CN110071342A - Waste and old lithium ion battery recovery method and device - Google Patents
Waste and old lithium ion battery recovery method and device Download PDFInfo
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- CN110071342A CN110071342A CN201910290231.3A CN201910290231A CN110071342A CN 110071342 A CN110071342 A CN 110071342A CN 201910290231 A CN201910290231 A CN 201910290231A CN 110071342 A CN110071342 A CN 110071342A
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- lithium ion
- waste
- ion battery
- old lithium
- gas
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- 238000000034 method Methods 0.000 title claims abstract description 117
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 102
- 239000002699 waste material Substances 0.000 title claims abstract description 97
- 238000011084 recovery Methods 0.000 title claims abstract description 21
- 238000010521 absorption reaction Methods 0.000 claims abstract description 106
- 239000007789 gas Substances 0.000 claims abstract description 86
- 230000008569 process Effects 0.000 claims abstract description 78
- 238000000197 pyrolysis Methods 0.000 claims abstract description 66
- 239000003513 alkali Substances 0.000 claims abstract description 59
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000006004 Quartz sand Substances 0.000 claims abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000008246 gaseous mixture Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 239000007787 solid Substances 0.000 claims abstract description 23
- 239000011261 inert gas Substances 0.000 claims abstract description 19
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003546 flue gas Substances 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 39
- 208000028659 discharge Diseases 0.000 claims description 30
- 239000003517 fume Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 24
- 230000007246 mechanism Effects 0.000 claims description 17
- 238000001179 sorption measurement Methods 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 15
- 238000009434 installation Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000007921 spray Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000012492 regenerant Substances 0.000 claims description 9
- 239000011780 sodium chloride Substances 0.000 claims description 8
- 239000003115 supporting electrolyte Substances 0.000 claims description 8
- 238000012546 transfer Methods 0.000 claims description 7
- 239000003463 adsorbent Substances 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 238000005096 rolling process Methods 0.000 claims description 3
- 238000010008 shearing Methods 0.000 claims description 3
- 230000003068 static effect Effects 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims 1
- 238000009938 salting Methods 0.000 claims 1
- 210000000952 spleen Anatomy 0.000 claims 1
- 238000013022 venting Methods 0.000 claims 1
- 239000002341 toxic gas Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 description 17
- 239000000243 solution Substances 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910014336 LiNi1-x-yCoxMnyO2 Inorganic materials 0.000 description 2
- 229910014446 LiNi1−x-yCoxMnyO2 Inorganic materials 0.000 description 2
- 229910014825 LiNi1−x−yCoxMnyO2 Inorganic materials 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002510 pyrogen Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 208000036142 Viral infection Diseases 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
-
- 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 present invention provides a kind of waste and old lithium ion battery recovery method and devices.Method includes the following steps: step S1, carries out break process for the waste and old lithium ion battery for being mixed with quartz sand, obtains mixture；Mixture is carried out pyrolytic reaction, obtains solid residue and pyrolysis gas by step S2 under the protection of nitrogen or inert gas；Step S3 collects the flue gas and pyrolysis gas generated during break process, forms gaseous mixture to be processed；Step S4 successively carries out physical absorption, Alkali absorption to gaseous mixture to be processed.Waste and old lithium ion battery is handled using method provided by the invention, is easy the presence of toxic gas discharge on fire, treatment process when can effectively solve the problem that broken worn-out lithium ion battery, keeps the processing of battery more safe and simple, green.
Description
Technical field
The present invention relates to waste and old lithium ion battery processing technology fields, in particular to a kind of waste and old lithium ion battery
Recovery method and device.
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.Although currently, the comprehensive recovering process type of waste and old lithium ion battery compared with
More, but still there are some problems, especially following two problem: one, waste and old lithium ion battery is easy hair during particle
Raw phenomenon on fire.During actual industrial production, the waste and old lithium ion battery after discharge treatment still may have micro electricity
Pressure (is less than 0.1V), can release big calorimetric after positive and negative anodes shorted contacts in shattering process, cause battery particle in shattering process
Phenomenon on fire occurs.In addition to this, casing of lithium ion battery and crusher metal parts occur to rub in shattering process and also can
Spark is generated, micro spark can light the plastic diaphragms in lithium ion battery, and (diaphragm ingredient is polypropylene (PP) or polyethylene
(PE)), and then phenomenon on fire is generated.Two, the electrolyte in waste and old lithium ion battery can volatilize and decompose, and it is virose to generate tool
Volatilize organic gas (VOCs) and HF gas.
