CN110323511B - Chemical method for treating waste lithium battery system and waste lithium battery treatment method - Google Patents
Chemical method for treating waste lithium battery system and waste lithium battery treatment method Download PDFInfo
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 138
- 239000002699 waste material Substances 0.000 title claims abstract description 77
- 238000000034 method Methods 0.000 title abstract description 34
- 239000000126 substance Substances 0.000 title abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 63
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 59
- 239000010941 cobalt Substances 0.000 claims abstract description 59
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000012216 screening Methods 0.000 claims abstract description 57
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 52
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000002386 leaching Methods 0.000 claims abstract description 49
- 238000000605 extraction Methods 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims description 40
- 238000007599 discharging Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001311 chemical methods and process Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 60
- 239000002253 acid Substances 0.000 description 17
- 238000004064 recycling Methods 0.000 description 16
- 239000002985 plastic film Substances 0.000 description 10
- 229920006255 plastic film Polymers 0.000 description 10
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 229910000838 Al alloy Inorganic materials 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000011889 copper foil Substances 0.000 description 8
- 239000011888 foil Substances 0.000 description 8
- 239000004033 plastic Substances 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000010926 waste battery Substances 0.000 description 5
- 210000003298 dental enamel Anatomy 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004880 explosion Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012806 monitoring device Methods 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
- B09B3/80—Destroying solid waste or transforming solid waste into something useful or harmless involving an extraction step
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
-
- 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
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- 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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Abstract
The invention relates to the technical field of chemical method disposal of waste lithium batteries, and discloses a chemical method disposal system of waste lithium batteries, which comprises a waste lithium battery storage device, a coarse crushing device, a coarse screening device, a fine crushing device, a fine screening device, an aluminum leaching device, a cobalt and lithium leaching device and a metal extraction device which are sequentially connected in series; the aluminum extraction device comprises a coarse screening device, a fine screening device, a recovery device I, a recovery device II, a recovery device III, a recovery device IV and a recovery device V, wherein the recovery device I is connected with the coarse screening device, the recovery device II is connected with the fine screening device, the recovery device III is connected with the aluminum leaching device, and the recovery device IV is connected with the metal extraction device. The invention also discloses a treatment method for treating the waste lithium battery system by using the chemical method. The invention solves the technical problem that the valuable resources in the waste lithium batteries can not be comprehensively recovered.
Description
Technical Field
The invention relates to the technical field of chemical treatment of waste lithium batteries, in particular to a chemical treatment method of a waste lithium battery system and a waste lithium battery treatment method.
Background
Lithium batteries can be broadly classified into two types: lithium metal batteries and lithium ion batteries; after the lithium ion battery undergoes 500-1000 charge-discharge cycles, the active material of the lithium ion battery loses activity, so that the capacity of the battery is reduced and the battery is scrapped. The wide use of lithium ion batteries tends to bring a large amount of waste batteries, and if the waste batteries are discarded at will, the environment is seriously polluted, and resources are wasted. If the resources in the waste lithium ion batteries can be recycled, the method has great significance in the aspects of environmental protection and resource recycling.
The invention discloses a waste lithium battery system treated by a chemical method and a waste lithium battery treatment method, which comprises a waste lithium battery material bin, a crushing and sorting machine, an anode feeder, a constant-temperature enamel reaction kettle, a first filter, a filter residue feeder, a normal-temperature acidic enamel reaction kettle and a second filter which are connected in series. The speed-adjustable stirrers arranged in the constant-temperature enamel reaction kettle and the normal-temperature acidic enamel reaction kettle are matched with a real-time monitoring device to control the reaction rate. The invention applies for recycling the LiCoO which is the anode material in the waste batteries by recycling the waste lithium batteries2The rare metal cobalt in the electrolyte aims to treat the problem of battery pollution and realize resource recovery.
However, the technical scheme of the invention patent application only solves the problem of recovering the rare metal cobalt in the waste lithium battery, does not solve the problem of recovering other metal materials in the waste lithium battery, and further does not solve the problem of recovering non-metal resources in the waste lithium battery.
