CN109852819A - A kind of broken recovery method of the wet type of waste and old lithium ion battery - Google Patents
A kind of broken recovery method of the wet type of waste and old lithium ion battery Download PDFInfo
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- CN109852819A CN109852819A CN201910139011.0A CN201910139011A CN109852819A CN 109852819 A CN109852819 A CN 109852819A CN 201910139011 A CN201910139011 A CN 201910139011A CN 109852819 A CN109852819 A CN 109852819A
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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
Abstract
A kind of wet type of waste and old lithium ion battery disclosed by the invention is crushed recovery method, comprising the following steps: 1. pairs of waste and old lithium ion battery dismantlings carry out discharge treatment at lithium battery monomer；2. pair lithium battery monomer carries out multistage continuous wet type break process；3. pair lithium salt mixture carries out screening process；4. the slurry that pair screening obtains successively carries out concussion processing and centrifuging treatment；5. one side starts the cleaning processing solid mixture, the TDS content of the aqueous mixture is on the other hand detected；6. pair solid mixture carries out drying and processing；7. carrying out sorting process to the solid mixture after drying using magnetic separating mode；8. carrying out sorting process to the surplus solid mixture that sorting obtains using pneumatic separating mode.Overall process of the present invention does not have discharge of wastewater, and exhaust gas can realize qualified discharge.
Description
Technical field
The present invention relates to power batteries to be recycled technical field, in particular to a kind of wet type of waste and old lithium ion battery is broken
Broken recovery method.
Background technique
Lithium ion battery has many advantages, such as high-energy, long-life, low pollution, be widely used in computer, electric bicycle,
The multiple fields such as electric car, national defence.Especially in recent years, with the explosive growth of electric car, the demand of lithium ion battery
Amount and learies are significantly increased.Largely discarded lithium ion battery causes the waste and environmental pollution of energy resource, waste and old lithium
Containing valuable metals such as a large amount of available resources, such as iron, copper, aluminium etc. in ion battery, if these applying waste lithium ionics are electric
Pond recycling is improper, it will causes the very big wasting of resources and environmental pollution.Positive and negative pole material, the electrolyte solution of lithium ion battery
Equal substances still have a significant impact to environmental and human health impacts.Therefore, if waste and old lithium ion battery to be taken to common rubbish
Processing method (including landfill, burning, compost etc.), the metals such as cobalt therein, nickel, lithium, manganese and inorganic, organic compound must
Serious pollution will be caused to big gas and water, soil, there is great harmfulness.If substance in waste and old lithium ion battery into
Heavy metal nickel, cobalt, arsenic pollution can be caused by entering in environment, fluoride pollution, organic pollution, dust and soda acid pollution.Applying waste lithium ionic
The electrolyte and its converted product of battery, such as LiPF6, LiCF3SO3、HF、P2O5Deng, solvent and its decomposition and hydrolysate,
Such as DME, EMC, methanol, formic acid are all poisonous and harmful substances, can cause personal injury, or even dead.
The recycling of waste lithium cell is at the early-stage at present, the dismantling side of existing waste lithium cell in removal process
Method has biggish limitation.The dismantling mode of existing waste lithium cell usually has dismantling and Mechanical Crushing etc. by hand.It tears open by hand
Solve time-consuming, and conventional Mechanical Crushing can generate a large amount of organic exhaust gas and dust, pollute the environment.
Also have in the prior art and case of wet attrition recycling is carried out to waste and old lithium ion battery, such as number of patent application is
201810162520.0 Chinese invention patent application disclosed in a kind of dismantling recovery method of waste lithium cell, it is broken using wet type
Broken recycling can occur hydrolysis to avoid electrolyte and generate the exhaust gas such as hydrogen fluoride, cause atmosphere pollution.The broken recycling of common wet type
Classification grinding mode is mostly used, carries out washing and corresponding to sorting after every grade of crushing, successively removes electrolyte, and gradually use waterpower
Sorting process separates diaphragm, metal material, positive and negative anodes powder.But it can generate in hydraulic separation technology and largely contain
There is the waste water of lithium salts and organic matter, if these waste water are without recycling, it will pollute the environment.
For this purpose, the applicant has carried out beneficial exploration and research, result of the above problems is had found, will be detailed below
The technical solution of introduction generates in this background.