Battery is crushed under nitrogen protection atmosphere using mechanical system by patent CN104009269A selection, is crushed
Nitrogen can prevent the generation of phenomenon on fire in journey, but can not prevent the volatilization and decomposition of electrolyte, be mixed in nitrogen
Toxic gas is not handled well.Patent CN103943911A first carries out discharge treatment to waste and old lithium ion battery,
Then spray means of arranging in pairs or groups in closed shear crusher are crushed.Although spray can be effectively prevented phenomenon on fire
Generation, but crushing device equipment can be caused to corrode after spray liquid absorption lithium hexafluoro phosphate, and later separation spray liquid and broken
The problems such as cumbersome there are technique when broken battery.A kind of highly pressurised liquid diced system is disclosed in patent CN105390764A, i.e., in height
Broken cutting process is carried out to waste and old lithium ion battery under press liquid environment, need to arrange in pairs or groups waste liquid recovery apparatus, and highly pressurised liquid without
Method is reused.
Based on the above reasons, it is necessary to a kind of more effective waste and old lithium ion battery recovery process is provided, preferably to solve
Certainly it is easy the presence of toxic gas discharge on fire, treatment process in prior art in broken worn-out lithium ion battery.
Summary of the invention
The main purpose of the present invention is to provide a kind of waste and old lithium ion battery recovery method and devices, to solve existing work
It is easy the presence of toxic gas discharge on fire, treatment process in skill in broken worn-out lithium ion battery.
To achieve the goals above, according to an aspect of the invention, there is provided a kind of waste and old lithium ion battery recycling side
Method comprising following steps: the waste and old lithium ion battery for being mixed with quartz sand is carried out break process, obtains mixture by step S1；
Mixture is carried out pyrolytic reaction, obtains solid residue and pyrolysis gas by step S2 under the protection of nitrogen or inert gas；
Step S3 collects the flue gas and pyrolysis gas generated during break process, forms gaseous mixture to be processed；Step S4, is successively treated
It handles gaseous mixture and carries out physical absorption, Alkali absorption.
Further, in step S2, the condition of pyrolytic reaction is as follows: mixture is protected under the conditions of 500~650 DEG C of temperature
Temperature 1~6 hour.
Further, in step S2, pyrolytic reaction carries out in tube furnace, the stream of nitrogen or inert gas in tube furnace
Speed is 0.2~2L/min.
Further, in step S1, the weight ratio of waste and old lithium ion battery and quartz sand is 1:1~10.
Further, in step S4, physical adsorption process is using active carbon as adsorbent, waste and old lithium ion battery and work
Property charcoal weight ratio be 1:0.2~2.
Further, 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.
Further, during Alkali absorption, the gaseous mixture to be processed after physical absorption is passed through in lye, alternatively, will
Lye is contacted in a manner of spraying with the gaseous mixture to be processed after physical absorption.
Further, by before carrying out break process, step S1 further includes that waste and old lithium ion battery is carried out discharge treatment
Process.
Further, discharge treatment step includes: that waste and old lithium ion battery is placed in neutral or alkalinity supporting electrolyte
It is middle impregnate 12~for 24 hours；Preferably, supporting electrolyte is NaCl aqueous solution or NaHCO3Aqueous solution, more preferable supporting electrolyte
Concentration is 1~5mol/L.
Further, after obtaining solid residue, method further include: step S5 carries out solid residue at gravity treatment
Reason, obtains quartz sand regenerant, metallic copper, metallic aluminium and positive and negative anodes powder；Preferably, by quartz sand regenerant return step S1
In recycle.
According to another aspect of the present invention, a kind of waste and old lithium ion battery recyclable device is additionally provided comprising: quartz sand
Feeding mechanism, for supplying quartz sand；Waste and old lithium ion battery feeding mechanism, for supplying waste and old lithium ion battery；Broken dress
Set, be connected with quartz sand feeding mechanism and waste and old lithium ion battery feeding mechanism, for will be mixed with the waste and old lithium of quartz sand from
Sub- battery carries out break process to obtain mixture；Pyrolysis installation is connected with crushing device, anti-for be pyrolyzed to mixture
It answers, pyrolysis installation has solid residue outlet and pyrolysis gas exhaust outlet；Gas supply device is connected with pyrolysis installation, uses
The supply of nitrogen or inert gas inside Yu Xiangqi；Physical absorption device is connected with pyrolysis gas exhaust outlet and crushing device, is used for
Physical absorption, physical absorption are carried out to the gaseous mixture of the flue gas generated in the pyrolysis gas and crushing device of the discharge of pyrolysis gas exhaust outlet
Device also has secondary exhaust mouth；And Alkali absorption device, it is connected with secondary exhaust mouth, the gas for secondary exhaust mouth to be discharged
Body carries out Alkali absorption.
