CN209526167U - Waste and old lithium ion battery pyrolysis system - Google Patents
Waste and old lithium ion battery pyrolysis system Download PDFInfo
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- CN209526167U CN209526167U CN201920489414.3U CN201920489414U CN209526167U CN 209526167 U CN209526167 U CN 209526167U CN 201920489414 U CN201920489414 U CN 201920489414U CN 209526167 U CN209526167 U CN 209526167U
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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
- 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 utility model provides a kind of waste and old lithium ion battery pyrolysis system.The system includes cooling device, cutter device, pyrolysis installation, gas supply device, physical absorption device, Alkali absorption device；Cooling device is for cooling down to waste and old lithium ion battery；Cutter device is connected with cooling device, for being cut the waste and old lithium ion battery after cooling with split cell battery core；Pyrolysis installation is connected with cutter device, and for carrying out pyrolytic reaction to battery battery core, pyrolysis installation has solid residue outlet and pyrolysis gas exhaust outlet；Gas supply device is connected with cutter device and pyrolysis installation respectively, is used for the supply of nitrogen inside the two or inert gas；Physical absorption device is connected with pyrolysis gas exhaust outlet, and physical absorption device also has secondary exhaust mouth；Alkali absorption device is connected with secondary exhaust mouth, and the gas for secondary exhaust mouth to be discharged carries out Alkali absorption.The electrolyte in waste and old lithium ion battery more effectively can be subjected to harmless treatment by the system.
Description
Technical field
The utility model relates to waste and old lithium ion battery processing technology fields, in particular to a kind of applying waste lithium ionic
Battery pyrolysis system.
Background technique
Lithium ion battery has many advantages, such as that voltage is high, small in size, specific energy is high, self discharge is small, highly-safe, by widely
Applied to fields such as consumer electronics product, electric vehicle, industrial energy storage.Studies have shown that the charging of lithium ion battery follows
The ring period is about 500 times, and service life is generally 3~5 years, with the quick increasing of lithium ion battery production quantity and usage quantity
Long, the quantity of waste and old lithium ion battery is also more and more huger.
Lithium ion battery is mainly made of anode, cathode, diaphragm, electrolyte and outer packing, both at home and abroad about waste and old lithium from
The technique of sub- battery recycling can be divided into physical separation method, pyrometallurgy and hydrometallurgy, research be concentrated mainly on discharge treatment,
Dismantling process and positive and negative pole material synthetical recovery process.Currently, work is recycled in the processing of waste lithium ion cell anode, negative electrode material
Skill is more perfect, but there is also very big problems for processing for the electrolyte in battery and recycling.
The electrolyte of waste and old lithium ion battery is mainly by organic solvent and electrolyte LiPF6Composition, in the mistake of recovery processing
Electrolyte is volatile in journey, meanwhile, electrolyte contacted with air or calcination process after can also generate toxic VOCs gas
With HF gas.A kind of waste and old lithium ion battery electrolysis is individually disclosed in patent CN104282962A and patent CN104009269A
Electrolyte, is separated and recovered from by the method for liquid recycling by supercentrifugal process from battery under inert gas protection.Patent
A kind of recovery method of waste and old lithium ionic cell electrolyte is disclosed in CN104600392A, by the way that battery battery core is put into centrifugation
Machine separation, obtains waste electrolyte, is filtered, decolourizes, is dehydrated to waste electrolyte, supplements electrolyte and electrolysis is made in organic solvent
Liquid product.Above three patent is all made of the electrolyte in supercentrifugal process processing old and useless battery, needs the electricity in old and useless battery
Qualitative change does not occur for solution liquid, if the organic solvent or electrolyte in electrolyte are degraded, which can not will give up
New electrolysis liquid product is made in electrolyte again.A kind of waste and old lithium ion battery is disclosed in patent CN103943911A to integrate back
The method utilized is received, waste and old lithium ion battery is broken into the sheet of 10~20mm of diameter in closed shear crusher,
It is sprayed when broken, by the LiPF in old and useless battery6It is dissolved into spray liquid.Although spray can effectively adsorb electrolyte
In LiPF6, but the organic solvent in electrolyte can not complete degradation or absorption by spray.
In order to reduce electrolyte pollution on the environment during waste and old lithium ion battery recovery processing, it is necessary to provide
A kind of harmless treatment process of more effectively waste and old lithium ionic cell electrolyte.