Summary of the invention
Technical problem to be solved by the present invention lies in: a kind of applying waste lithium ionic electricity is provided in view of the deficiencies of the prior art
The wet type in pond is crushed recovery method, and this method avoids while avoiding generating the atmosphere pollutions such as hydrogen fluoride in sorting process
Discharge of wastewater is generated, realizes the cleaning recycling of full constituent.
The technical problems to be solved by the invention can adopt the following technical scheme that realize:
A kind of broken recovery method of the wet type of waste and old lithium ion battery, comprising the following steps:
Step S1 disassembles at lithium battery monomer, and to the lithium battery monomer after dismantling waste and old lithium ion battery and puts
Electric treatment；
Step S2 carries out multistage continuous wet type break process to the lithium battery monomer after discharge treatment, obtains water-soluble
The lithium salt mixture of property；
Step S3 carries out screening process to the lithium salt mixture, obtains slurry and screening object, and the screening object is returned
It returns in the step S2 and carries out multistage continuous wet type break process；
Step S4 successively carries out concussion processing and centrifuging treatment to the slurry that screening obtains, so that the slurry quilt
Separation forms lightweight diaphragm material, aqueous mixture and the solid mixture being made of heavy metal and electrode powder, and to institute
Lightweight diaphragm material is stated to be recycled；
On the one hand step S5 is started the cleaning processing to described by heavy metal and the solid mixture that electrode powder forms,
Generated cleaning solution is delivered in the multistage continuous wet type break process in cleaning treatment, for broken to multistage continuous wet type
Broken processing carries out cooling and electrolyte ingredient hydrolysis；On the other hand the TDS content of the aqueous mixture is detected, and described in judgement
Whether the TDS content of aqueous mixture reaches preset standard, if reaching preset standard, is evaporated to the aqueous mixture
Crystallization treatment, evaporative crystallization processing in generated condensed water be delivered in the cleaning treatment, for the solid mix
Object is cleaned, while being recycled to the mixing lithium salts that evaporative crystallization is handled, will if not up to preset standard
The aqueous mixture is delivered in the multistage continuous wet type break process, for carrying out to multistage continuous wet type break process
Cooling and electrolyte ingredient hydrolysis；
Step S6 carries out drying and processing to the solid mixture after cleaning；
Step S7 carries out sorting process to the solid mixture after drying using magnetic separating mode, obtains ferromagnetism original
Material and surplus solid mixture, and the ferromagnetism raw material obtained to sorting is recycled；
Step S8 carries out sorting process to the obtained surplus solid mixture of sorting using pneumatic separating mode, obtain copper,
The mixture of aluminum metal and positive and negative anodes electrode powder.
In a preferred embodiment of the invention, in the step S1, the lithium battery monomer after described pair of dismantling is adopted
Discharge treatment is carried out with salt water immersion.
In a preferred embodiment of the invention, in the step S2, the multistage continuous wet type break process is adopted
It is realized with continuous multi-stage wet crusher, includes at least one level impact crusher structure in the continuous multi-stage wet crusher.
In a preferred embodiment of the invention, described that the lithium salt mixture is sieved in the step S4
The screening precision for dividing processing is 50 μm~200 μm.
In a preferred embodiment of the invention, in the step S5, the TDS content of the aqueous mixture it is pre-
Bidding standard is greater than 2%.
In a preferred embodiment of the invention, in the step S5, using evaporator to the aqueous mixture
It is evaporated crystallization treatment.
In a preferred embodiment of the invention, in the step S7, using magnetic grader to consolidating after drying
Body mixture carries out sorting process.
In a preferred embodiment of the invention, mixed to remaining solid using pneumatic separator in the step S8
It closes object and carries out sorting process.
Due to using technical solution as above, the beneficial effects of the present invention are:
1, recovery method of the invention recycles lithium in the form of salt-mixture, and the rate of recovery is more than 90%；
2, the present invention realizes diaphragm recycling by centrifuge separation, and the rate of recovery is more than 85%；
3, the present invention is more than using materials, the rate of recovery such as magnetic separation separation iron nickel to the mixed-powder after washing and drying
98%；
4, the present invention obtains copper, aluminium and mixed electrode powder, the rate of recovery of copper aluminium is more than 95% by pneumatic separating；
5, sundries ratio is very low in mixed electrode powder of the invention, efficiently reduces the acid of downstream hydrometallurgical processes
Consumption improves process efficiency；
6, overall process of the present invention does not have discharge of wastewater, and exhaust gas can realize qualified discharge.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is process flow chart of the invention.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Conjunction is specifically illustrating, and the present invention is further explained.
