CN114566729B - Comprehensive recovery method of waste lithium iron phosphate battery - Google Patents
Comprehensive recovery method of waste lithium iron phosphate battery Download PDFInfo
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- CN114566729B CN114566729B CN202210209224.8A CN202210209224A CN114566729B CN 114566729 B CN114566729 B CN 114566729B CN 202210209224 A CN202210209224 A CN 202210209224A CN 114566729 B CN114566729 B CN 114566729B
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- 238000000034 method Methods 0.000 title claims abstract description 104
- 239000002699 waste material Substances 0.000 title claims abstract description 56
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 39
- 238000011084 recovery Methods 0.000 title abstract description 23
- 238000002386 leaching Methods 0.000 claims abstract description 110
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052802 copper Inorganic materials 0.000 claims abstract description 46
- 239000010949 copper Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 26
- 229910052598 goethite Inorganic materials 0.000 claims abstract description 21
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 claims abstract description 21
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 238000012216 screening Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000002893 slag Substances 0.000 claims abstract description 7
- 238000007670 refining Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 82
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 37
- 229910052744 lithium Inorganic materials 0.000 claims description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 32
- 239000002184 metal Substances 0.000 claims description 32
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 239000004033 plastic Substances 0.000 claims description 9
- 229920003023 plastic Polymers 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000010533 azeotropic distillation Methods 0.000 claims description 2
- 239000012267 brine Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 2
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000011812 mixed powder Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 230000000813 microbial effect Effects 0.000 description 3
- 229910000497 Amalgam Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000005686 electrostatic field Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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 provides a method for comprehensively recycling waste lithium iron phosphate batteries. The method comprises the following steps: (1) Crushing waste lithium iron phosphate batteries to obtain lithium iron phosphate waste, performing ultrasonic treatment on the lithium iron phosphate waste, and sequentially washing, screening and centrifuging to obtain anode and cathode powder and a copper-containing mixture; (2) And (3) carrying out electrostatic separation on the copper-containing mixture in the step (1) to obtain a copper-aluminum mixture, carrying out alkaline leaching treatment on the copper-aluminum mixture to obtain metallic copper and aluminum-containing waste liquid, carrying out acid leaching treatment on the anode powder and the cathode powder in the step (1) to obtain graphite and primary leaching solution, carrying out oxygen pressure leaching iron removal on the primary leaching solution by a goethite method to obtain secondary leaching solution and iron-containing slag, and refining the secondary leaching solution in an alcohol-water system to obtain battery-grade lithium carbonate. The recovery method has the beneficial effects of green environment protection and high recovery rate.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a method for comprehensively recycling waste lithium iron phosphate batteries.
Background
At present, most of new energy automobiles adopt lithium batteries as power sources, so that the gap of lithium salt demand at home and abroad is large, and the price of the lithium market is increased. Meanwhile, the peak period of the retirement of the lithium battery is about to come, and the problem of recycling the waste lithium battery is about to come. How to realize the efficient treatment of the metal lithium in the waste lithium battery, and form the virtuous circle of the industrial chain, not only can save resources, but also is helpful for solving the problem of environmental pollution.
The recovery methods of lithium batteries are numerous and mainly include a solid-liquid combination method, a mechanical force activation method, an electrochemical method, a microbial decomposition method and the like.
(1) Solid-liquid bonding method: CN 108110360A discloses a method for recovering alumina from ceramic diaphragms of waste lithium batteries, which comprises discharging waste lithium batteries, taking out battery cores and crushing the battery cores; the broken battery cell comprises a ceramic diaphragm, a metal product and an electrode material: placing the ceramic diaphragm in a muffle furnace for roasting: dissolving out the roasted ceramic diaphragm by alkali liquor, and introducing carbon dioxide gas into the solution to generate precipitate; filtering, and calcining the obtained precipitate to obtain the alpha or y type alumina powder.
The waste materials are crushed, sieved and calcined in an oxidizing atmosphere, the sintered materials are filtered to obtain filtrate and lithium slag after being pulped by adding water, and then the filtrate and the lithium slag are purified by acid or alkali solution to obtain refined lithium solution, but the method has the defects of more recovery steps, long flow and the like, and increases the recovery process cost.
(2) Mechanical force activation method: CN 109830773A discloses a method for recovering and treating waste lithium batteries, which comprises the steps of disassembly and separation, crushing, sieving, rolling and crushing, primary magnetic separation, ball milling and crushing, secondary magnetic separation and final classification. The method is convenient to operate, green and environment-friendly, and the recovery yield of lithium is less than 30%.