Further, crushing device is shearing or oppositely rolling roller crusher.
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 arranged in series in waste and old lithium ion battery feeding mechanism
Between crushing device, for carrying out discharge treatment to waste and old lithium ion battery before break process.
Further, device further includes exhaust fume collecting hood, and exhaust fume collecting hood is arranged in above the feed opening and discharge port of crushing device, and
It is connected with physical absorption device by gas transfer pipeline, and pyrolysis gas exhaust outlet is connected with gas transfer pipeline.
Further, device further includes gravitational separation equipment, and gravitational separation equipment is connected with solid residue outlet, for solid-state
The solid residue of residue outlet discharge carries out re-selection process to obtain quartz sand regenerant, metallic copper, metallic aluminium and just
Cathode powder.
Further, gravitational separation equipment is chute, shaking table or jigging machine.
Further, device further includes air extractor, and air extractor is connected with Alkali absorption device, for Alkali absorption device
Carry out vacuumize process.
The present invention provides a kind of waste and old lithium ion battery recovery methods comprising following steps: step S1 will be mixed with stone
The waste and old lithium ion battery of sand carries out break process, obtains mixture；Step S2, under the protection of nitrogen or inert gas,
Mixture is subjected to pyrolytic reaction, obtains solid residue and pyrolysis gas；Step S3 collects the cigarette generated during break process
Gas and pyrolysis gas form gaseous mixture to be processed；Step S4 successively carries out physical absorption, Alkali absorption to gaseous mixture to be processed.
Using the above method, quartz sand is subjected to break process together with waste and old lithium ion battery, can be effectively prevent brokenly
Problem on fire during broken.Compared to being crushed under nitrogen protection or in the case where water spray soaks state, joined using quartz sand
Be crushed simpler convenience.In addition to this, quartz sand will not impact subsequent pyrolytic process, and it is remaining to enter solid-state
It also can be easily separated after object.When mixture being carried out pyrolytic reaction under the protection of nitrogen or inert gas, electrolyte can occur
Degradation reaction generates HF gas and VOCs gas, forms pyrolysis gas together with nitrogen or inert gas.Collect break process process
It, will be to be processed after the flue gas (wherein also containing because of the HF gas and VOCs gas for decompositing and that volatilizees in shattering process) of middle generation
Gaseous mixture successively carries out physical absorption and Alkali absorption.After physical absorption, the VOCs gas in gas is adsorbed removal, HF
Gas is then absorbed removal during Alkali absorption.
In short, using method provided by the invention handle waste and old lithium ion battery, can effectively solve the problem that broken worn-out lithium from
Be easy the presence of toxic gas discharge on fire, treatment process when sub- battery, make the processing of battery it is more safe and simple,
Green.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present invention, and of the invention shows
Examples and descriptions thereof are used to explain the present invention for meaning property, does not constitute improper limitations of the present invention.In the accompanying drawings:
Fig. 1 shows waste and old lithium ion battery recovery method flow diagram according to an embodiment of the present；
Fig. 2 shows the structural block diagrams of waste and old lithium ion battery recyclable device according to an embodiment of the present.
Wherein, the above drawings include the following reference numerals:
10, quartz sand feeding mechanism；20, waste and old lithium ion battery feeding mechanism；30, crushing device；40, pyrolysis installation；
50, gas supply device；60, physical absorption device；70, Alkali absorption device；80, electric discharge device；90, exhaust fume collecting hood；100, gravity treatment
Equipment；110, 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 present invention will be described in detail below with reference to the accompanying drawings and embodiments.
As described in background technology part, for the prior art when handling waste and old lithium ion battery, there are broken worn-outs
It is easy the presence of toxic gas discharge on fire, treatment process when lithium ion battery.
To solve the above-mentioned problems, the present invention provides a kind of waste and old lithium ion battery recovery methods, as shown in Figure 1, should
The waste and old lithium ion battery for being mixed with quartz sand is carried out break process, obtains mixture by method the following steps are included: step S1；
Mixture is carried out pyrolytic reaction, obtains solid residue and pyrolysis gas by step S2 under the protection of nitrogen or inert gas；
Step S3 collects the flue gas and pyrolysis gas generated during break process, forms gaseous mixture to be processed；Step S4, is successively treated
It handles gaseous mixture and carries out physical absorption, Alkali absorption.
