CN113908977A - Recovery process of waste lithium battery - Google Patents
Recovery process of waste lithium battery Download PDFInfo
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- CN113908977A CN113908977A CN202111314639.3A CN202111314639A CN113908977A CN 113908977 A CN113908977 A CN 113908977A CN 202111314639 A CN202111314639 A CN 202111314639A CN 113908977 A CN113908977 A CN 113908977A
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- copper
- waste lithium
- powder
- lithium batteries
- sorting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03B—SEPARATING SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS
- B03B9/00—General arrangement of separating plant, e.g. flow sheets
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a recovery process of waste lithium batteries. According to the invention, the waste lithium ion batteries are disassembled through shearing and crushing, then the waste lithium ion batteries enter a pyrolysis furnace for high-temperature pyrolysis, the PVDF glue and the electrolyte on the waste lithium battery pole pieces are pyrolyzed in a high-temperature anaerobic state, the pyrolyzed materials directly enter a hydrodynamic sorting system for sorting, so that the shell pile heads in the waste batteries are separated from copper-aluminum foil pole powder, and the copper-aluminum foil is further stripped from the pole powder attached to the surface through a wet stripping system. The battery powder from the pyrolysis system does not need to be subjected to processes such as dry screening or wind sorting, the battery powder directly enters the water power sorting to avoid dust raising of the electrode powder, and because lithium-containing compounds and graphite powder in the battery are electric conductors and combustible materials, if the powder dust raises and adheres to an electrical switch for a long time in the sorting process, electrical short circuit and ignition spontaneous combustion are easily caused, and potential safety hazards exist.
Description
Technical Field
The invention relates to recovery of lithium batteries, in particular to a recovery process of waste lithium batteries.
Background
China has become the largest new energy automobile market in the world, the sales volume of electric automobiles is 7 thousands in 2014, 30 thousands in 2015, and 50 thousands in 2016. The scrappage of the power battery is increased along with the gradual expiration of the service life of the battery of the key part of the electric automobile. The accumulated retirement amount of the power battery in China reaches about 20 ten thousand tons in 2020, and the number is increased to about 78 ten thousand tons by 2025.
The scrapped lithium ion battery contains lithium hexafluorophosphate, carbonate organic matters, heavy metals such as cobalt, lithium, copper and the like and plastics, which are valuable resources and have extremely high recovery value. At present, the recovery of waste power lithium ion batteries mainly has 2 modes: firstly, the echelon is utilized, secondly disassemble the recovery, can't continue to use to the battery that battery capacity drops to below 50%, can only disassemble the battery and resource recycle, to the condemned battery of echelon utilization simultaneously, finally also need disassemble and resource recycle.
The lithium ion battery is composed of a shell, a positive plate (aluminum foil), positive powder (lithium-containing compound), a negative plate (copper foil), negative powder (graphite), electrolyte, a diaphragm and the like, wherein each part of the lithium ion battery is separated out to the maximum extent by adopting a mechanical method, a physical method, a chemical method and the like in the disassembling process, so that the recycling rate of the lithium ion battery is improved, the economic benefit and the social benefit are maximized, and the aim of reducing environmental pollution is fulfilled.
The existing process is that after being crushed and pyrolyzed, waste batteries are separated into pole powder, copper aluminum foil and a shell pile head by a dry screening or wind power winnowing technology, the process has the phenomena of dust flying of the positive and negative pole powder, potential safety hazards such as electrical short circuit, ignition and spontaneous combustion and the like, the influence on the field air environment and noise is great, the body health of workers is seriously influenced, and the process also needs to be provided with high-suction dust collection and purification equipment, so that the system operation cost and the investment cost are increased.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a waste lithium battery recovery process.
