decomposition to form lithium carbonate precipitate, heating and stirring at 95 ℃ to react for 4 h, filtering, washing with deionized water with the wet weight of the filtered lithium carbonate precipitate being 2 times of 80 ℃ for 20 min, filtering again, and washing the precipitate with saturated lithium carbonate solution with the temperature of 80 ℃ for 3 times. And (3) returning filtrate and washing liquid generated by thermal decomposition after filtration to the second step for recycling, and finally drying the washed lithium carbonate precipitate in a drying box at the temperature of 95 ℃ to obtain a lithium carbonate product with the purity of 99.82%.
Example 5
Step one, mixing black powder material of positive and negative electrodes of lithium cobaltate, 2mol/L acetic acid and 15g/L tannic acid of a waste lithium battery according to 1g:10 mL: the 2mL are respectively added into a reactor, and the leaching rates of lithium and cobalt are respectively 99 percent and 94 percent under the conditions of stirring reaction rate of 400 r/min and reaction temperature of 60 ℃ for 2 h.
And step two, carrying out suction filtration on the solution obtained in the step one to obtain primary leaching solution and primary leaching slag, simultaneously adding the primary leaching solution and alkaline solution into a reaction kettle, wherein the feeding rate of the primary leaching solution is 5. 5 mL/min, the feeding rate of 30% KOH solution is 0.2-0.3 mL/min, the reaction temperature is 50 ℃, the reaction time is 8 h, and the reaction pH value is controlled to be 10-10.1. Carrying out suction filtration to obtain secondary leaching liquid and secondary leaching slag containing Ni, mn and Co;
evaporating and concentrating the secondary leaching solution obtained in the step II until the mass concentration of lithium reaches 18-20g/L, and conveying the secondary leaching residue obtained in the step II into an extraction workshop for reprocessing;
and fourthly, flowing the concentrated solution obtained in the third step into D860 type chelating ion exchange resin filled with 1.5L at the flow rate of 1 mL/min for ion exchange impurity removal. The impurities of nickel, cobalt, manganese, copper, aluminum, iron, calcium and magnesium are all less than 0.0006/g/L, so as to obtain a purifying liquid;
and fifthly, adding the purified solution obtained in the step four into a sodium carbonate solution with the concentration of 2mol/L which is 1.2 times of the theoretical amount by adopting an electromagnetic heating stirrer to carry out thermal decomposition to form lithium carbonate precipitate, heating and stirring at 95 ℃ to react for 4 h, filtering, washing with deionized water with the wet weight of the filtered lithium carbonate precipitate being 1.5 times of the wet weight of the filtered lithium carbonate precipitate for 20 min, filtering again, and washing the precipitate with a saturated lithium carbonate solution with the temperature of 80 ℃ for 2 times. And (3) returning filtrate and washing liquid generated by thermal decomposition after filtration to the second step for recycling, and finally drying the washed lithium carbonate precipitate in a drying box at the temperature of 95 ℃ to obtain a lithium carbonate product with the purity of 99.74%. The leaching rates of lithium and cobalt in different experiments are shown in table 1.
TABLE 1 Leaching Rate of lithium and cobalt from different experiments
| Experiment | Comparative example | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| |
60% | 99% | 96% | 95% | 97% | 99% |
| Co | 42% | 94% | 92% | 91% | 94% | 94% |
As can be seen from the results of the above table, the leaching rate of lithium and cobalt is higher by the synergistic leaching of tannic acid and acetic acid as compared with the comparative example.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A method for selectively recovering lithium from waste lithium batteries, comprising the steps of:
step one, mixing mixed black powder containing positive and negative electrodes of waste lithium batteries with a leaching agent, and placing the mixed black powder and the leaching agent into a reactor for reaction; the leaching agent is tannic acid-acetic acid mixture;
step two, carrying out suction filtration on the solution obtained in the step one to obtain primary leaching solution and primary leaching slag, adding alkaline solution into the primary leaching solution to adjust the pH value of the solution to 10-10.1, and carrying out suction filtration to obtain secondary leaching solution and secondary leaching slag containing Co;
evaporating and concentrating the secondary leaching solution obtained in the step II until the mass concentration of lithium reaches 18-20g/L, and conveying the secondary leaching residue obtained in the step II into an extraction workshop for reprocessing;
step four, carrying out ion exchange on the concentrated solution obtained in the step three by using resin to remove soluble impurities, thereby obtaining a purified solution;
and fifthly, adding the purified solution obtained in the step four into carbonate solution with the theoretical amount of 1.1-1.2 times by adopting an electromagnetic heating stirrer to carry out thermal decomposition to form lithium carbonate precipitate, heating and stirring at 80-95 ℃ to react for 1-5 h, filtering, returning filtrate and washing solution generated by thermal decomposition to the step two for recycling, washing the lithium carbonate precipitate, and drying in a drying box at 95 ℃ to obtain the battery grade lithium carbonate product.
2. The method for selectively recovering lithium from waste lithium batteries according to claim 1, wherein the method comprises the steps of: in the first step, the waste lithium battery black powder comprises one or two of lithium cobaltate anode and cathode mixture and lithium cobaltate anode material.
3. The method for selectively recovering lithium from waste lithium batteries according to claim 1, wherein the method comprises the steps of: in the first step, the liquid-solid ratio of the black powder of the waste lithium battery to acetic acid is 3-10 mL:1g.
4. The method for selectively recovering lithium from waste lithium batteries according to claim 1, wherein the method comprises the steps of: in the first step, the concentration of acetic acid is 1-3 mol/L, and the concentration of tannic acid is 10-20 g/L.
5. The method for selectively recovering lithium from waste lithium batteries according to claim 1, wherein the method comprises the steps of: the first reaction condition is that the stirring reaction rate is 400-600 r/min, the stirring time is 2-4 h, and the reaction temperature is 50-80 ℃.
6. The method for selectively recovering lithium from waste lithium batteries according to claim 1, wherein the method comprises the steps of: and step two, the alkaline solution is at least one or a combination of a plurality of liquid alkali, ammonia water and potassium hydroxide.
7. The method for selectively recovering lithium from waste lithium batteries according to claim 1, wherein the method for adding alkaline solution to the primary leachate to adjust the pH value of the solution in the second step is a parallel flow precipitation method: adding primary leaching solution and alkaline solution into a reaction kettle at the same time, wherein the feeding rate of the primary leaching solution is 5 mL/min, the feeding rate of the alkaline solution is 0.2-0.3 mL/min, the reaction temperature is 50 ℃, and the reaction time is 8 h.
8. The method for selectively recovering lithium from waste lithium batteries according to claim 1, wherein the method comprises the steps of: and step four, the resin is D860 chelate resin.
9. The method for selectively recovering lithium from waste lithium batteries according to claim 1, wherein the method comprises the steps of: in the fifth step, the carbonate solution is at least one or a combination of a plurality of sodium carbonate solution with the concentration of 2mol/L, potassium carbonate solution with the concentration of 2mol/L and ammonium carbonate solution with the concentration of 2 mol/L.
10. The method for selectively recovering lithium from waste lithium batteries according to claim 1, wherein in the step five, the lithium carbonate precipitation washing process is as follows: washing with deionized water at 80deg.C 1.5-2 times the wet weight of the filtered lithium carbonate precipitate for 15-20 min, filtering again, and washing the precipitate with saturated lithium carbonate solution at 80deg.C for 2-3 times.
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