The invention provides a chemical method for disposing a waste lithium battery system and a waste lithium battery treatment method, and aims to solve the technical problem that valuable resources in waste lithium batteries cannot be comprehensively recovered.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a chemical method for treating a waste lithium battery system and a waste lithium battery treatment method, and solves the technical problem that the valuable resources in the waste lithium batteries cannot be comprehensively recovered.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme:
the system for treating the waste lithium batteries by a chemical method comprises a waste lithium battery storage device, a coarse crushing device, a coarse screening device, a fine crushing device, a fine screening device, an aluminum leaching device, a cobalt and lithium leaching device and a metal extraction device which are sequentially connected in series; the recovery device comprises a coarse screening device, a fine screening device, an aluminum leaching device, a recovery device I, a recovery device II, a recovery device III, a recovery device IV and a recovery device V, wherein the coarse screening device and the recovery device I are connected with each other;
the discharge port of the waste lithium battery storage device and the feed port of the coarse crushing device are mutually communicated, the discharge port of the coarse crushing device and the feed port of the coarse screening device are mutually communicated, the discharge port of the oversize recovered materials of the coarse screening device and the feed port of the first recovery device are mutually communicated, the discharge port of the undersize materials of the coarse screening device and the feed port of the fine screening device are mutually communicated, the discharge port of the fine screening device and the feed port of the fine screening device are mutually communicated, the discharge port of the oversize recovered materials of the fine screening device and the feed port of the second recovery device are mutually communicated, and the discharge port of the undersize materials of the fine screening device and the feed port of the aluminum leaching device are mutually communicated;
the discharge port of the aluminum dissolving liquid in the aluminum leaching device is communicated with the feed port of the third recovery device, the discharge port of the cobalt and lithium containing residues in the aluminum leaching device is communicated with the feed port of the cobalt and lithium leaching device, the discharge port of the cobalt and lithium dissolving liquid in the cobalt and lithium leaching device is communicated with the feed port of the metal extraction device, the discharge port of the cobalt containing extract liquid in the metal extraction device is communicated with the feed port of the fourth recovery device, and the discharge port of the lithium containing precipitate in the metal extraction device is communicated with the feed port of the fifth recovery device.
Further, the discharge gate of old and useless lithium cell storage device is intercommunication setting each other with discharge device's feed inlet, and discharge device's discharge gate is intercommunication setting each other with coarse breaker's feed inlet.
Furthermore, an air inlet of the coarse crushing device is communicated with an air exhaust port I of the vacuumizing device.
Furthermore, the air inlet of the fine crushing device is communicated with the air exhaust port II of the vacuumizing device.
The treatment method for treating the waste lithium battery system by a chemical method comprises the following steps:
s1, discharging treatment of waste lithium batteries
The waste lithium battery is transmitted into a discharging device from a waste lithium battery storage device, and the discharging device completely releases the residual electric quantity in the waste lithium battery;
s2, coarse crushing treatment of waste lithium batteries
Firstly, a rough crushing cavity in the rough crushing device is vacuumized by the vacuumizing device, and then the rough crushing device carries out rough crushing treatment on the waste lithium batteries in a vacuum state;
s3, recycling treatment of plastic, aluminum alloy, copper foil and aluminum foil resources in waste lithium batteries
Plastics, aluminum alloy, copper foil and aluminum foil above the filter screen of the coarse screening device are conveyed to a first recovery device for recovery, and other coarse crushing materials penetrate through the screen holes of the filter screen of the coarse screening device and are conveyed to a fine crushing device;
s4, fine crushing treatment of residual coarse crushed materials
The vacuumizing device firstly vacuumizes a fine crushing cavity in the fine crushing device into a vacuum state, and the fine crushing device carries out fine crushing treatment on the residual coarse crushed materials in the vacuum state;
s5, recycling treatment of aluminum plastic film resources in waste lithium batteries