Fig. 1 is participated in, what is provided in figure is a kind of broken recovery method of wet type of waste and old lithium ion battery, including following step
It is rapid:
Step S1 disassembles at lithium battery monomer, and to the lithium battery monomer after dismantling waste and old lithium ion battery and puts
Electric treatment.In the present embodiment, discharge treatment is carried out to the lithium battery monomer after dismantling using salt water immersion process.
Step S2 carries out multistage continuous wet type break process to the lithium battery monomer after discharge treatment, obtains water-soluble
The lithium salt mixture of property.In the present embodiment, the continuous wet type break process of the multistage is realized using continuous multi-stage wet crusher,
It include at least one level impact crusher structure in continuous multi-stage wet crusher.Graded crushing is substituted using continuous multi-stage is broken,
Process flow can be reduced, while reducing the washing dosage in crushing process, it is more environmentally-friendly.
Step S3, to lithium salt mixture obtained in step S2 carry out screening process, obtain slurry and screening object, and by this
A little screening objects, which are back in the step S2, carries out multistage continuous wet type break process.In the present embodiment, the sieve of screening process
Dividing precision is 50 μm~200 μm.In step s3, the solid circulation that cannot be sieved is crushed using screening mode, it is ensured that crush
Thoroughly, so that solid matter is sufficiently mixed with water, the complete hydrolysis of the electrolyte such as lithium hexafluoro phosphate is realized.
Step S4 successively carries out concussion processing and centrifuging treatment to the slurry that screening obtains, so that slurry is separated
Form lightweight diaphragm material, aqueous mixture and the solid mixture being made of heavy metal and electrode powder, and to lightweight every
Membrane material is recycled.In the present embodiment, concussion processing is realized using horizontal oscillator or overturning oscillator, centrifugation point
Supercentrifuge is used from processing, centrifuge speed is 3000rpm~10000rpm.
On the one hand step S5 is started the cleaning processing to by heavy metal and the solid mixture that electrode powder forms, remove
Remaining a small amount of lithium salts on solid mixture, realization soluble salt are completely separated with insoluble solid.Produced by cleaning treatment
Cleaning solution be delivered in the continuous wet type break process of multistage of step S2, for being dropped to multistage continuous wet type break process
Mild electrolyte ingredient hydrolysis.On the other hand the TDS content of aqueous mixture is detected, and judges the TDS content of aqueous mixture
Whether reach preset standard, if reaching preset standard, crystallization treatment is evaporated to aqueous mixture using evaporator, is evaporated
Generated condensed water is delivered in the cleaning treatment in crystallization treatment, for being cleaned to solid mixture, and meanwhile it is right
The mixing lithium salts that evaporative crystallization is handled is recycled, if not up to preset standard, the aqueous mixture is defeated
It send into the continuous wet type break process of multistage of step S2, for carrying out cooling and electrolyte to multistage continuous wet type break process
Ingredient hydrolysis.In the present embodiment, the preset standard of the TDS content of aqueous mixture is greater than 2%.
Step S6 carries out drying and processing to the solid mixture after cleaning.In step S6, dried using baking oven
Dry, drying temperature is 80 DEG C~130 DEG C, drying time 2h.
Step S7 carries out sorting process to the solid mixture after drying using magnetic grader, it is ferromagnetic to obtain iron, nickel etc.