Using the above method, quartz sand is subjected to break process together with waste and old lithium ion battery, can be effectively prevent brokenly
Problem on fire during broken.Compared to being crushed under nitrogen protection or in the case where water spray soaks state, joined using quartz sand
Be crushed simpler convenience.In addition to this, quartz sand will not impact subsequent pyrolytic process, and it is remaining to enter solid-state
It also can be easily separated after object.When mixture being carried out pyrolytic reaction under the protection of nitrogen or inert gas, electrolyte can occur
Degradation reaction generates HF gas and VOCs gas, forms pyrolysis gas together with nitrogen or inert gas.Collect break process process
It, will be to be processed after the flue gas (wherein also containing because of the HF gas and VOCs gas for decompositing and that volatilizees in shattering process) of middle generation
Gaseous mixture successively carries out physical absorption and Alkali absorption.After physical absorption, the VOCs gas in gas is adsorbed removal, HF
Gas is then absorbed removal during Alkali absorption.
In short, using method provided by the invention handle waste and old lithium ion battery, can effectively solve the problem that broken worn-out lithium from
Be easy the presence of toxic gas discharge on fire, treatment process when sub- battery, make the processing of battery it is more safe and simple,
Green.
In a preferred embodiment, in step S2, the condition of pyrolytic reaction is as follows: by mixture 500~650
1~6 hour is kept the temperature under the conditions of DEG C temperature.Under this condition, the cell reaction of electrolyte is more thorough.Above-mentioned pyrolytic reaction uses
Equipment can be conventional pyrolysis plant, in a preferred embodiment, in step S2, pyrolytic reaction is in tube furnace
It carries out, the flow velocity of nitrogen or inert gas in tube furnace is 0.2~2L/min.The flow control of nitrogen or inert gas is existed
In above range, be on the one hand conducive to provide inert atmosphere for pyrolytic reaction, on the one hand, in the carrying institute of nitrogen or inert gas
Under, also HF gas and VOCs gas that pyrolytic reaction generates more stably can be delivered to subsequent physical absorption and alkali is inhaled
The receipts stage.
It is on fire in shattering process in order to more efficiently prevent from, it is in a preferred embodiment, waste and old in step S1
The weight ratio of lithium ion battery and quartz sand is 1:1~10.
In a preferred embodiment, in step S4, physical adsorption process uses active carbon as adsorbent, waste and old
The weight ratio of lithium ion battery and active carbon is 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 i.e. with the HF gas in gaseous mixture to be processed
Can, in a preferred embodiment, in step S4, the lye used during Alkali absorption is Ca (OH)2、NaOH、KOH、
NaHCO3And KHCO3In one or more aqueous solution, concentration is 1~5mol/L preferably in lye.In specific implementation procedure
In, during above-mentioned Alkali absorption, the gaseous mixture to be processed after physical absorption can be passed through in lye and be absorbed, it can also be with
Lye is contacted in a manner of spraying with the gaseous mixture to be processed after physical absorption to absorb.
In order to improve operational safety, in a preferred embodiment, by before carrying out break process, step S1 is also
Process including waste and old lithium ion battery to be carried out to discharge treatment.Above-mentioned discharge treatment process is using the common method of this field
Can, in a preferred embodiment, above-mentioned discharge treatment step includes: that waste and old lithium ion battery is placed in neutral or alkalinity
Supporting electrolyte in impregnate 12~for 24 hours；Preferably, supporting electrolyte is NaCl aqueous solution or NaHCO3Aqueous solution, more preferably
The concentration of supporting electrolyte is 1~5mol/L.
Battery battery core in mixture is positive and negative other than electrolyte can degrade after pyrolytic reaction
Pole material can also react, specific as follows: the negative electrode material carbon in battery battery core can be with positive electrode LiNi1-x-yCoxMnyO2
It reacts and generates positive and negative anodes pyrogen, main component C, CoO, MnO, NiO, Li2CO3And Ni.In addition to positive and negative anodes powder with
Outside, also containing Cu, Al piece etc. in positive/negative plate in the solid residue after pyrolysis.In a preferred embodiment, exist
After obtaining solid residue, method further include: solid residue is carried out re-selection process by step S5, obtain quartz sand regenerant,
Metallic copper, metallic aluminium and positive and negative anodes powder.It is highly preferred that can will be recycled in quartz sand regenerant return step S1.
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.