(3) Electrochemical method: CN 113174614A discloses a method for recovering lithium from waste lithium batteries by a mercury electrode electrolysis method, which adopts a constant current continuous electrolysis method to electrochemically reduce lithium ions in lithium waste liquid to form lithium amalgam, the lithium amalgam flows into a mercury decomposition tank outside an electrolysis tank to react with hot water to generate lithium hydroxide, and the aqueous solution after mercury decomposition is concentrated, crystallized, filtered and dried to recover lithium hydroxide, thereby realizing the recovery of lithium from waste lithium ion batteries. Part of elements in the waste materials are separated in an ionic form through electrolysis and then are respectively recovered, and the method is difficult to popularize and apply in a short period because of potential safety hazards, low efficiency and possibly deteriorated effect during batch treatment in large-scale application.
(4) Microbial decomposition method: CN 110265676A discloses a method for leaching lithium diamond by using microbial fuel cell, the biological decomposition method utilizes the metabolite of microorganism to dissolve and leach the material, and mainly uses the multi-element comprehensive recovery of mixed cell, and the method is green and pollution-free, but the comprehensive recovery rate of element is to be improved, and at the same time the popularization and application of the method also face the problems of long microorganism culture period and easy pollution.
Although related technicians do much work, the problems of difficult large-scale application, low recovery yield, environmental pollution and the like still exist, and the development of a method for recovering the lithium battery anode material with green and environment protection and high yield is important.
Disclosure of Invention
The invention aims to provide a method for comprehensively recycling waste lithium iron phosphate batteries.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the invention aims to provide a method for comprehensively recycling waste lithium iron phosphate batteries, which comprises the following steps:
(1) Crushing waste lithium iron phosphate batteries to obtain lithium iron phosphate waste, performing ultrasonic treatment on the lithium iron phosphate waste, and sequentially washing, screening and centrifuging to obtain anode and cathode powder and a copper-containing mixture;
(2) And (3) carrying out electrostatic separation on the copper-containing mixture in the step (1) to obtain a copper-aluminum mixture, carrying out alkaline leaching treatment on the copper-aluminum mixture to obtain graphite and a primary leaching solution, carrying out needle iron ore oxygen pressure leaching iron removal on the primary leaching solution to obtain a secondary leaching solution and iron-containing slag, and refining the secondary leaching solution in an alcohol-water system to obtain battery-grade lithium carbonate.
According to the invention, the waste lithium iron phosphate battery is directly treated, so that the complex work of separating and selecting the positive and negative plates/shells in the earlier stage is avoided, and the method is convenient for large-scale application. According to the invention, after salt water of a waste lithium iron phosphate battery is subjected to immersion discharge, a pole piece and positive and negative electrodes are separated in an ultrasonic reaction kettle, copper aluminum plastic and positive and negative electrode powder are centrifugally separated by washing and screening, elemental copper is extracted by electrostatic separation and alkali leaching, graphite is separated by acid leaching from the positive and negative electrode powder, lithium solution is obtained after iron removal by a goethite method, sodium carbonate is adopted for precipitating lithium, and the characteristic that lithium carbonate is slightly soluble in water and insoluble in alcohols is utilized for refining and extracting battery-grade lithium carbonate.
The ultrasonic treatment in the step (1) is performed in an ultrasonic reaction kettle, the ultrasonic reaction kettle periodically undergoes the processes of growth, shrinkage and final fracture through the cavitation effect of ultrasonic waves, the shock wave generated by the fracture can immediately act on the surface of the positive and negative electrode powder layers, the corresponding powder layers can generate compression stress waves, and the powder layers can reflect to generate tensile stress when the compression stress waves propagate to the surface of the powder layers according to the compression stress wave principle. Therefore, when numerous micro-bubbles break, the tensile stress between the powder layer and the foil will increase until the powder layer is peeled off.
The electrostatic separation in the step (2) uses the difference of charges of the raw materials in the high-voltage electrostatic field to achieve the screening purpose, and when the raw materials are brought into the high-voltage electrostatic field, the raw materials are subjected to the actions of various electric power, centripetal force and acting force. Because the electric characteristics of various raw materials are different, the motion trail is different when the raw materials fall due to the difference of the bearing conditions, and then the metal materials and the nonmetal plastics are separated, the method is purely physical sorting, no pollution exists, meanwhile, no environmental protection pressure exists, and the operation cost of the electrostatic plastic separation equipment is low and the operation is simple.
As a preferable technical scheme of the invention, the waste lithium iron phosphate battery in the step (1) is subjected to salt leaching treatment before being crushed.
Preferably, the salt solution of the salt leaching treatment is industrial brine.
Preferably, the solvent for the ultrasonic treatment of step (1) is NMP.
Preferably, the temperature of the ultrasonic treatment in the step (1) is 65 to 95 ℃, wherein the temperature may be 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, 95 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable, preferably 82 to 87 ℃.