The aluminum-plastic film separated above the filter screen of the fine screening device is conveyed to a second recovery device for recovery, and other fine crushed materials penetrate through the screen holes of the filter screen of the fine screening device and are conveyed to an aluminum leaching device;
s6, recycling treatment of aluminum resources in waste lithium batteries
Adjusting the sodium hydroxide solution in the aluminum leaching device into a sodium hydroxide solution with the mass fraction of 10-15%, heating the sodium hydroxide solution to 30-40 ℃, soaking other fine crushed materials in the sodium hydroxide solution for 1-3 hours, dissolving and leaching aluminum in the fine crushed materials in the sodium hydroxide solution, conveying the aluminum dissolved in the sodium hydroxide solution to a third recovery device for recovery, and conveying the rest fine crushed materials containing cobalt and lithium residues to the cobalt and lithium leaching device;
s7, dissolving and leaching treatment of cobalt and lithium in fine crushed materials
The acid dissolving solution in the cobalt and lithium leaching device is prepared into 2mol-1H2SO4And 2-6 vol% H2O2Heating the formed acid dissolving solution to 60-80 ℃, dissolving and leaching cobalt and lithium in the finely crushed material in the acid dissolving solution, and conveying the acid dissolving solution with the cobalt and the lithium dissolved and leached into a metal extraction device;
s8, recycling cobalt and lithium resources in waste batteries
The extractant PC-88A is prepared to have the concentration of 0.9-1mol-1And adding the PC-88A extract with the pH value of 5.5-6 into a metal extraction device, extracting for 2-5h, extracting cobalt in the extract, conveying the extract containing cobalt into a recovery device IV for recovery, and conveying lithium which does not enter the organic phase of the extract into a recovery device V for recovery in the form of lithium carbonate.
Further, in the step S6, the sodium hydroxide solution is adjusted to be a 10% sodium hydroxide solution by mass and heated to 30 ℃.
Further, in the step S7, the acid dissolution solution is 2mol-1H2SO4And 6 vol% H2O2Composition, heated to 60 ℃.
Further, in the step S8, the concentration of the PC-88A extract is 0.9mol-1And PH 6.
(III) advantageous effects
Compared with the prior art, the invention provides a chemical method for treating a waste lithium battery system and a waste lithium battery treatment method, which have the following beneficial effects:
1. according to the waste lithium battery disposal system, the plastic, aluminum alloy, copper foil and aluminum foil resources in the waste lithium batteries are sequentially and gradually recovered, the aluminum plastic film resources are recovered, the aluminum resources are recovered, and finally the cobalt and lithium resources are recovered, so that the technical effect of comprehensively recovering valuable resources in the waste lithium batteries is realized.
2. This deal with old and useless lithium battery system releases the remaining electric quantity in the old and useless lithium battery completely through discharge device, and this technical scheme has solved at broken old and useless lithium battery's in-process, because of remaining electric quantity in the battery, takes place the short circuit easily, causes dangerous technical problem.
3. This deal with old and useless lithium battery system carries out broken handle to old and useless lithium cell under vacuum state through making thick breaker and thin breaker, and this technical scheme has solved remaining metallic lithium on the old and useless lithium cell negative pole, can take place violent oxidation in humid environment or air to take place burning or explosion, produce the technical problem of potential safety hazard.
4. According to the treatment method for disposing the waste lithium battery system, the technical effect of gradually and selectively separating and recycling the plastic, the aluminum alloy, the copper foil, the aluminum foil and the aluminum plastic film is realized by a pretreatment method of crushing and screening in different degrees for two times;
then the technical effect of selectively separating and recycling the aluminum resource is realized by an alkali solution dissolving and leaching method; then dissolving and leaching cobalt and lithium resources by using an acid solution dissolving and leaching method, and finally separating and recovering the cobalt and the lithium by using an extraction method, thereby realizing the technical effect of selectively separating and recovering the cobalt and the lithium;
the technical scheme realizes the technical effect of comprehensively recovering various valuable resources in the waste lithium batteries.
5. According to the treatment method for disposing the waste lithium battery system, the sodium hydroxide solution is adjusted to be the sodium hydroxide solution with the mass fraction of 10%, the sodium hydroxide solution is heated to 30 ℃, so that cobalt and aluminum can be thoroughly separated, and the technical effect of thoroughly separating and recycling the cobalt and the aluminum is achieved.