According to another aspect of the present invention, a kind of waste and old lithium ion battery recyclable device is additionally provided, as shown in Fig. 2, its
Including quartz sand feeding mechanism 10, waste and old lithium ion battery feeding mechanism 20, crushing device 30, pyrolysis installation 40, gas supply
Device 50, physical absorption device 60 and Alkali absorption device 70, quartz sand feeding mechanism 10 is for supplying quartz sand；Applying waste lithium ionic
Battery supplied device 20 is for supplying waste and old lithium ion battery；Crushing device 30 and quartz sand feeding mechanism 10 and applying waste lithium ionic
Battery supplied device 20 is connected, for the waste and old lithium ion battery for being mixed with quartz sand to be carried out break process to be mixed
Object；Pyrolysis installation 40 is connected with crushing device 30, and for carrying out pyrolytic reaction to mixture, pyrolysis installation 40 has solid-state remaining
Object outlet and pyrolysis gas exhaust outlet；Gas supply device 50 is connected with pyrolysis installation 40, for its internal the supply of nitrogen or
Inert gas；Physical absorption device 60 is connected with pyrolysis gas exhaust outlet and crushing device 30, for arranging pyrolysis gas exhaust outlet
The gaseous mixture of the flue gas generated in pyrolysis gas and crushing device 30 out carries out physical absorption, and physical absorption device 60 also has two
Secondary exhaust outlet；Alkali absorption device 70 is connected with secondary exhaust mouth, and the gas for secondary exhaust mouth to be discharged carries out Alkali absorption.
Using above-mentioned apparatus, quartz sand is subjected to break process together with waste and old lithium ion battery, can be effectively prevent brokenly
Problem on fire during broken.Compared to being crushed under nitrogen protection or in the case where water spray soaks state, joined using quartz sand
Be crushed simpler convenience.In addition to this, quartz sand will not impact subsequent pyrolytic process, and it is remaining to enter solid-state
It also can be easily separated after object.When mixture being carried out pyrolytic reaction under the protection of nitrogen or inert gas, electrolyte can occur
Degradation reaction generates HF gas and VOCs gas, forms pyrolysis gas together with nitrogen or inert gas.Collect break process process
It, will be to be processed after the flue gas (wherein also containing because of the HF gas and VOCs gas for decompositing and that volatilizees in shattering process) of middle generation
Gaseous mixture successively carries out physical absorption and Alkali absorption.After physical absorption, the VOCs gas in gas is adsorbed removal, HF
Gas is then absorbed removal during Alkali absorption.
Above-mentioned crushing device 30 can use type commonly used in the art, it is preferable that crushing device 30 is shearing or right
Kibbler roll.
In a preferred embodiment, pyrolysis installation 40 is tubular type pyrolysis oven.The temperature control of tubular type pyrolysis oven is more preferable,
It can provide temperature stable reaction environment for pyrolytic reaction.
In a preferred embodiment, above-mentioned physical absorption device 60 is activated carbon adsorption device.Activated carbon adsorption
Using active carbon as adsorbent in device, 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 70 is that the gaseous mixture to be processed and lye after making absorption absorb, so that HF therein
Gas and alkaline reaction.In a preferred embodiment, above-mentioned Alkali absorption device 70 is static akaline liquid absorption plant
Or spray akaline liquid device.In this way, the gaseous mixture to be processed after absorption can be passed directly into alkali in specific implementation procedure
With alkaline reaction in liquid, it can also be contacted and be reacted with the gaseous mixture to be processed after absorption by the way of lye spray.
In actual operation, physical absorption device 60 and Alkali absorption device 70 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, above-mentioned apparatus further includes electric discharge device 80, is put
Electric installation 80 is arranged in series between waste and old lithium ion battery feeding mechanism 20 and crushing device 30, for before break process
Discharge treatment is carried out to waste and old lithium ion battery.Above-mentioned discharge treatment process uses the usual means of this field.
In a preferred embodiment, above-mentioned apparatus further includes exhaust fume collecting hood 90, and exhaust fume collecting hood 90 is arranged in crushing device
Above 30 feed opening and discharge port, and it is connected with physical absorption device 60 by gas transfer pipeline, and pyrolysis gas exhaust outlet
It is connected with gas transfer pipeline.The fume collection that can will be generated in shattering process using exhaust fume collecting hood 90, then passes through gas
The pyrolysis gas generated during flue gas and pyrolytic reaction is mixed and is delivered in physical absorption device 60 together by body transfer pipeline
It is handled.
After battery battery core in mixture carries out pyrolytic reaction, other than electrolyte can degrade, anode and cathode
Material can also react, specific as follows: the negative electrode material carbon in battery battery core can be with positive electrode LiNi1-x-yCoxMnyO2Hair
Raw reaction generates positive and negative anodes pyrogen, main component C, CoO, MnO, NiO, Li2CO3And Ni.In addition to positive and negative anodes powder with
Outside, also containing Cu, Al piece etc. in positive/negative plate in the solid residue after pyrolysis.In a preferred embodiment, it fills
Setting further includes gravitational separation equipment 100, and gravitational separation equipment 100 is connected with solid residue outlet, for solid residue outlet
The solid residue of discharge carries out re-selection process to obtain quartz sand regenerant, metallic copper, metallic aluminium and positive and negative anodes powder.