Utility model content
The main purpose of the utility model is to provide a kind of waste and old lithium ion battery pyrolysis systems, more have to provide one kind
The harmless treatment process of effect ground waste and old lithium ionic cell electrolyte.
To achieve the goals above, one aspect according to the present utility model provides a kind of waste and old lithium ion battery heat
Solution system comprising: cooling device, for carrying out cooling processing to waste and old lithium ion battery to reduce electrolyte in subsequent handling
In volatilization；Cutter device is connected with cooling device, for being cut the waste and old lithium ion battery after cooling to separate electricity
Pond battery core；Pyrolysis installation is connected with cutter device, and for carrying out pyrolytic reaction to battery battery core, pyrolysis installation is surplus with solid-state
Excess outlet and pyrolysis gas exhaust outlet；Gas supply device is connected with cutter device and pyrolysis installation respectively, is used for the two
Internal the supply of nitrogen or inert gas；Physical absorption device is connected with pyrolysis gas exhaust outlet, for pyrolysis gas exhaust outlet to be discharged
Pyrolysis gas carry out physical absorption, physical absorption device also has secondary exhaust mouth；And Alkali absorption device, with secondary exhaust mouth
It is connected, the gas for secondary exhaust mouth to be discharged carries out Alkali absorption.
Further, cooling device is cryogenic refrigerator.
Further, pyrolysis installation is tubular type pyrolysis oven.
Further, physical absorption device is activated carbon adsorption device.
Further, Alkali absorption device is static akaline liquid absorption plant or spray akaline liquid device.
Further, device further includes electric discharge device, and electric discharge device is connected with cooling device, for before cooling processing
Discharge treatment is carried out to waste and old lithium ion battery.
Further, device further includes crushing device, and crushing device is connected with the solid residue outlet of pyrolysis installation,
Solid residue for solid residue outlet to be discharged carries out break process.
Further, crushing device is ball mill or rod mill.
Further, device further includes preparation equipment, and preparation equipment is connected with crushing device, for broken solid-state
Residue carries out gravity treatment or flotation.
Further, device further includes air extractor, and air extractor is connected with Alkali absorption device, for Alkali absorption device
Carry out vacuumize process.
Waste and old lithium ion battery is handled using above system provided by the utility model, before splitting battery battery core, first
Cooling processing is carried out to waste and old lithium ion battery using cooling device 10, electrolyte activity is can reduce in this way, reduces electrolyte
It volatilizees in split process, avoids atmosphere pollution caused by the volatilization because of the fractionation stage.Under the protection of nitrogen or inert gas,
When battery battery core to be carried out to pyrolytic reaction in pyrolysis installation 30, degradation reaction can occur for electrolyte, generate HF gas and
VOCs gas forms pyrolysis gas with nitrogen or inert gas together.In physical absorption device 50 after physical absorption, pyrolysis
VOCs gas in gas is adsorbed removal, and HF gas is then absorbed removal by Alkali absorption in Alkali absorption device 60.Therefore, lead to
Above system provided by the utility model is crossed, the electrolyte in waste and old lithium ion battery more effectively can be subjected to innoxious place
Reason.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide a further understanding of the present invention, this is practical
Novel illustrative embodiments and their description are not constituteed improper limits to the present invention for explaining the utility model.
In the accompanying drawings:
Fig. 1 shows a kind of structural frames of the waste and old lithium ion battery pyrolysis system of embodiment according to the present utility model
Figure；And the positive and negative anodes powder handled Fig. 2 shows waste and old lithium ion battery method for pyrolysis according to the present utility model
Stereoscan photograph.
Wherein, the above drawings include the following reference numerals:
10, cooling device；20, cutter device；30, pyrolysis installation；40, gas supply device；50, physical absorption device；
60, Alkali absorption device；70, electric discharge device；80, crushing device；90, preparation equipment；100, air extractor.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.The utility model will be described in detail below with reference to the accompanying drawings and embodiments.