6. The treatment method for disposing the waste lithium battery system comprises the step of mixing 2mol-1H2SO4And 6 vol% H2O2Acid dissolving solution is prepared and heated to 60 ℃, the leaching dissolution rate of cobalt and lithium reaches 99 percent, and the cobalt and lithium are obviously improvedThe leaching dissolution rate of (2).
7. The treatment method for disposing the waste lithium battery system is characterized in that the concentration of the PC-88A extract liquor is prepared to be 0.9mol-1And PH is 6, the extraction rate of cobalt can reach 100%, and the technical effect of remarkably improving the extraction rate of cobalt is realized.
Drawings
FIG. 1 is a logic block diagram of a system for chemically treating waste lithium batteries according to the present invention;
fig. 2 is a logic block diagram of a treatment method for disposing a waste lithium battery system by a chemical method.
Detailed Description
The system for treating the waste lithium battery by a chemical method comprises a waste lithium battery storage device, a discharge device, a coarse crushing device, a coarse screening device, a fine crushing device, a fine screening device, an aluminum leaching device, a cobalt and lithium leaching device and a metal extraction device which are sequentially connected in series, and also comprises a vacuumizing device which is mutually connected with the coarse crushing device and the fine crushing device, and also comprises a first recovery device which is mutually connected with the coarse screening device, a second recovery device which is mutually connected with the fine screening device, a third recovery device which is mutually connected with the aluminum leaching device, a fourth recovery device and a fifth recovery device which are mutually connected with the metal extraction device;
the waste lithium battery storage device is mainly used for storing waste lithium batteries, and a discharge hole of the waste lithium battery storage device is communicated with a feed hole of the discharge device;
the discharging device is mainly used for completely releasing residual electric quantity in the waste lithium battery, and a discharging port of the discharging device is communicated with a feeding port of the coarse crushing device;
the rough crushing device is mainly used for roughly crushing the waste lithium batteries, so that the lithium battery shells are separated from the inner core, and simultaneously the current collectors are separated from active component substances on the positive and negative electrodes, an air inlet of the rough crushing device is communicated with an air exhaust opening I of the vacuumizing device, and a discharge opening of the rough crushing device is communicated with a feed inlet of the rough screening device;
the coarse screening device is mainly used for separating and recycling plastic and aluminum alloy which are arranged on the shell, and copper foil and aluminum foil which are used as current collectors from coarse crushed aggregates, a discharge port of materials recycled on a screen of the coarse screening device is communicated with a feed port of the first recycling device, and a discharge port of materials below the screen of the coarse screening device is communicated with a feed port of the fine crushing device;
the fine crushing device is mainly used for performing fine crushing treatment on the coarse crushed materials to separate an aluminum plastic film serving as a lithium battery diaphragm from active component substances, an air inlet of the fine crushing device and an air exhaust opening II of the vacuumizing device are arranged in a mutually communicated mode, and a discharge opening of the fine crushing device and a feed opening of the fine screening device are arranged in a mutually communicated mode;
the fine screening device is mainly used for recovering the aluminum-plastic film from the fine crushed materials, a discharge port of materials recovered on a screen of the fine screening device is communicated with a feed port of the second recovery device, and a discharge port of materials below a screen of the fine screening device is communicated with a feed port of the aluminum leaching device;
a sodium hydroxide solution is stored in the aluminum leaching device, the sodium hydroxide solution is mainly used for dissolving and leaching aluminum resources to thoroughly separate cobalt and aluminum, a discharge port of an aluminum dissolving solution in the aluminum leaching device is connected with a feed port of the recovery device III, and a discharge port containing cobalt and lithium residues in the aluminum leaching device is communicated with feed ports of the cobalt and lithium leaching devices;
the cobalt and lithium leaching device is internally stored with an acid dissolving solution consisting of sulfuric acid and hydrogen peroxide, the acid dissolving solution is mainly used for dissolving cobalt and lithium, and a discharge port of the cobalt and lithium dissolving solution of the cobalt and lithium leaching device is communicated with a feed port of the metal extraction device;
an extracting agent PC-88A is stored in the metal extraction device, the extracting agent PC-88A is mainly used for thoroughly separating cobalt and lithium, a discharge port of a cobalt-containing extracting solution of the metal extraction device is communicated with a feed port of the recovery device IV, and a discharge port of a lithium-containing precipitate of the metal extraction device is communicated with a feed port of the recovery device V.