The technical scheme of the invention is as follows:
a recovery process of waste lithium batteries comprises the following steps:
(1) carrying out insulation treatment on the waste lithium batteries and then transferring the waste lithium batteries to a feeding system;
(2) the material falls to a crushing system through a feeding system, the material is subjected to charged shear type crushing under the protection of nitrogen, and the fragments are conveyed to a high-temperature pyrolysis system through a screw;
(3) the crushed materials enter a high-temperature pyrolysis system, PVDF (polyvinylidene fluoride) glue and electrolyte on the waste lithium battery pole pieces are pyrolyzed in a high-temperature anaerobic state, and pyrolysis gas is butted with an organic gas collecting and processing system through an exhaust port to realize standard emission of flue gas;
(4) the materials from the pyrolysis system fall to a hydrodynamic sorting system, after meeting flowing liquid rushing from the bottom, the steel shell and the copper column head with higher specific gravity in the materials quickly fall down and are conveyed to a storage hopper or a rear-end device through a bottom spiral for further separation, and the copper-aluminum foil with low specific gravity is conveyed to a wet stripping system along with the flowing liquid;
(5) after the copper-aluminum foil sorted by the hydrodynamic sorting system is soaked and washed by dilute acid in a wet stripping system, the anode powder and the cathode powder adhered to the foil are stripped and fall off, so that the recovery rate of precious metals in the battery can be effectively improved;
(6) and drying the stripped copper-aluminum foil in a copper-aluminum separation system, shearing and granulating, and sending the copper-aluminum foil into a color separator or a specific gravity separator for copper-aluminum separation.
Further, the feeding system realizes vibration feeding, weighing and belt conveying.
Further, the crushing system comprises a feed valve, a shear crusher, a transfer screw and a nitrogen protection device.
Further, the pyrolysis temperature is 500-600 ℃, and the pyrolysis time is 1-3 hours.
Further, the hydrodynamic force sorting technology sends flowing liquid of copper-aluminum foil with light specific gravity in the materials to a wet stripping system at the rear end.
Further, the wet stripping system comprises a wet stripping circulating device, a wet stripping screen belt machine, a wet vibrating screen, a dilute acid configuration machine and a pump.
Further, the copper-aluminum sorting system comprises a dryer, a shearing granulator, a color sorter or a specific gravity sorter.
Further, the mother liquor obtained by hydrodynamic separation can be recycled to a wet stripping system, and can also be added into subsequent pole powder size mixing, if the size concentration is to be increased, pole powder made by a filter press or a belt filter or concentration equipment is added into size mixing to increase the size concentration, and the filtered mother liquor can be recycled as system liquid supplement.
Further, the hydrodynamic sorting system can be replaced by a shaker or a jump sorting device, etc.
Further, wet stripping can be replaced with a single device of soaking, scrubbing, sieving, and cleaning.
According to the invention, the waste lithium ion batteries are disassembled through shearing and crushing, then the waste lithium ion batteries enter a pyrolysis furnace for high-temperature pyrolysis, the PVDF glue and the electrolyte on the waste lithium battery pole pieces are pyrolyzed in a high-temperature anaerobic state, the pyrolyzed materials directly enter a hydrodynamic sorting system for sorting, so that the shell pile heads in the waste batteries are separated from copper-aluminum foil pole powder, and the copper-aluminum foil is further stripped from the pole powder attached to the surface through a wet stripping system. The battery powder from the pyrolysis system does not need to be subjected to processes such as dry screening or wind sorting, the battery powder directly enters the water power sorting to avoid dust raising of the electrode powder, and because lithium-containing compounds and graphite powder in the battery are electric conductors and combustible materials, if the powder dust raises and adheres to an electrical switch for a long time in the sorting process, electrical short circuit and ignition spontaneous combustion are easily caused, and potential safety hazards exist.
The invention has the beneficial effects that:
(1) the hydrodynamic sorting is adopted to replace dry screening or wind power winnowing, so that the phenomenon of dust raising of the electrode powder does not exist in the sorting process, and potential safety hazards such as electric short circuit, ignition and spontaneous combustion do not exist.
(2) The hydrodynamic separation and wet stripping technology both adopt liquid as carriers, and can be mutually independent and mutually connected and can also be combined for operation.