In order to which waste and old lithium ionic cell electrolyte is more effectively carried out harmless treatment, the utility model provides one kind
Waste and old lithium ion battery pyrolysis system, as shown in Figure 1 comprising cooling device 10, cutter device 20, pyrolysis installation 30, gas
Feeding mechanism 40, physical absorption device 50, Alkali absorption device 60；Cooling device 10 is for cooling down to waste and old lithium ion battery
Processing is to reduce volatilization of the electrolyte in subsequent handling；Cutter device 20 is connected with cooling device 10, after to cooling
Waste and old lithium ion battery is cut with split cell battery core；Pyrolysis installation 30 is connected with cutter device 20, for battery electricity
Core carries out pyrolytic reaction, and pyrolysis installation 30 has solid residue outlet and pyrolysis gas exhaust outlet；Gas supply device 40 divides
It is not connected with cutter device 20 and pyrolysis installation 30, is used for the supply of nitrogen inside the two or inert gas；Physical absorption device
50 are connected with pyrolysis gas exhaust outlet, and the pyrolysis gas for pyrolysis gas exhaust outlet to be discharged carries out physical absorption, physical absorption device
50 also have secondary exhaust mouth；Alkali absorption device 60 is connected with secondary exhaust mouth, the gas for secondary exhaust mouth to be discharged into
Row Alkali absorption.
Waste and old lithium ion battery is handled using above system provided by the utility model, before splitting battery battery core, first
Cooling processing is carried out to waste and old lithium ion battery using cooling device 10, electrolyte activity is can reduce in this way, reduces electrolyte
It volatilizees in split process, avoids atmosphere pollution caused by the volatilization because of the fractionation stage.Under the protection of nitrogen or inert gas,
When battery battery core to be carried out to pyrolytic reaction in pyrolysis installation 30, degradation reaction can occur for electrolyte, generate HF gas and
VOCs gas forms pyrolysis gas with nitrogen or inert gas together.In physical absorption device 50 after physical absorption, pyrolysis
VOCs gas in gas is adsorbed removal, and HF gas is then absorbed removal by Alkali absorption in Alkali absorption device 60.Therefore, lead to
Above system provided by the utility model is crossed, the electrolyte in waste and old lithium ion battery more effectively can be subjected to innoxious place
Reason.
In a preferred embodiment, cooling device 10 is cryogenic refrigerator.The equipment that above-mentioned pyrolytic reaction uses can
To be conventional pyrolysis plant, in a preferred embodiment, pyrolysis installation 30 is tubular type pyrolysis oven.
In a preferred embodiment, physical absorption device 50 is activated carbon adsorption device.Activated carbon adsorption device
Middle to use active carbon as adsorbent, large specific surface area, absorption property is preferable, can more fully adsorb in pyrolysis gas
VOCs gas.
The purpose of above-mentioned Alkali absorption device is that the pyrolysis gas and lye after making absorption absorb, so that HF gas therein and alkali
Liquid reaction.In a preferred embodiment, Alkali absorption device 60 is static akaline liquid absorption plant or spray alkalies
Body device.In this way, in specific implementation procedure, the pyrolysis gas after absorption can be passed directly into lye with alkaline reaction,
It with the pyrolysis gases contact after absorption and can be reacted by the way of lye spray.
In actual operation, physical absorption device 50 and Alkali absorption device 60 should increase as far as possible the same adsorbent of gas,
The contact area of lye is conducive to the adsorption treatment of VOCs gas and HF gas.
In order to improve operational safety, in a preferred embodiment, device further includes electric discharge device 70, electric discharge dress
It sets 70 to be connected with cooling device 10, for carrying out discharge treatment to waste and old lithium ion battery before cooling processing.Above-mentioned electric discharge
Treatment process uses the usual means of this field.
After battery battery core carries out pyrolytic reaction, other than electrolyte can degrade, anode and negative electrode material can also be sent out
Raw reaction, specific as follows: the negative electrode material carbon in battery battery core can be with positive electrode LiNi1-x-yCoxMnyO2React generation
Positive and negative anodes pyrogen, main component C, CoO, MnO, NiO, Li2CO3And Ni.Other than positive and negative anodes powder, after pyrolysis
Also containing Cu, Al piece etc. in positive/negative plate in solid residue.In a preferred embodiment, device further includes being crushed
Device 80, crushing device 80 are connected with the solid residue outlet of pyrolysis installation 30, for arranging solid residue outlet
Solid residue out carries out break process.It is highly preferred that above-mentioned apparatus further includes preparation equipment 90, preparation equipment 90 and broken
Device 80 is connected, for carrying out gravity treatment or flotation to broken solid residue.Solid-state can be remained using preparation equipment 90
Metallic copper, metallic aluminium and positive and negative anodes powder in excess are separated.Preferably, above-mentioned apparatus further includes wet metallurgy device,
For extracting the valuable metals elements such as metal Li, Ni, Co and Mn in positive and negative anodes powder.