Above-mentioned gravitational separation equipment 100 can use type commonly used in the art, such as chute, shaking table or jigging machine.
In a preferred embodiment, above-mentioned apparatus further includes air extractor 110, air extractor 110 and Alkali absorption
Device 70 is connected, for carrying out vacuumize process to Alkali absorption device 70.Air extractor can accelerate the flow velocity of gas in the paths,
Treatment effeciency is improved, air extractor can be using common types such as vacuum pumps.
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
Using the process and the waste and old ternary lithium ion battery of device processing in Fig. 1 and 2:
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 and quartz sand are mixed according to mass ratio 1:10 and are sent into oppositely rolling roller crusher, it is broken to obtain mixed material,
And shattering process does not occur spark.The inlet port and outlet port of crusher are all connected with exhaust fume collecting hood, and exhaust fume collecting hood is connected into active carbon suction
Adsorption device and Alkali absorption device.By 11kg mixed material be sent into pyrolysis oven in, under 1L/min nitrogen protection atmosphere with 10 DEG C/
Min heating rate rises to 650 DEG C, keeps the temperature cooled to room temperature after 2h.Pyrolysis oven gas outlet is connected by exhaust fume collecting hood export pipeline
Connect activated carbon adsorption device and Alkali absorption device, quality of activated carbon 1kg, the hydrogen for being 2mol/L equipped with concentration in Alkali absorption device
Sodium hydroxide solution.The obtained material of pyrolysis is sent into shaking table and carries out Gravity separation, finally obtains quartz sand, copper powder, aluminium powder and black
Color powder.Quartz sand can be repeated for mixing shattering process, and black powder can be used for wet underwater welding valuable metal Ni, Co, Mn, Li
Deng.
Absorption detecting result:
1 tube furnace gas outlet of table and Alkali absorption device testing result
Embodiment 2
Using the process and the waste and old ternary lithium ion battery of device processing in Fig. 1 and 2:
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 and quartz sand are mixed according to mass ratio 1:5 and are sent into shear crusher, it is broken to obtain mixed material,
And shattering process does not occur spark.The inlet port and outlet port of crusher are all connected with exhaust fume collecting hood, and exhaust fume collecting hood is connected into active carbon suction
Adsorption device and Alkali absorption device.By 12kg mixed material be sent into pyrolysis oven in, under 1.5L/min nitrogen protection atmosphere with 5 DEG C/
Min heating rate rises to 650 DEG C, keeps the temperature cooled to room temperature after 2h.Pyrolysis oven gas outlet is connected by exhaust fume collecting hood export pipeline
Connect activated carbon adsorption device and Alkali absorption device, quality of activated carbon 1kg, the hydrogen for being 4mol/L equipped with concentration in Alkali absorption device
Sodium hydroxide solution.The obtained material of pyrolysis is sent into shaking table and carries out Gravity separation, finally obtains quartz sand, copper powder, aluminium powder and black
Color powder.Quartz sand can be repeated for mixing shattering process, and black powder can be used for wet underwater welding valuable metal Ni, Co, Mn, Li
Deng.
Absorption detecting result:
2 tube furnace gas outlet of table and Alkali absorption device testing result
Embodiment 3
Using the process and the waste and old ternary lithium ion battery of device processing in Fig. 1 and 2:
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 and quartz sand are mixed according to mass ratio 1:5 and are sent into shear crusher, it is broken to obtain mixed material,
And shattering process does not occur spark.The inlet port and outlet port of crusher are all connected with exhaust fume collecting hood, and exhaust fume collecting hood is connected into active carbon suction
Adsorption device and Alkali absorption device.By 12kg mixed material be sent into pyrolysis oven in, under 0.2L/min nitrogen protection atmosphere with 5 DEG C/
Min heating rate rises to 500 DEG C, keeps the temperature cooled to room temperature after 6h.Pyrolysis oven gas outlet is connected by exhaust fume collecting hood export pipeline
Connect activated carbon adsorption device and Alkali absorption device, quality of activated carbon 0.4kg equipped with concentration is 5mol/L's in Alkali absorption device
Sodium hydroxide solution.The obtained material of pyrolysis is sent into shaking table and carries out Gravity separation, finally obtain quartz sand, copper powder, aluminium powder and
Black powder.Quartz sand can be repeated for mixing shattering process, black powder can be used for wet underwater welding valuable metal Ni, Co, Mn,
Li et al..