Preferably, the stirring rate of the ultrasonic treatment in the step (1) is 200-600 r/min, wherein the stirring rate can be 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, 550r/min or 600r/min, etc., but is not limited to the listed values, and other non-listed values in the range of the values are equally applicable, preferably 350-450 r/min.
Preferably, the frequency of the ultrasonic treatment in the step (1) is 15-40 KHz, wherein the frequency can be 15KHz, 20KHz, 25KHz, 30KHz, 35KHz or 40KHz, etc., but is not limited to the recited value, and other non-recited values within the range of the recited value are equally applicable, preferably 35-40 KHz;
preferably, the time of the ultrasonic treatment in the step (1) is 30 to 90min, wherein the time may be 30min, 35min, 40min, 45min, 50min, 55min, 60min, 65min, 70min, 75min, 80min, 85min or 90min, etc., but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable, preferably 45 to 55min.
The function of the salt leaching in the invention is to discharge the waste lithium iron phosphate battery, the anode and the cathode are separated from the foil by the NMP added during ultrasonic treatment combined with an ultrasonic reaction kettle, and NMP is selected because NMP can be recovered after centrifugal heating, thus meeting the green circulation requirement.
As a preferred embodiment of the present invention, the copper-containing mixture of step (1) comprises metallic copper, metallic aluminum and plastic.
Preferably, the copper-containing mixture is subjected to a drying treatment prior to the electrostatic separation in step (2).
Preferably, the copper-aluminum mixture of step (2) comprises metallic copper and metallic aluminum.
As a preferable technical scheme of the invention, the solution of the alkaline leaching treatment in the step (2) is NaOH solution.
Preferably, the concentration of the NaOH solution is 150-250 g/L, wherein the concentration can be 150g/L, 160g/L, 170g/L, 180g/L, 190g/L, 200g/L, 210g/L, 220g/L, 230g/L, 240g/L or 250g/L, etc., but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable, preferably 180-220 g/L.
Preferably, the alkaline leaching treatment in the step (2) is performed at a temperature of 80 to 100 ℃, wherein the temperature may be 800 ℃, 820 ℃, 840 ℃, 860 ℃, 880 ℃, 900 ℃, 920 ℃, 940 ℃, 960 ℃, 980 ℃, or 1000 ℃, etc., but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable, preferably 85 to 95 ℃.
Preferably, the stirring speed of the alkaline leaching treatment in the step (2) is 200-600 r/min, wherein the stirring speed can be 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, 550r/min or 600r/min, and the like, but not limited to the listed values, other non-listed values in the range of the values are equally applicable, and the range of the values is preferably 350-450 r/min.
Preferably, the time of the alkaline leaching treatment in the step (2) is 1 to 5 hours, wherein the time can be 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, and the like, but the alkaline leaching treatment is not limited to the listed values, and other non-listed values in the range of the values are equally applicable, and preferably 2.5 to 3.5 hours.
As a preferred technical solution of the present invention, the ratio of sodium hydroxide to the sum of metallic copper and metallic aluminum in the alkaline leaching solution in the step (2) is 5:1 to 10:1, wherein the ratio may be 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable, preferably 6:1 to 8:1.
Preferably, the aluminum-containing solution in the step (2) is subjected to cooling crystallization treatment to obtain Al (OH) 3 。
In the invention, al (OH) can be obtained by adding seed crystals into the aluminum-containing waste liquid and cooling and crystallizing 3 And NaOH which can be recycled.
As a preferable technical scheme of the invention, the solution of the acid leaching treatment in the step (2) is sulfuric acid solution.
Preferably, the concentration of the sulfuric acid solution is 100-200 g/L, wherein the concentration can be 100g/L, 110g/L, 120g/L, 130g/L, 140g/L, 150g/L, 160g/L, 170g/L, 180g/L, 190g/L or 200g/L, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, the oxygen pressure of the goethite oxygen pressure leaching iron removal in the step (2) is 1.0-1.5 Mpa, wherein the oxygen pressure can be 1.0Mpa, 1.1Mpa, 1.2Mpa, 1.3Mpa, 1.4Mpa or 1.5Mpa, and the like, but the goethite oxygen pressure leaching iron removal method is not limited to the listed values, and other non-listed values in the range of the values are applicable.