In order to improve crushing efficiency, in a preferred embodiment, crushing device 80 includes but is not limited to ball mill
Or rod mill.
In a preferred embodiment, device further includes air extractor 100, air extractor 100 and Alkali absorption device
60 are connected, for carrying out vacuumize process to Alkali absorption device 60.Air extractor can accelerate the flow velocity of gas in the paths, improve
Treatment effeciency, air extractor can be using common types such as vacuum pumps.
Another aspect according to the present utility model additionally provides a kind of waste and old lithium ion battery method for pyrolysis, this method packet
Include following steps: waste and old lithium ion battery is carried out cooling processing by step S1；Step S2, in the protection of nitrogen or inert gas
Under, the outer packaging shell of the waste and old lithium ion battery after removal cooling obtains battery battery core；Step S3, in nitrogen or indifferent gas
Under the protection of body, battery battery core is subjected to pyrolytic reaction, obtains solid residue and pyrolysis gas；Step S4, successively to pyrolysis gas
Carry out physical absorption, Alkali absorption.
Before splitting battery battery core, cooling processing first is carried out to waste and old lithium ion battery, can reduce electrolyte in this way
Activity reduces electrolyte and volatilizees in split process, avoids atmosphere pollution caused by the volatilization because of the fractionation stage.In nitrogen or lazy
Property gas protection under when battery battery core is carried out pyrolytic reaction, degradation reaction can occur for electrolyte, generate HF gas and
VOCs gas forms pyrolysis gas with nitrogen or inert gas together.In the VOCs gas quilt after physical absorption, in pyrolysis gas
Adsorption, HF gas are then absorbed removal during Alkali absorption.It therefore, can by method provided by the utility model
The electrolyte in waste and old lithium ion battery is more effectively subjected to harmless treatment.
Electrolyte activity is preferably reduced in order to reach, the purpose for inhibiting it to volatilize in split process, a kind of preferred
Embodiment in, in step S1, cooling handle during, cooling temperature be -80~-20 DEG C, temperature fall time be greater than 3h.It adopts
With above-mentioned temperature reduction technology, one side electrolyte activity is lower, not volatile, on the other hand also avoids the energy under lower temperature
Consume.
In a preferred embodiment, in step S3, the condition of pyrolytic reaction is as follows: by battery battery core with 5~20
DEG C/min heating rate is warming up to 500~650 DEG C, keep the temperature 1~6 hour.Under this condition, the cell reaction of electrolyte is more thorough
Bottom.The equipment that above-mentioned pyrolytic reaction uses can be conventional pyrolysis plant, in a preferred embodiment, step S3
In, pyrolytic reaction carries out in tube furnace, and the flow velocity of nitrogen or inert gas in tube furnace is 0.2~2L/min.By nitrogen
Or the flow control of inert gas is within the above range, is on the one hand conducive to provide inert atmosphere for pyrolytic reaction, on the one hand,
Under the carrying of nitrogen or inert gas is used, the HF gas and VOCs gas that also can more stably generate pyrolytic reaction are conveyed
To subsequent physical absorption and Alkali absorption stage.
In a preferred embodiment, in step S4, physical adsorption process is using active carbon as adsorbent, battery
Battery core and the weight ratio of active carbon are 1:0.2~2.The VOCs gas in pyrolysis gas can be more fully adsorbed in this way.
As long as the lye used during above-mentioned Alkali absorption can be reacted with the HF gas in pyrolysis gas, one
In kind preferred embodiment, in step S4, the lye used during Alkali absorption is Ca (OH)2、NaOH、KOH、NaHCO3With
KHCO3In one or more aqueous solution, concentration is 1~5mol/L preferably in lye.In specific implementation procedure, after absorption
Pyrolysis gas can be passed directly into lye with alkaline reaction, can also be by the way of lye spray by itself and the heat after absorption
It vents one's spleen and contact and reacts.