Absorption detecting result:
3 tube furnace gas outlet of table and Alkali absorption device testing result
Embodiment 4
Using the process and the waste and old ternary lithium ion battery of device processing in Fig. 1 and 2:
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 and quartz sand are mixed according to mass ratio 1:1 and are sent into shear crusher, it is broken to obtain mixed material,
And shattering process does not occur spark.The inlet port and outlet port of crusher are all connected with exhaust fume collecting hood, and exhaust fume collecting hood is connected into active carbon suction
Adsorption device and Alkali absorption device.By 4kg mixed material be sent into pyrolysis oven in, under 0.2L/min nitrogen protection atmosphere with 5 DEG C/
Min heating rate rises to 600 DEG C, keeps the temperature cooled to room temperature after 3h.Pyrolysis oven gas outlet is connected by exhaust fume collecting hood export pipeline
Connect activated carbon adsorption device and Alkali absorption device, quality of activated carbon 8kg, the hydrogen for being 5mol/L equipped with concentration in Alkali absorption device
Sodium hydroxide solution.The obtained material of pyrolysis is sent into shaking table and carries out Gravity separation, finally obtains quartz sand, copper powder, aluminium powder and black
Color powder.Quartz sand can be repeated for mixing shattering process, and black powder can be used for wet underwater welding valuable metal Ni, Co, Mn, Li
Deng.
Absorption detecting result:
4 tube furnace gas outlet of table and Alkali absorption device testing result
Embodiment 5
Using the process and the waste and old ternary lithium ion battery of device processing in Fig. 1 and 2:
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 and quartz sand are mixed according to mass ratio 1:10 and are sent into shear crusher, it is broken to obtain mixed material,
And shattering process does not occur spark.The inlet port and outlet port of crusher are all connected with exhaust fume collecting hood, and exhaust fume collecting hood is connected into active carbon suction
Adsorption device and Alkali absorption device.11kg mixed material is sent into pyrolysis oven, with 5 DEG C/min under 2L/min nitrogen protection atmosphere
Heating rate rises to 400 DEG C, keeps the temperature cooled to room temperature after 6h.It is lived by the connection of exhaust fume collecting hood export pipeline pyrolysis oven gas outlet
Property charcoal adsorbent equipment and Alkali absorption device, quality of activated carbon 0.2kg, the hydrogen for being 0.8mol/L equipped with concentration in Alkali absorption device
Sodium hydroxide solution.The obtained material of pyrolysis is sent into shaking table and carries out Gravity separation, finally obtains quartz sand, copper powder, aluminium powder and black
Color powder.Quartz sand can be repeated for mixing shattering process, and black powder can be used for wet underwater welding valuable metal Ni, Co, Mn, Li
Deng.
Absorption detecting result:
5 tube furnace gas outlet of table and Alkali absorption device testing result
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (20)
1. a kind of waste and old lithium ion battery recovery method, which comprises the following steps:
The waste and old lithium ion battery for being mixed with quartz sand is carried out break process, obtains mixture by step S1；
Step S2, under the protection of nitrogen or inert gas, by the mixture carry out pyrolytic reaction, obtain solid residue and
Pyrolysis gas；
Step S3 collects the flue gas and the pyrolysis gas generated during the break process, forms gaseous mixture to be processed；
Step S4 successively carries out physical absorption, Alkali absorption to the gaseous mixture to be processed.
2. waste and old lithium ion battery recovery method according to claim 1, which is characterized in that described in the step S2
The condition of pyrolytic reaction is as follows: the mixture is kept the temperature 1~6 hour under the conditions of 500~650 DEG C of temperature.
3. waste and old lithium ion battery recovery method according to claim 2, which is characterized in that described in the step S2
Pyrolytic reaction carries out in tube furnace, and the flow velocity of nitrogen or inert gas in the tube furnace is 0.2~2L/min.
4. waste and old lithium ion battery recovery method according to claim 1, which is characterized in that described in the step S1
The weight ratio of waste and old lithium ion battery and the quartz sand is 1:1~10.
5. waste and old lithium ion battery recovery method according to any one of claim 1 to 4, which is characterized in that the step
In rapid S4, the physical adsorption process is using active carbon as adsorbent, the waste and old lithium ion battery and the active carbon
Weight ratio is 1:0.2~2.
6. waste and old lithium ion battery recovery method according to any one of claim 1 to 4, which is characterized in that the step
In rapid S4, the lye used during the Alkali absorption is Ca (OH)2、NaOH、KOH、NaHCO3And KHCO3In it is one or more
Aqueous solution, concentration is 1~5mol/L in the preferably described lye.
7. waste and old lithium ion battery recovery method according to claim 6, which is characterized in that during the Alkali absorption,
The gaseous mixture to be processed after the physical absorption is passed through in the lye, alternatively, the side by the lye to spray
Formula is contacted with the gaseous mixture to be processed after the physical absorption.