Preferably, the pH of the goethite oxygen pressure leaching iron removal is 5.0 to 6.0, wherein the pH may be 5.0, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6, 5.7, 5.8, 5.9 or 6.0, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable;
preferably, the temperature for iron removal by oxygen pressure leaching in the goethite method is 85-95 ℃, wherein the temperature can be 85 ℃, 86 ℃, 87 ℃, 88 ℃, 89 ℃, 90 ℃, 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃ or the like, but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
Preferably, the reaction time for iron removal by oxygen pressure leaching of the goethite method is 1.8-2.2 h, wherein the reaction time can be 1.8h, 1.9h, 2h, 2.1h or 2.2h, etc., but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
Preferably, the stirring rate of the goethite oxygen pressure leaching iron removal is 100-300 r/min, wherein the stirring rate can be 100r/min, 150r/min, 200r/min, 250r/min or 300r/min, and the like, but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
As a preferable technical scheme of the invention, the alcohol-water system in the step (2) comprises alcohol liquid and sodium carbonate.
Preferably, the temperature of the alcohol-water system is 15 to 35 ℃, wherein the temperature can be 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the mass ratio of the alcohol to the water in the alcohol solution is 0.5:1-1.5:1, wherein the mass ratio can be 0.5:1, 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1 or 1.5:1, but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
In the preferred technical scheme of the invention, the secondary leaching solution in the step (2) is refined in an alcohol-water system, and alcohol solution and sodium carbonate are added into the secondary leaching solution for reaction.
Preferably, the rate of adding the alcohol solution into the secondary leaching solution is 20-60L/min, wherein the rate can be 20L/min, 25L/min, 30L/min, 35L/min, 40L/min, 45L/min, 50L/min, 55L/min or 60L/min, etc., but the rate is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
Preferably, the mass ratio of the sodium carbonate to the lithium in the secondary leaching solution is 0.6:1-1.2:1, wherein the mass ratio can be 0.6:1, 0.7:1, 0.8:1, 0.9:1, 1.0:1, 1.1:1 or 1.2:1, etc., but is not limited to the recited values, and other non-recited values in the range of the values are equally applicable.
Preferably, the reaction time is 0.8 to 1.2 hours, wherein the time can be 0.8 hours, 0.9 hours, 1.0 hours, 1.1 hours or 1.2 hours, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the stirring rate of the reaction is 100-300 r/min, wherein the stirring rate can be 100r/min, 150r/min, 200r/min, 250r/min or 300r/min, etc., but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the alcoholic water system purifies the alcoholic liquid by constant temperature distillation or azeotropic distillation.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) Crushing the waste lithium iron phosphate battery subjected to the salt leaching treatment to obtain lithium iron phosphate waste, performing ultrasonic treatment on the lithium iron phosphate waste for 30-90 min at the temperature of 65-95 ℃ and the stirring speed of 200-600 r/min and the frequency of 15-40 KHz, and then sequentially washing, screening and centrifuging to obtain anode and cathode powder and a copper-containing mixture;
(2) Carrying out electrostatic separation on the copper-containing mixture obtained in the step (1) of drying treatment to obtain a copper-aluminum mixture, and carrying out alkaline leaching treatment on the copper-aluminum mixture at 80-100 ℃ for 1-5 h to obtain metallic copperAnd aluminum-containing waste liquid, cooling and crystallizing the aluminum-containing waste liquid to obtain Al (OH) 3 And (3) carrying out acid leaching treatment on the anode and cathode powder in the step (1) to obtain graphite and a primary leaching solution, carrying out oxygen pressure leaching iron removal by a goethite method with oxygen pressure of 1.0-1.5 Mpa, pH of 5.0-6.0 and temperature of 85-95 ℃ on the primary leaching solution to obtain a secondary leaching solution and iron-containing slag, adding alcohol solution and sodium carbonate into the secondary leaching solution, and refining the secondary leaching solution in an alcohol-water system to obtain battery grade lithium carbonate.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a method for comprehensively recycling waste lithium iron phosphate batteries, which avoids complicated separation and selection work of positive and negative plates/shells and is convenient for large-scale application; the invention provides a method for preparing battery grade lithium carbonate by an alcohol water system, wherein the recovery yield of lithium is more than 95%, in addition, the recovery yield of copper is more than 97.8%, and the recovery yield of graphite is more than 91.9%; the method promotes a green low-carbon cyclic development economic system with carbon reaching peak/carbon neutralization.
Drawings
FIG. 1 is a process flow diagram for the integrated recovery of spent lithium iron phosphate batteries of examples 1-5, examples 7-14 and comparative example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a method for comprehensively recycling waste lithium iron phosphate batteries (a process flow chart is shown in fig. 1), which comprises the following steps:
(1) And (3) immersing and discharging the waste lithium iron phosphate battery by using salt water, crushing, adding NMP into an ultrasonic reaction kettle, heating to 85 ℃, stirring at a speed of 400r/min, performing ultrasonic working at a frequency of 40KHz for 50min, washing, screening, and centrifuging to separate anode and cathode powder.