In order to improve operational safety, in a preferred embodiment, waste and old lithium ion battery is carried out at cooling
Before reason process, step S1 further includes the process that waste and old lithium ion battery is carried out to discharge treatment.Above-mentioned discharge treatment process is adopted
With the common method of this field, in a preferred embodiment, above-mentioned discharge treatment step include: by waste and old lithium from
Sub- battery be placed in neutral or alkalinity supporting electrolyte impregnate 12~for 24 hours.Discharge treatment is more abundant in this way.Preferably, it leads
Electric salting liquid is NaCl aqueous solution or NaHCO3Aqueous solution, the concentration of more preferable supporting electrolyte are 1~5mol/L.
After battery battery core carries out pyrolytic reaction, other than electrolyte can degrade, anode and negative electrode material can also be sent out
Raw reaction, specific as follows: the negative electrode material carbon in battery battery core can be with positive electrode LiNi1-x-yCoxMnyO2React generation
Positive and negative anodes pyrogen, main component C, CoO, MnO, NiO, Li2CO3And Ni.Other than positive and negative anodes powder, after pyrolysis
Also containing Cu, Al piece etc. in positive/negative plate in solid residue.In a preferred embodiment, solid-state residue is being obtained
After object, the above method further include: solid residue is crushed by step S5；Step S6, by broken solid residue into
Row gravity treatment or flotation obtain metallic copper, metallic aluminium and the positive and negative anodes powder (stereoscan photograph of positive and negative anodes powder such as Fig. 2 institute
Show).Ball mill or rod mill can be used in shattering process, revolving speed is preferably 100~300r/min.
For positive and negative anodes powder, can also be extracted using Wet-process metallurgy method commonly used in the art metal Li, Ni therein,
The valuable metals element such as Co and Mn, specific method are known to the skilled in the art, and details are not described herein.
Above-mentioned waste and old lithium ion battery is preferably waste and old ternary lithium ion battery.
The application is described in further detail below in conjunction with specific embodiment, these embodiments should not be understood as limitation originally
Apply for range claimed.
Embodiment 1
Waste and old ternary lithium ion battery is handled using Fig. 1 device:
Waste and old ternary lithium ion battery is put into the NaCl solution of 2mol/L and is discharged for 24 hours, battery taking-up is dried in the air after electric discharge
It is dry.Battery after drying is put into -80 DEG C of cryogenic refrigerators and freezes 3h, reduces its electrolyte activity.Battery after freezing is taken
Out, outside batteries pack case is cut under nitrogen gas protection, takes out battery battery core.300g battery battery core is put into tube furnace
In, 650 DEG C are risen to 10 DEG C/min heating rate under 0.8L/min nitrogen protection atmosphere, naturally cools to room after keeping the temperature 3h
Temperature.Tube furnace gas outlet connects activated carbon adsorption device and Alkali absorption device, quality of activated carbon 100g, fills in Alkali absorption device
Having 2L concentration is the sodium hydroxide solution of 2mol/L.Table 1 is that discharge hole of crusher in reaction process, tube furnace gas outlet and alkali are inhaled
VOCs the and HF gas concentration measured in receiving apparatus.Battery after pyrolysis is taken out, is put into ball mill with 100r/min revolving speed
Ball milling 1h, the material after ball milling pass through the available Cu powder of flotation, Al powder and black powder.Black powder main component be C,
CoO、MnO、NiO、Li2CO3And Ni, excute a law metallurgical extraction metal Li, Ni, Co and Mn can be further used for.
1 tube furnace gas outlet of table and Alkali absorption device testing result
Embodiment 2
Waste and old ternary lithium ion battery is handled using Fig. 1 device:
Waste and old ternary lithium ion battery is put into the NaCl solution of 4mol/L and is discharged for 24 hours, battery taking-up is dried in the air after electric discharge
It is dry.Battery after drying is put into -60 DEG C of cryogenic refrigerators and freezes 8h, reduces its electrolyte activity.Battery after freezing is taken
Out, outside batteries pack case is cut under nitrogen gas protection, takes out battery battery core.300g battery battery core is put into tube furnace
In, 600 DEG C are risen to 5 DEG C/min heating rate under 1L/min nitrogen protection atmosphere, keeps the temperature cooled to room temperature after 5h.Pipe
Formula furnace gas outlet connects activated carbon adsorption device and Alkali absorption device, quality of activated carbon 200g, and 2L is housed in Alkali absorption device
Concentration is the sodium hydroxide solution of 4mol/L.Table 2 is discharge hole of crusher in reaction process, tube furnace gas outlet and Alkali absorption dress
Set VOCs the and HF gas concentration of interior measurement.Battery after pyrolysis is taken out, is put into ball mill with 200r/min revolving speed ball milling
1h, the material after ball milling pass through the available Cu powder of flotation, Al powder and black powder.Black powder main component be C, CoO,
MnO、NiO、Li2CO3And Ni, excute a law metallurgical extraction metal Li, Ni, Co and Mn can be further used for.