(3) And the hydrodynamic separation is adopted, so that no dust collecting and purifying equipment is required, and the operation cost and the investment cost of the system are reduced.
(4) And the hydrodynamic separation is adopted to replace dry screening and wind power winnowing, so that the noise can be reduced, the dust raising phenomenon is avoided, and the operation environment can be effectively improved.
(5) The mother liquor obtained by hydrodynamic separation can be recycled to a wet stripping system, and can also be added into subsequent pole powder size mixing, and the mother liquor obtained after filter pressing can be used as system fluid infusion without separate purification treatment; the wet stripping solution can be one or more of mother liquor separated by hydrodynamic force, prepared dilute acid solution and slag washing water of wet metallurgy, and can be recycled and supplemented at proper time.
(6) Diluted acid for wet stripping can also be used as mother liquor for hydrodynamic separation to participate in hydraulic separation, and dynamic diluted acid soaking can be carried out on copper-aluminum foil during the hydraulic separation of the positive and negative electrode powder copper-aluminum foil and the iron shell pile head, so that the aim of flushing and stripping the electrode powder on the surface of the copper-aluminum foil is achieved during the turbulent flow process
Drawings
FIG. 1 is a block diagram of the process flow of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the present invention is not limited thereto.
Example 1
A recovery process of waste lithium batteries comprises the following steps:
(1) carrying out insulation treatment on the waste lithium batteries and then transferring the waste lithium batteries to a feeding system;
(2) the material falls to a crushing system through a feeding system, the material is subjected to charged shear type crushing under the protection of nitrogen, and the fragments are conveyed to a high-temperature pyrolysis system through a screw;
(3) the crushed materials enter a high-temperature pyrolysis system, PVDF (polyvinylidene fluoride) glue on the waste lithium battery pole pieces and electrolyte are pyrolyzed for 1.5 hours at 550 ℃ in a high-temperature anaerobic state, and pyrolysis gas is butted with an organic gas collecting and processing system through an exhaust port to realize standard emission of flue gas;
(4) the materials from the pyrolysis system fall to a hydrodynamic sorting system, after meeting flowing liquid rushing from the bottom, the steel shell and the copper column head with higher specific gravity in the materials quickly fall down and are conveyed to a storage hopper or a rear-end device through a bottom spiral for further separation, and the copper-aluminum foil with low specific gravity is conveyed to a wet stripping system along with the flowing liquid;
(5) after the copper-aluminum foil sorted by the hydrodynamic sorting system is soaked and washed by about 5 percent of dilute sulfuric acid in a wet stripping system, the anode powder and the cathode powder adhered to the foil are stripped and fall off;
(6) and drying the stripped copper-aluminum foil in a copper-aluminum separation system, shearing and granulating, and sending the copper-aluminum foil into a color separator or a specific gravity separator for copper-aluminum separation.
Technical index of recovery rate of each component material
| Principal product | Yield (%) | Recovery (%) |
| Powder of positive and negative electrode | 43.70 | ≥98 |
| Copper (Cu) | 11.40 | ≥98 |
| Aluminium | 3.80 | ≥98 |
| Pile head and iron shell | 15.2 | ≥98 |
Claims (10)
1. The recovery process of the waste lithium battery is characterized by comprising the following steps:
(1) carrying out insulation treatment on the waste lithium batteries and then transferring the waste lithium batteries to a feeding system;
(2) the material falls to a crushing system through a feeding system, the material is subjected to charged shear type crushing under the protection of nitrogen, and the fragments are conveyed to a high-temperature pyrolysis system through a screw;
(3) the crushed materials enter a high-temperature pyrolysis system, PVDF (polyvinylidene fluoride) glue and electrolyte on the waste lithium battery pole pieces are pyrolyzed in a high-temperature anaerobic state, and pyrolysis gas is butted with an organic gas collecting and processing system through an exhaust port to realize standard emission of flue gas;
(4) the materials from the pyrolysis system fall to a hydrodynamic sorting system, after meeting flowing liquid rushing from the bottom, the steel shell and the copper column head with higher specific gravity in the materials quickly fall down and are conveyed to a storage hopper or a rear-end device through a bottom spiral for further separation, and the copper-aluminum foil with low specific gravity is conveyed to a wet stripping system along with the flowing liquid;
(5) after the copper-aluminum foil sorted by the hydrodynamic sorting system is soaked and washed by dilute acid in a wet stripping system, the anode powder and the cathode powder adhered to the foil are stripped and fall off, so that the recovery rate of precious metals in the battery can be effectively improved;
(6) and drying the stripped copper-aluminum foil in a copper-aluminum separation system, shearing and granulating, and sending the copper-aluminum foil into a color separator or a specific gravity separator for copper-aluminum separation.