(2) Baking copper, aluminum and plasticAfter drying, extracting metal copper and aluminum through electrostatic separation, leaching mixed metal alkali to separate aluminum, obtaining metal copper, carrying out alkali leaching on the mixed metal, heating to 90 ℃, and stirring at a speed of 400r/min, wherein the liquid-solid ratio is 7:1 (L/kg), the concentration of NaOH is 200g/L, the reaction time is 3h, and the metal copper is obtained by centrifugal cleaning. And leaching the anode and cathode mixed powder by sulfuric acid to obtain a graphite product. Oxygen pressure leaching of primary leaching solution by goethite method to remove iron and O 2 The pressure was 1.2mpa, ph=5.4, the temperature was 85 ℃, the reaction time was 2h, and the stirring rate was 200r/min. The secondary leaching solution is refined into battery grade lithium carbonate through an alcohol-water system, and the addition amount of sodium carbonate at normal temperature is Na 2 CO 3 Li=0.8, the addition amount of the alcohol solution is alcohol: water=0.8, the rate of addition of the alcohol solution was 40L/min, the reaction time was 1h, and the stirring rate was 150r/min.
Example 2
The embodiment provides a method for comprehensively recycling waste lithium iron phosphate batteries (a process flow chart is shown in fig. 1), which comprises the following steps:
(1) And (3) immersing and discharging the waste lithium iron phosphate battery by using salt water, crushing, adding NMP into an ultrasonic reaction kettle, heating to 95 ℃, stirring at 600r/min, performing ultrasonic working frequency of 40KHz for 90min, washing, screening, and centrifuging to separate anode and cathode powder.
(2) After copper, aluminum and plastic are dried, extracting metal copper and aluminum through electrostatic separation, leaching mixed metal alkali to separate aluminum, obtaining metal copper, carrying out alkali leaching on the mixed metal, heating to 90 ℃, and stirring at a speed of 600r/min, wherein the liquid-solid ratio is 10:1 (L/kg), the concentration of NaOH is 250g/L, the reaction time is 5h, and the metal copper is obtained by centrifugal cleaning. And leaching the anode and cathode mixed powder by sulfuric acid to obtain a graphite product. Oxygen pressure leaching of primary leaching solution by goethite method to remove iron and O 2 The pressure was 1.5mpa, ph=5.8, the temperature was 95 ℃, the reaction time was 2h, and the stirring rate was 200r/min. The secondary leaching solution is refined into battery grade lithium carbonate through an alcohol-water system, and the addition amount of sodium carbonate at normal temperature is Na 2 CO 3 Li=1.2, the addition amount of the alcohol solution is alcohol: water=1.2, the rate of addition of the alcohol solution was 30L/min, the reaction time was1h, stirring rate was 200r/min.
Example 3
The embodiment provides a method for comprehensively recycling waste lithium iron phosphate batteries (a process flow chart is shown in fig. 1), which comprises the following steps:
(1) And (3) immersing and discharging the waste lithium iron phosphate battery by using salt water, crushing, adding NMP into an ultrasonic reaction kettle, heating to 65 ℃, stirring at the speed of 200r/min, performing ultrasonic working at the frequency of 20KHz for 30min, washing, screening, and centrifuging to separate anode and cathode powder.
(2) After copper, aluminum and plastic are dried, extracting metal copper and aluminum through electrostatic separation, leaching mixed metal alkali to separate aluminum, obtaining metal copper, carrying out alkali leaching on the mixed metal, heating to 80 ℃, and stirring at a speed of 300r/min, wherein the liquid-solid ratio is 5:1 (L/kg), the concentration of NaOH is 150g/L, the reaction time is 2h, and the metal copper is obtained by centrifugal cleaning. And leaching the anode and cathode mixed powder by sulfuric acid to obtain a graphite product. Oxygen pressure leaching of primary leaching solution by goethite method to remove iron and O 2 The pressure was 1.1mpa, ph=5.0, the temperature was 85 ℃, the reaction time was 2h, and the stirring rate was 200r/min. The secondary leaching solution is refined into battery grade lithium carbonate through an alcohol-water system, and the addition amount of sodium carbonate at normal temperature is Na 2 CO 3 Li=0.6, the addition amount of the alcohol solution is alcohol: water=0.6, the rate of addition of the alcohol solution was 60L/min, the reaction time was 1h, and the stirring rate was 200r/min.
Example 4
The embodiment provides a method for comprehensively recycling waste lithium iron phosphate batteries (a process flow chart is shown in fig. 1), which comprises the following steps:
(1) And (3) immersing and discharging the waste lithium iron phosphate battery by using salt water, crushing, adding NMP into an ultrasonic reaction kettle, heating to 85 ℃, stirring at a speed of 200r/min, performing ultrasonic working at a frequency of 30KHz for 40min, washing, screening, and centrifuging to separate anode and cathode powder.