2 tube furnace gas outlet of table and Alkali absorption device testing result
Embodiment 3
Waste and old ternary lithium ion battery is handled using Fig. 1 device:
Waste and old ternary lithium ion battery is put into the NaCl solution of 1mol/L and is discharged for 24 hours, battery taking-up is dried in the air after electric discharge
It is dry.Battery after drying is put into -20 DEG C of cryogenic refrigerators and freezes 8h, reduces its electrolyte activity.Battery after freezing is taken
Out, outside batteries pack case is cut under nitrogen gas protection, takes out battery battery core.300g battery battery core is put into tube furnace
In, 650 DEG C are risen to 20 DEG C/min heating rate under 0.2L/min nitrogen protection atmosphere, naturally cools to room after keeping the temperature 1h
Temperature.Tube furnace gas outlet connects activated carbon adsorption device and Alkali absorption device, quality of activated carbon 600g, fills in Alkali absorption device
Having 2L concentration is the NaHCO of 5mol/L3Solution.Table 3 is discharge hole of crusher in reaction process, tube furnace gas outlet and Alkali absorption
VOCs the and HF gas concentration measured in device.Battery after pyrolysis is taken out, is put into ball mill with 200r/min revolving speed ball
1h is ground, the material after ball milling passes through the available Cu powder of flotation, Al powder and black powder.Black powder main component be C, CoO,
MnO、NiO、Li2CO3And Ni, excute a law metallurgical extraction metal Li, Ni, Co and Mn can be further used for.
3 tube furnace gas outlet of table and Alkali absorption device testing result
Embodiment 4
Waste and old ternary lithium ion battery is handled using Fig. 1 device:
Waste and old ternary lithium ion battery is put into the NaCl solution of 5mol/L the 12h that discharges, battery taking-up is dried in the air after electric discharge
It is dry.Battery after drying is put into -60 DEG C of cryogenic refrigerators and freezes 5h, reduces its electrolyte activity.Battery after freezing is taken
Out, outside batteries pack case is cut under nitrogen gas protection, takes out battery battery core.300g battery battery core is put into tube furnace
In, 500 DEG C are risen to 5 DEG C/min heating rate under 2L/min nitrogen protection atmosphere, keeps the temperature cooled to room temperature after 1h.Pipe
Formula furnace gas outlet connects activated carbon adsorption device and Alkali absorption device, quality of activated carbon 60g, dense equipped with 2L in Alkali absorption device
Degree is the Ca (OH) of 1mol/L2Solution.Table 4 is discharge hole of crusher in reaction process, tube furnace gas outlet and Alkali absorption device
VOCs the and HF gas concentration of interior measurement.Battery after pyrolysis is taken out, is put into ball mill with 200r/min revolving speed ball milling 1h,
Material after ball milling passes through the available Cu powder of flotation, Al powder and black powder.Black powder main component be C, CoO, MnO,
NiO、Li2CO3And Ni, excute a law metallurgical extraction metal Li, Ni, Co and Mn can be further used for.