The treatment method for chemically disposing the waste lithium battery system, referring to fig. 2, comprises the following steps:
s1, discharging treatment of waste lithium batteries
The waste lithium battery is transmitted into a discharging device from a waste lithium battery storage device, and the discharging device completely releases the residual electric quantity in the waste lithium battery;
the technical scheme that the discharging device completely releases the residual electric quantity in the waste lithium battery is used for solving the technical problem that the waste lithium battery is in short circuit in the crushing process to cause danger;
s2, coarse crushing treatment of waste lithium batteries
Conveying the completely discharged waste lithium battery in the step S1 from the discharging device into a coarse crushing device, vacuumizing a coarse crushing cavity in the coarse crushing device into a vacuum state by a vacuumizing device, performing coarse crushing treatment on the waste lithium battery by the coarse crushing device in the vacuum state to separate a lithium battery shell from an inner core, and separating a current collector from active component substances on a positive electrode and a negative electrode to prepare a coarse crushed material;
the technical scheme that the waste lithium batteries are subjected to rough crushing treatment by the rough crushing device in a vacuum state is to solve the technical problems that metal lithium on a negative electrode of a lithium battery is residual, and the residual metal lithium can be violently oxidized in a humid environment or air, so that combustion or explosion occurs and potential safety hazards are generated;
s3, recycling treatment of plastic, aluminum alloy, copper foil and aluminum foil resources in waste lithium batteries
Conveying the coarse crushed materials prepared in the step S2 into a coarse screening device from the coarse crushing device, separating the plastic, the aluminum alloy, the copper foil and the aluminum foil from other coarse crushed materials by the coarse screening device, conveying the plastic, the aluminum alloy, the copper foil and the aluminum foil which are separated above a filter screen of the coarse screening device into a first recovery device to achieve the purpose of recovery, and conveying other coarse crushed materials into a fine crushing device after penetrating through screen holes of the filter screen of the coarse screening device;
s4, fine crushing treatment of residual coarse crushed materials
The vacuumizing device is used for vacuumizing a fine crushing cavity in the fine crushing device to be in a vacuum state, and the fine crushing device is used for performing fine crushing treatment on the residual coarse crushed material in the vacuum state to separate an aluminum-plastic film from active component substances to prepare a fine crushed material;
the technical scheme that the fine crushing device performs fine crushing treatment on the residual coarse crushed materials in a vacuum state is to further solve the technical problems that metal lithium on a negative electrode of a lithium battery has residues, and the residual metal lithium can be violently oxidized in a humid environment or air, so that combustion or explosion occurs and potential safety hazards are generated;
s5, recycling treatment of aluminum plastic film resources in waste lithium batteries
Conveying the fine crushed materials prepared in the step S4 into a fine screening device from the fine crushing device, separating an aluminum-plastic film from other fine crushed materials by the fine screening device, conveying the aluminum-plastic film blocked above a filter sieve of the fine screening device into a second recovery device to achieve the purpose of recovery, and conveying the other fine crushed materials into an aluminum leaching device after penetrating through sieve holes of the filter sieve of the fine screening device;
s6, recycling treatment of aluminum resources in waste lithium batteries
Adjusting the sodium hydroxide solution in the aluminum leaching device into a sodium hydroxide solution with the mass fraction of 10-15%, heating the sodium hydroxide solution to 30-40 ℃, soaking other fine crushed materials obtained in the step S5 in the sodium hydroxide solution for 1-3 hours, dissolving and leaching aluminum in the fine crushed materials into the sodium hydroxide solution, conveying the aluminum dissolved in the sodium hydroxide solution to a third recovery device to achieve the recovery purpose, and conveying the other fine crushed materials containing cobalt and lithium residues into the cobalt and lithium leaching device;
wherein, the sodium hydroxide solution is adjusted into 10 percent by mass and heated to 30 ℃, and the technical proposal can realize more thorough separation of cobalt and aluminum;