(2) Drying copper, aluminum and plastic, extracting metal copper and aluminum by electrostatic separation, leaching mixed metal alkali to separate aluminum to obtain metal copper, leaching mixed metal alkali, heating to 80 ℃, and stirring at a speedThe degree is 600r/min, and the liquid-solid ratio is 8:1 (L/kg), the concentration of NaOH is 200g/L, the reaction time is 2h, and the metal copper is obtained by centrifugal cleaning. And leaching the anode and cathode mixed powder by sulfuric acid to obtain a graphite product. Oxygen pressure leaching of primary leaching solution by goethite method to remove iron and O 2 The pressure was 1.2mpa, ph=5.3, the temperature was 85 ℃, the reaction time was 2h, and the stirring rate was 300r/min. The secondary leaching solution is refined into battery grade lithium carbonate through an alcohol-water system, and the addition amount of sodium carbonate at normal temperature is Na 2 CO 3 Li=0.8, the addition amount of the alcohol solution is alcohol: water=0.8, the rate of addition of the alcohol solution was 50L/min, the reaction time was 1h, and the stirring rate was 200r/min.
Example 5
The embodiment provides a method for comprehensively recycling waste lithium iron phosphate batteries (a process flow chart is shown in fig. 1), which comprises the following steps:
(1) And (3) immersing and discharging the waste lithium iron phosphate battery by using salt water, crushing, adding NMP into an ultrasonic reaction kettle, heating to 95 ℃, stirring at 600r/min, performing ultrasonic working frequency of 40KHz for 50min, washing, screening, and centrifuging to separate anode and cathode powder.
(2) After copper, aluminum and plastic are dried, extracting metal copper and aluminum through electrostatic separation, leaching mixed metal alkali to separate aluminum, obtaining metal copper, carrying out alkali leaching on the mixed metal, heating to 80 ℃, and stirring at a speed of 600r/min, wherein the liquid-solid ratio is 6:1 (L/kg), the concentration of NaOH is 250g/L, the reaction time is 2h, and the metal copper is obtained by centrifugal cleaning. And leaching the anode and cathode mixed powder by sulfuric acid to obtain a graphite product. Oxygen pressure leaching of primary leaching solution by goethite method to remove iron and O 2 The pressure was 1.2mpa, the ph=5.4, the temperature was 90 ℃, the reaction time was 2h, and the stirring rate was 200r/min. The secondary leaching solution is refined into battery grade lithium carbonate through an alcohol-water system, and the addition amount of sodium carbonate at normal temperature is Na 2 CO 3 Li=1.2, the addition amount of the alcohol solution is alcohol: water=1.0, the rate of addition of the alcohol solution was 30L/min, the reaction time was 1h, and the stirring rate was 200r/min.
Example 6
This example is identical to example 1 except that NMP from step (1) is replaced with deionized water.
Example 7
In this example, except that the liquid-solid ratio in step (2) is 7:1 (L/kg) is replaced by 11:1 (L/kg), the other conditions were the same as those in example 1. Wherein the process flow diagram is shown in fig. 1.
Example 8
In this example, except that the liquid-solid ratio in step (2) is 7:1 (L/kg) is replaced by 4:1 (L/kg), the other conditions were the same as those in example 1. Wherein the process flow diagram is shown in fig. 1.
Example 9
In this example, O in step (2) is divided into 2 The same conditions as in example 1 were followed except that the pressure was changed to 0.8MPa and 1.2 MPa. Wherein the process flow diagram is shown in fig. 1.
Example 10
In this example, O in step (2) is divided into 2 The same conditions as in example 1 were followed except that the pressure was changed to 1.5MPa and 1.2 MPa. Wherein the process flow diagram is shown in fig. 1.
Example 11
In this example, the sodium carbonate added at room temperature in the step (2) was added as Na 2 CO 3 Li=0.8 is replaced by sodium carbonate at normal temperature, and the addition amount is Na 2 CO 3 Except for li=0.5, the other conditions were the same as in example 1. Wherein the process flow diagram is shown in fig. 1.
Example 12
In this example, the sodium carbonate added at room temperature in the step (2) was added as Na 2 CO 3 Li=0.8 is replaced by sodium carbonate at normal temperature, and the addition amount is Na 2 CO 3 Except for li=1.3, the other conditions were the same as in example 1. Wherein the process flow diagram is shown in fig. 1.
Example 13
In this example, except that the amount of alcohol added in step (2) is alcohol: water = 0.8 replaced by alcohol solution with the addition of alcohol: except for water=0.4, the conditions were the same as in example 1. Wherein the process flow diagram is shown in fig. 1.