Property raw material and surplus solid mixture, and the ferromagnetism raw material obtained to sorting is recycled.Step S8, using wind-force point
It selects machine to carry out sorting process to the surplus solid mixture that sorting obtains, obtains copper, aluminum metal and positive and negative anodes electrode powder
Mixture.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (8)
1. a kind of wet type of waste and old lithium ion battery is crushed recovery method, which comprises the following steps:
Step S1 disassembles at lithium battery monomer, and to the lithium battery monomer after dismantling waste and old lithium ion battery and carries out at electric discharge
Reason；
Step S2 carries out multistage continuous wet type break process to the lithium battery monomer after discharge treatment, obtains water-soluble
Lithium salt mixture；
Step S3 carries out screening process to the lithium salt mixture, obtains slurry and screening object, and the screening object is returned to institute
It states and carries out multistage continuous wet type break process in step S2；
Step S4 successively carries out concussion processing and centrifuging treatment to the slurry that screening obtains, so that the slurry is separated
Lightweight diaphragm material, aqueous mixture and the solid mixture being made of heavy metal and electrode powder are formed, and to described light
Matter diaphragm material is recycled；
On the one hand step S5 is started the cleaning processing to described by heavy metal and the solid mixture that electrode powder forms, cleaning
Generated cleaning solution is delivered in the multistage continuous wet type break process in processing, for the broken place of multistage continuous wet type
Reason carries out cooling and electrolyte ingredient hydrolysis；On the other hand the TDS content of the aqueous mixture is detected, and judges the water phase
Whether the TDS content of mixture reaches preset standard, if reaching preset standard, is evaporated crystallization to the aqueous mixture
Processing, evaporative crystallization processing in generated condensed water be delivered in the cleaning treatment, for the solid mixture into
Row cleaning, while the mixing lithium salts that evaporative crystallization is handled is recycled, it, will be described if not up to preset standard
Aqueous mixture is delivered in the multistage continuous wet type break process, for cooling down to multistage continuous wet type break process
It is hydrolyzed with electrolyte ingredient；
Step S6 carries out drying and processing to the solid mixture after cleaning；
Step S7, using magnetic separating mode to after drying solid mixture carry out sorting process, obtain ferromagnetism raw material and
Surplus solid mixture, and the ferromagnetism raw material obtained to sorting is recycled；
Step S8 carries out sorting process to the surplus solid mixture that sorting obtains using pneumatic separating mode, obtains copper, aluminium gold
The mixture of category and positive and negative anodes electrode powder.
2. the wet type of waste and old lithium ion battery as described in claim 1 is crushed recovery method, which is characterized in that in the step
In S1, the lithium battery monomer after described pair of dismantling is impregnated using salt water carries out discharge treatment.
3. the wet type of waste and old lithium ion battery as described in claim 1 is crushed recovery method, which is characterized in that in the step
In S2, the multistage continuous wet type break process realizes that the continuous multi-stage wet type is broken using continuous multi-stage wet crusher
It include at least one level impact crusher structure in machine.
4. the wet type of waste and old lithium ion battery as described in claim 1 is crushed recovery method, which is characterized in that in the step
In S4, the screening precision for carrying out screening process to the lithium salt mixture is 50 μm~200 μm.
5. the wet type of waste and old lithium ion battery as described in claim 1 is crushed recovery method, which is characterized in that in the step
In S5, the preset standard of the TDS content of the aqueous mixture is greater than 2%.
6. the wet type of waste and old lithium ion battery as described in claim 1 is crushed recovery method, which is characterized in that in the step
In S5, crystallization treatment is evaporated to the aqueous mixture using evaporator.
7. the wet type of waste and old lithium ion battery as described in claim 1 is crushed recovery method, which is characterized in that in the step
In S7, sorting process is carried out to the solid mixture after drying using magnetic grader.
8. the wet type of waste and old lithium ion battery as described in claim 1 is crushed recovery method, which is characterized in that in the step
In S8, sorting process is carried out to surplus solid mixture using pneumatic separator.
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Cited By (5)
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| CN110734080A (en) * | 2019-12-04 | 2020-01-31 | 青海东台吉乃尔锂资源股份有限公司 | Method for washing lithium carbonate |
| CN110902701A (en) * | 2019-12-04 | 2020-03-24 | 青海东台吉乃尔锂资源股份有限公司 | Device for washing lithium carbonate |
| WO2022032345A1 (en) * | 2020-08-12 | 2022-02-17 | Resource Conservation and Recycling Corporation Pty Ltd | Process for recovering values from batteries |
| CN114082492A (en) * | 2021-11-18 | 2022-02-25 | 北方化学工业股份有限公司 | Particle size control method for firework cotton |
| CN117577991A (en) * | 2024-01-16 | 2024-02-20 | 深圳市杰成镍钴新能源科技有限公司 | Wet recovery method of poor positive electrode material, positive electrode material and lithium iron phosphate battery |
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| CN114082492A (en) * | 2021-11-18 | 2022-02-25 | 北方化学工业股份有限公司 | Particle size control method for firework cotton |
| CN117577991A (en) * | 2024-01-16 | 2024-02-20 | 深圳市杰成镍钴新能源科技有限公司 | Wet recovery method of poor positive electrode material, positive electrode material and lithium iron phosphate battery |
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