s7, dissolving and leaching treatment of cobalt and lithium in waste lithium batteries
The acid dissolving solution in the cobalt and lithium leaching device is prepared into 2mol-1H2SO4And 2-6 vol% H2O2Heating the formed acid dissolving solution to 60-80 ℃, and soaking the fine crushed material containing the cobalt and lithium residues obtained in the step S6 in the acid dissolving solution for 2-4h, wherein the cobalt and the lithium in the fine crushed material are dissolved and leached in the acid dissolving solution to prepare the acid dissolving solution in which the cobalt and the lithium are dissolved and leached;
wherein the acid dissolving solution is 2mol.L-1H2SO4And 6 vol% H2O2The components are heated to 60 ℃, and the leaching dissolution rates of cobalt and lithium can reach 99 percent by the technical scheme;
s8, recycling cobalt and lithium resources in waste batteries
The acid-dissolved solution prepared in step S7, in which cobalt and lithium are dissolved and leached, is transferred to a metal extraction apparatus, and an extractant PC-88A in the metal extraction apparatus is prepared to have a concentration of 0.9 to 1mol-1Adding a PC-88A extract with the pH value of 5.5-6 into an acid dissolving solution in which cobalt and lithium are dissolved and leached, extracting for 2-5h, extracting the cobalt in the acid dissolving solution into the extract, conveying the extract containing the cobalt into a fourth recovery device to achieve the recovery purpose, and precipitating the lithium which does not enter an organic phase of the extract in the form of lithium carbonate and conveying the lithium into a fifth recovery device to achieve the recovery purpose;
wherein the concentration of the PC-88A extract is 0.9mol-1And when the PH is 6, the extraction rate of the cobalt can reach 100 percent.
Claims (1)
1. Waste lithium battery system is dealt with to chemical process, its characterized in that: the device comprises a waste lithium battery storage device, a coarse crushing device, a coarse screening device, a fine crushing device, a fine screening device, an aluminum leaching device, a cobalt and lithium leaching device and a metal extraction device which are sequentially connected in series; the recovery device comprises a coarse screening device, a fine screening device, an aluminum leaching device, a recovery device I, a recovery device II, a recovery device III, a recovery device IV and a recovery device V, wherein the coarse screening device and the recovery device I are connected with each other;
the discharge port of the waste lithium battery storage device and the feed port of the coarse crushing device are mutually communicated, the discharge port of the coarse crushing device and the feed port of the coarse screening device are mutually communicated, the discharge port of the oversize recovered materials of the coarse screening device and the feed port of the first recovery device are mutually communicated, the discharge port of the undersize materials of the coarse screening device and the feed port of the fine screening device are mutually communicated, the discharge port of the fine screening device and the feed port of the fine screening device are mutually communicated, the discharge port of the oversize recovered materials of the fine screening device and the feed port of the second recovery device are mutually communicated, and the discharge port of the undersize materials of the fine screening device and the feed port of the aluminum leaching device are mutually communicated;
a discharge port of the aluminum dissolving liquid in the aluminum leaching device is communicated with a feed port of the third recovery device, a discharge port containing cobalt and lithium residues in the aluminum leaching device is communicated with a feed port of the cobalt and lithium leaching device, a discharge port containing cobalt extraction liquid in the cobalt and lithium leaching device is communicated with a feed port of the metal extraction device, a discharge port containing cobalt extraction liquid in the metal extraction device is communicated with a feed port of the fourth recovery device, and a discharge port containing lithium precipitates in the metal extraction device is communicated with a feed port of the fifth recovery device;
the discharge port of the waste lithium battery storage device is communicated with the feed port of the discharging device, and the discharge port of the discharging device is communicated with the feed port of the coarse crushing device;
the air inlet of the coarse crushing device is communicated with the first air exhaust port of the vacuumizing device;
and the air inlet of the fine crushing device is communicated with the air exhaust port II of the vacuumizing device.
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