4 tube furnace gas outlet of table and Alkali absorption device testing result
Comparative example 1
Waste and old ternary lithium ion battery is handled using Fig. 1 device:
Waste and old ternary lithium ion battery is put into the NaCl solution of 0.8mol/L the 12h that discharges, takes out battery after electric discharge
It dries.Battery after electric discharge is cut into outside batteries pack case under nitrogen gas protection, takes out battery battery core.By 300g battery
Battery core is put into tube furnace, rises to 480 DEG C under 2L/min nitrogen protection atmosphere with 5 DEG C/min heating rate, keep the temperature after 1h from
So it is cooled to room temperature.Tube furnace gas outlet connects activated carbon adsorption device and Alkali absorption device, quality of activated carbon 50g, and alkali is inhaled
The Ca (OH) for being 1mol/L equipped with 2L concentration in receiving apparatus2Solution.Table 5 is that discharge hole of crusher in reaction process, tube furnace go out
VOCs the and HF gas concentration measured in port and Alkali absorption device.By after pyrolysis battery take out, be put into ball mill with
200r/min revolving speed ball milling 1h, the material after ball milling pass through the available Cu powder of flotation, Al powder and black powder.Black powder master
Wanting ingredient is C, CoO, MnO, NiO, Li2CO3And Ni, excute a law metallurgical extraction metal Li, Ni, Co and Mn can be further used for.
5 tube furnace gas outlet of table and Alkali absorption device testing result
The above descriptions are merely preferred embodiments of the present invention, is not intended to limit the utility model, for this
For the technical staff in field, various modifications and changes may be made to the present invention.It is all in the spirit and principles of the utility model
Within, any modification, equivalent replacement, improvement and so on should be included within the scope of protection of this utility model.
Claims (10)
1. a kind of waste and old lithium ion battery pyrolysis system characterized by comprising
Cooling device (10), for carrying out cooling processing to the waste and old lithium ion battery to reduce electrolyte in subsequent handling
Volatilization；
Cutter device (20) is connected with the cooling device (10), for carrying out to the waste and old lithium ion battery after cooling
Cutting is with split cell battery core；
Pyrolysis installation (30) is connected with the cutter device (20), for carrying out pyrolytic reaction, the heat to the battery battery core
Solving device (30) has solid residue outlet and pyrolysis gas exhaust outlet；
Gas supply device (40) is connected with the cutter device (20) and the pyrolysis installation (30) respectively, is used for the two
Internal the supply of nitrogen or inert gas；
Physical absorption device (50) is connected with the pyrolysis gas exhaust outlet, the pyrolysis for the pyrolysis gas exhaust outlet to be discharged
Gas carries out physical absorption, and the physical absorption device (50) also has secondary exhaust mouth；And
Alkali absorption device (60) is connected with the secondary exhaust mouth, and the gas for the secondary exhaust mouth to be discharged carries out alkali
It absorbs.
2. waste and old lithium ion battery pyrolysis system according to claim 1, which is characterized in that the cooling device (10) is
Cryogenic refrigerator.
3. waste and old lithium ion battery pyrolysis system according to claim 1, which is characterized in that the pyrolysis installation (30) is
Tubular type pyrolysis oven.
4. waste and old lithium ion battery pyrolysis system according to claim 1, which is characterized in that the physical absorption device
It (50) is activated carbon adsorption device.
5. waste and old lithium ion battery pyrolysis system according to claim 1, which is characterized in that the Alkali absorption device (60)
For static akaline liquid absorption plant or spray akaline liquid device.
6. waste and old lithium ion battery pyrolysis system according to any one of claim 1 to 5, which is characterized in that the dress
Setting further includes electric discharge device (70), and the electric discharge device (70) is connected with the cooling device (10), at the cooling
Discharge treatment is carried out to the waste and old lithium ion battery before reason.
7. waste and old lithium ion battery pyrolysis system according to any one of claim 1 to 5, which is characterized in that the dress
Setting further includes crushing device (80), the solid residue outlet of the crushing device (80) and the pyrolysis installation (30)
It is connected, the solid residue for the solid residue outlet to be discharged carries out break process.
8. waste and old lithium ion battery pyrolysis system according to claim 7, which is characterized in that the crushing device (80) is
Ball mill or rod mill.
9. waste and old lithium ion battery pyrolysis system according to claim 7, which is characterized in that described device further includes ore dressing
Equipment (90), the preparation equipment (90) are connected with the crushing device (80), for carrying out to broken solid residue
Gravity treatment or flotation.
10. waste and old lithium ion battery pyrolysis system according to any one of claim 1 to 5, which is characterized in that the dress
Setting further includes air extractor (100), and the air extractor (100) is connected with the Alkali absorption device (60), for the alkali
Absorption plant (60) carries out vacuumize process.
Priority Applications (1)
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