Example 14
In this example, except that the amount of alcohol added in step (2) is alcohol: water = 0.8 replaced by alcohol solution with the addition of alcohol: except for water=1.6, the conditions were the same as in example 1. Wherein the process flow diagram is shown in fig. 1.
Comparative example 1
Dividing O in the step (2) by the comparative example 2 The same conditions as in example 1 were followed except that the pressure was changed to 0MPa and 1.2 MPa. Wherein the process flow diagram is shown in fig. 1.
Comparative example 2
In the comparative example, lithium carbonate is prepared by replacing the secondary leaching solution in the step (2) with an ammonia water system through an alcohol-water system refined battery-grade lithium carbonate.
The recovery rates of the products in examples 1-14 and comparative examples 1-2 are shown in Table 1.
TABLE 1
From the above results, it is possible to obtain that example 1 is better in recovering copper and lithium metal than examples 2 to 14 and comparative examples 1 to 2, resulting in higher economic effects.
In comparison with example 1 and example 6, the positive and negative electrodes were hardly peeled off from the electrode sheet without using NMP as a solvent but deionized water; in example 7, the liquid-solid ratio was increased, increasing the cost of production; example 8 reduced the liquid-solid ratio and reduced the copper recovery; examples 9 to 10 change O 2 Pressure, lithium recovery rate decreases; example 11 the amount of sodium carbonate added was reduced, and the recovery rate of lithium was lowered; in example 12, the addition amount of sodium carbonate was increased, but sodium carbonate was easily introduced as a slightly soluble impurity, so that the recovery rate of lithium was decreased; examples 13 to 14 are inferior to comparative example 1 in lithium recovery rate when the alcohol-water ratio is lowered and in production cost when the alcohol-water ratio is increased.
Comparative example 1O 2 The pressure is reduced to 0Mpa, and the recovery rate of lithium is reduced; in comparative example 2, the alcohol-water system refining is replaced by an ammonia precipitation method, and impurities are introduced, so that the preparation cost is increased.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (32)
1. The method for comprehensively recycling the waste lithium iron phosphate battery is characterized by comprising the following steps of:
(1) Crushing waste lithium iron phosphate batteries to obtain lithium iron phosphate waste, performing ultrasonic treatment on the lithium iron phosphate waste, and sequentially washing, screening and centrifuging to obtain anode and cathode powder and a copper-containing mixture;
wherein the solvent for ultrasonic treatment is NMP;
(2) Carrying out electrostatic separation on the copper-containing mixture in the step (1) to obtain a copper-aluminum mixture, carrying out alkaline leaching treatment on the copper-aluminum mixture to obtain metallic copper and aluminum-containing waste liquid, carrying out acid leaching treatment on the anode powder and the cathode powder in the step (1) to obtain graphite and primary leaching solution, carrying out oxygen pressure leaching iron removal on the primary leaching solution by a goethite method to obtain secondary leaching solution and iron-containing slag, and refining the secondary leaching solution in an alcohol-water system to obtain battery-grade lithium carbonate;
wherein the alkaline leaching solution is NaOH solution;
the ratio of the sodium hydroxide to the sum of the metal copper and the metal aluminum in the alkaline leaching treatment solution is 5:1-7:1;
the oxygen pressure of the goethite method oxygen pressure leaching iron removal is 1.0-1.4 mpa;
the pH value of the goethite method oxygen pressure leaching iron removal is 5.0-6.0;
the temperature of oxygen pressure leaching iron removal by the goethite method is 85-95 ℃;
the reaction time of oxygen pressure leaching iron removal by the goethite method is 1.8-2.2 h;
the stirring rate of the goethite method oxygen pressure leaching iron removal is 100-300 r/min;
the alcohol-water system comprises alcohol liquid and sodium carbonate;
the mass ratio of the alcohol to the water in the alcohol solution is 0.7:1-1.4:1;
the mass ratio of the sodium carbonate to the lithium in the secondary leaching solution is 0.7:1-1.1:1.
2. The method of claim 1, wherein the waste lithium iron phosphate battery of step (1) is subjected to a salt leaching treatment prior to the crushing treatment.