8. waste and old lithium ion battery recovery method according to any one of claim 1 to 4, which is characterized in that will carry out
Before the break process, the step S1 further includes the process that the waste and old lithium ion battery is carried out to discharge treatment.
9. waste and old lithium ion battery recovery method according to claim 8, which is characterized in that the discharge treatment step packet
Include: the waste and old lithium ion battery is placed in neutral or alkalinity supporting electrolyte impregnate 12~for 24 hours；Preferably, described to lead
Electric salting liquid is NaCl aqueous solution or NaHCO3Aqueous solution, the concentration of the more preferable supporting electrolyte are 1~5mol/L.
10. waste and old lithium ion battery recovery method according to any one of claim 1 to 4, which is characterized in that obtaining
After the solid residue, the method also includes:
The solid residue is carried out re-selection process, obtains quartz sand regenerant, metallic copper, metallic aluminium and positive and negative by step S5
Pole powder；
Preferably, the quartz sand regenerant is returned in the step S1 and is recycled.
11. a kind of waste and old lithium ion battery recyclable device characterized by comprising
Quartz sand feeding mechanism (10), for supplying quartz sand；
Waste and old lithium ion battery feeding mechanism (20), for supplying the waste and old lithium ion battery；
Crushing device (30), it is homogeneous with the quartz sand feeding mechanism (10) and the waste and old lithium ion battery feeding mechanism (20)
Even, for the waste and old lithium ion battery for being mixed with the quartz sand to be carried out break process to obtain mixture；
Pyrolysis installation (40) is connected with the crushing device (30), for carrying out pyrolytic reaction, the pyrolysis to the mixture
Device (40) has solid residue outlet and pyrolysis gas exhaust outlet；
Gas supply device (50) is connected with the pyrolysis installation (40), is used for its internal the supply of nitrogen or inert gas；
Physical absorption device (60) is connected with the pyrolysis gas exhaust outlet and the crushing device (30), for the heat
The gaseous mixture of the flue gas generated in the pyrolysis gas and the crushing device (30) of exhaust outlet of venting one's spleen discharge carries out physical absorption, described
Physical absorption device (60) also has secondary exhaust mouth；And
Alkali absorption device (70) is connected with the secondary exhaust mouth, and the gas for the secondary exhaust mouth to be discharged carries out alkali
It absorbs.
12. waste and old lithium ion battery recyclable device according to claim 11, which is characterized in that the crushing device (30)
For shearing or oppositely rolling roller crusher.
13. waste and old lithium ion battery recyclable device according to claim 11, which is characterized in that the pyrolysis installation (40)
For tubular type pyrolysis oven.
14. waste and old lithium ion battery recyclable device according to claim 11, which is characterized in that the physical absorption device
It (60) is activated carbon adsorption device.
15. waste and old lithium ion battery recyclable device according to claim 11, which is characterized in that the Alkali absorption device
It (70) is static akaline liquid absorption plant or spray akaline liquid device.
16. waste and old lithium ion battery recyclable device described in any one of 1 to 15 according to claim 1, which is characterized in that described
Device further includes electric discharge device (80), and the electric discharge device (80) is arranged in series in the waste and old lithium ion battery feeding mechanism
(20) between the crushing device (30), for discharging before the break process the waste and old lithium ion battery
Processing.
17. waste and old lithium ion battery recyclable device described in any one of 1 to 15 according to claim 1, which is characterized in that described
Device further includes exhaust fume collecting hood (90), and the exhaust fume collecting hood (90) is arranged on the feed opening and discharge port of the crushing device (30)
Side, and be connected with the physical absorption device (60) by gas transfer pipeline, and the pyrolysis gas exhaust outlet and the gas
Transfer pipeline is connected.
18. waste and old lithium ion battery recyclable device according to claim 17, which is characterized in that described device further includes weight
Optional equipment (100), the gravitational separation equipment (100) are connected with the solid residue outlet, for the solid residue
The solid residue of outlet discharge carries out re-selection process to obtain quartz sand regenerant, metallic copper, metallic aluminium and positive and negative anodes powder
End.
19. waste and old lithium ion battery recyclable device according to claim 18, which is characterized in that the gravitational separation equipment
It (100) is chute, shaking table or jigging machine.
20. waste and old lithium ion battery recyclable device described in any one of 1 to 15 according to claim 1, which is characterized in that described
Device further includes air extractor (110), and the air extractor (110) is connected with the Alkali absorption device (70), for described
Alkali absorption device (70) carries out vacuumize process.
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| CN113540605A (en) * | 2021-07-16 | 2021-10-22 | 南昌航空大学 | Harmless treatment method for pyrolysis tail gas of retired old lithium battery |
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