2. The recycling process of waste lithium batteries according to claim 1, characterized in that the feeding system realizes vibratory feeding, weighing and belt conveying.
3. The process for recycling spent lithium batteries according to claim 1, wherein the crushing system comprises a feed valve, a shear crusher, a transfer screw and a nitrogen protection device.
4. The recycling process of waste lithium batteries as claimed in claim 1, wherein the pyrolysis temperature is 500-600 ℃ and the pyrolysis time is 1-3 hours.
5. The recycling process of waste lithium batteries as claimed in claim 1, wherein the hydrodynamic separation technique is a wet stripping system which takes liquid as a carrier, the liquid is pumped to generate power, and the flowing liquid rising from the bottom is merged with the material falling from the top to convey the flowing liquid of copper-aluminum foil with light specific gravity to the rear end.
6. The recycling process of waste lithium batteries according to claim 1, wherein the wet stripping system comprises a wet stripping circulation device, a wet stripping mesh belt machine, a wet vibrating screen, a dilute acid configuration machine and a pump.
7. The recycling process of the waste lithium batteries according to claim 1, wherein the copper-aluminum sorting system comprises a dryer, a shearing granulator, a color sorter or a specific gravity sorter.
8. The recycling process of waste lithium batteries according to claim 1, wherein the mother liquor of the hydrodynamic sorting system can be reused in the wet stripping system, and can also be added into subsequent pole powder slurry preparation, and the mother liquor after pressure filtration can be used as a supplementary liquor of the hydrodynamic sorting system.
9. The process for recycling spent lithium batteries according to claim 1, wherein the hydrodynamic sorting system can replace a shaker or a jump sorting device.
10. The process for recycling spent lithium batteries according to claim 1, characterized in that wet stripping can replace single plants for soaking, scrubbing, screening and washing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111314639.3A CN113908977A (en) | 2021-11-08 | 2021-11-08 | Recovery process of waste lithium battery |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111314639.3A CN113908977A (en) | 2021-11-08 | 2021-11-08 | Recovery process of waste lithium battery |
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| CN113908977A true CN113908977A (en) | 2022-01-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114381603A (en) * | 2022-01-17 | 2022-04-22 | 湖南江冶机电科技股份有限公司 | Method for fully recycling valuable metal components of waste lithium batteries from anode powder stripped by hydrodynamic sorting wet method |
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- 2021-11-08 CN CN202111314639.3A patent/CN113908977A/en not_active Withdrawn
Patent Citations (9)
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| JP2017174517A (en) * | 2016-03-18 | 2017-09-28 | 三菱マテリアル株式会社 | Method for collecting valuable substance from used lithium ion battery |
| WO2018047147A1 (en) * | 2016-09-12 | 2018-03-15 | Attero Recycling Pvt. Ltd. | Process for recovering pure cobalt and nickel from spent lithium batteries |
| CN108550942A (en) * | 2018-05-21 | 2018-09-18 | 金川集团股份有限公司 | A kind of innoxious recovery and treatment method of waste and old lithium ion battery full constituent |
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| CN209205453U (en) * | 2018-11-08 | 2019-08-06 | 山东锂想新能源科技有限公司 | A kind of retired lithium battery electrification processing equipment for pulverizing |
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Application publication date: 20220111 |