3. The method of claim 2, wherein the salt solution of the salt leaching treatment is industrial brine.
4. The method of claim 1, wherein the temperature of the ultrasonic treatment in step (1) is 65-95 ℃.
5. The method of claim 4, wherein the temperature of the ultrasonic treatment in step (1) is 82-87 ℃.
6. The method of claim 1, wherein the ultrasonic treatment in step (1) has a stirring rate of 200 to 600r/min.
7. The method of claim 6, wherein the stirring rate of the ultrasonic treatment in the step (1) is 350-450 r/min.
8. The method of claim 1, wherein the frequency of the ultrasonic treatment in step (1) is 15-40 khz.
9. The method of claim 8, wherein the frequency of the ultrasonic treatment in step (1) is 35-40 KHz.
10. The method of claim 1, wherein the time of the ultrasonic treatment in step (1) is 30-90 min.
11. The method of claim 10, wherein the time of the ultrasonic treatment in step (1) is 45-55 min.
12. The method of claim 1, wherein the copper-containing mixture of step (1) comprises metallic copper, metallic aluminum, and plastic.
13. The method of claim 1, wherein the copper-containing mixture is subjected to a drying process prior to the electrostatic separation of step (2).
14. The method of claim 1, wherein the copper-aluminum mixture of step (2) comprises metallic copper and metallic aluminum.
15. The method of claim 1, wherein the concentration of the NaOH solution in step (2) is 150-250 g/L.
16. The method of claim 15, wherein the concentration of the NaOH solution is 180-220 g/L.
17. The method of claim 1, wherein the alkaline leaching treatment in step (2) is performed at a temperature of 80-100 ℃.
18. The method of claim 17, wherein the alkaline leaching treatment in step (2) is performed at a temperature of 85-95 ℃.
19. The method of claim 1, wherein the stirring speed of the alkaline leaching treatment in the step (2) is 200-600 r/min.
20. The method of claim 19, wherein the stirring speed of the alkaline leaching treatment in the step (2) is 350-450 r/min.
21. The method of claim 1, wherein the alkaline leaching treatment in step (2) is performed for 1-5 hours.
22. The method of claim 21, wherein the alkaline leaching treatment in step (2) is performed for 2.5-3.5 hours.
23. The method of claim 1, wherein the aluminum-containing waste liquid of step (2) is subjected to a cooling crystallization treatment to obtain Al (OH) 3 。
24. The method of claim 1, wherein the acid leaching solution of step (2) is a sulfuric acid solution.
25. The method of claim 24, wherein the sulfuric acid solution has a concentration of 100-200 g/L.
26. The method of claim 1, wherein the temperature of the aqueous-alcoholic system of step (2) is 15-35 ℃.
27. The method according to claim 1, wherein the secondary leach solution in step (2) is refined in an alcohol-water system to add alcohol solution and sodium carbonate to the secondary leach solution for reaction.
28. The method of claim 1, wherein the rate of adding the alcohol solution to the secondary leach solution in step (2) is 20-60L/min.
29. The method of claim 27, wherein the reaction time in step (2) is 0.8 to 1.2 hours.
30. The method of claim 27, wherein the stirring rate of the reaction in step (2) is 100-300 r/min.
31. The method of claim 1, wherein the alcoholic water system of step (2) purifies the alcoholic liquid by constant temperature distillation or azeotropic distillation.
32. The method according to claim 1, characterized in that it comprises the steps of:
(1) Crushing the waste lithium iron phosphate battery subjected to the salt leaching treatment to obtain lithium iron phosphate waste, performing ultrasonic treatment on the lithium iron phosphate waste for 30-90 min at the temperature of 65-95 ℃ and the stirring speed of 200-600 r/min and the frequency of 15-40 KHz, and sequentially washing, screening and centrifuging to obtain anode and cathode powder and a copper-containing mixture;
(2) Carrying out electrostatic separation on the copper-containing mixture obtained in the step (1) of drying treatment to obtain a copper-aluminum mixture, carrying out alkaline leaching treatment on the copper-aluminum mixture at 80-100 ℃ for 1-5 h, wherein the alkaline leaching treatment solution is a NaOH solution, the ratio of sodium hydroxide to the sum of metal copper and metal aluminum in the alkaline leaching treatment solution is 5:1-7:1 to obtain metal copper and aluminum-containing waste liquid, and carrying out cooling crystallization treatment on the aluminum-containing waste liquid to obtain Al (OH) 3 And (3) carrying out acid leaching treatment on the anode powder and the cathode powder in the step (1) to obtain graphite and a primary leaching solution, carrying out oxygen pressure leaching iron removal by a goethite method with oxygen pressure of 1.0-1.4 mpa, pH of 5.0-6.0, temperature of 85-95 ℃ and stirring rate of 100-300 r/min to obtain a secondary leaching solution and iron-containing slag, adding alcohol solution and sodium carbonate into the secondary leaching solution for reaction, wherein the mass ratio of the alcohol in the alcohol solution to the water is 0.7:1-1.4:1, and the mass ratio of the sodium carbonate to the lithium in the secondary leaching solution is 0.7:1-1.1:1, so as to obtain the battery grade lithium carbonate.
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