CN207398307U - The processing system of waste and old lithium ion battery - Google Patents
The processing system of waste and old lithium ion battery Download PDFInfo
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- CN207398307U CN207398307U CN201721512345.0U CN201721512345U CN207398307U CN 207398307 U CN207398307 U CN 207398307U CN 201721512345 U CN201721512345 U CN 201721512345U CN 207398307 U CN207398307 U CN 207398307U
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The utility model provides a kind of processing system of waste and old lithium ion battery.The system includes breaker, low temperature gasification pyrolysis furnace, burner, smoke eliminator, grinding and sieving device, apparatus for recovering metal, acidleach device and positive electrode material precursor preparation facilities, and breaker is used to crush the battery core of waste and old lithium ion battery；Low temperature gasification pyrolysis furnace is used to crack to obtain cracking gas and solid residue by battery core particle progress low temperature gasification；The air inlet of burner is connected respectively with cracking gas outlet and volatile organic compounds outlet；Smoke eliminator includes purification furnace, milk of lime injection apparatus and deduster；Apparatus for recovering metal, for recycling the iron in sheet metal, aluminium and copper；Acidleach device obtains filtrate for carrying out acidleach to powder；Positive electrode material precursor preparation facilities is used to prepare persursor material using filtrate.The utility model can carry out recycling and harmless treatment to waste and old lithium ion battery, be effective processing system of waste and old lithium ion battery.
Description
Technical field
The utility model is related to solid waste to be recycled field, in particular to a kind of waste and old lithium ion battery
Processing system.
Background technology
Lithium ion battery is a kind of preferably chargeable chemical cell of comprehensive performance, have operating voltage it is high, it is higher than energy,
It has extended cycle life, the advantages that self discharge is small, is widely used in mobile communication, laptop, portable dam, electric vehicle
The fields of grade.Since the consumption of lithium ion battery is very big, environment can be caused seriously to pollute, while waste and old lithium ion battery is especially
It is that will also result in the waste of resource containing resources such as a large amount of iron, aluminium, copper, lithium, graphite in battery core.Therefore, it is necessary to waste and old lithium
Ion battery is recycled.
However, the recycling of the present waste and old lithium ion battery in China is currently in industrialization early period, there are no form complete money
Source, innoxious environmentally protective recovery process.
Utility model content
The main purpose of the utility model is that a kind of processing system of waste and old lithium ion battery is provided, to solve existing skill
Waste and old lithium ion battery recycling in art, the problem of innoxious degree is low.
To achieve these goals, one side according to the present utility model provides a kind of waste and old lithium ion battery
Processing system, including：Breaker, breaker are provided with the outlet of battery core particle and volatile organic compounds outlet, breaker
For the battery core of waste and old lithium ion battery to be crushed to obtain battery core particle and volatile organic compounds；Low temperature gasification pyrolysis furnace is low
Warm cracking furnace is provided with the import of battery core particle, cracking gas outlet and solid residue outlet, the import of battery core particle and battery core
Particle outlet is connected, and low temperature gasification pyrolysis furnace is used to crack to obtain cracking gas by battery core particle progress low temperature gasification and solid is remaining
Object；Burner, burner are provided with air inlet and exhanst gas outlet, and air inlet is exported respectively with cracking gas and volatile organic compounds
Outlet is connected；Smoke eliminator, smoke eliminator include purification furnace, milk of lime injection apparatus and deduster, purification furnace and set
Gas inlet and depickling exhanst gas outlet are equipped with, gas inlet is connected with exhanst gas outlet；Milk of lime injection apparatus is used for purification furnace
Fluorine-containing sour gas is changed into fluorination by middle injection milk of lime the phosphorous sour gas in flue gas is changed into calcium phosphate
Calcium；Deduster is connected with depickling exhanst gas outlet；Grinding and sieving device, grinding and sieving device are provided with solid residue import, gold
Belong to piece outlet and powder outlet, grinding and sieving device is used to obtain powder and sheet metal to solid residue progress grinding and sieving；
Apparatus for recovering metal is connected with sheet metal outlet, for recycling the iron in sheet metal, aluminium and copper；Acidleach device, acidleach device with
Powder outlet is connected, and filtrate is obtained for carrying out acidleach to powder；And positive electrode material precursor preparation facilities, with acidleach device
It is connected, for preparing the persursor material of anode material for lithium-ion batteries using filtrate.
Further, low temperature gasification pyrolysis furnace includes：Housing is provided with the import of battery core particle, cracking gas exports, solid remains
Excess exports and superheated steam import, and housing is used to provide reacting environment for low temperature gasification cracking；Chuck is arranged on the outer of housing
Portion, chuck are provided with heat smoke import, and heat smoke import is carried out for being passed through heat smoke into chuck with being cracked to low temperature gasification
Concurrent heating.
Further, processing system further includes heat smoke feeding mechanism, and heat smoke feeding mechanism is connected with heat smoke import,
The heat smoke generated for the aftercombustion fuel oil into chuck and/or natural gas.
Further, the battery core particle entrance of low temperature gasification pyrolysis furnace is provided with the first sealing, cracks gas outlet
The second sealing is provided with, solid residue exit is provided with the 3rd sealing；Processing system further includes inert gas supply
Device, inert gas feeding mechanism are connected respectively at the first sealing, the second sealing and the 3rd sealing.
Further, burner is waste heat boiler, and burner is additionally provided with steam (vapor) outlet, and processing system further includes height
Frequency heater, the entrance of heating generator are connected with steam (vapor) outlet, and the outlet of heating generator is connected with superheated steam outlet.
Further, smoke eliminator further includes activated carbon injection apparatus, and activated carbon injection apparatus is used for purification furnace
Middle injection activated carbon is with bioxin and peculiar smell in adsorbing and removing flue gas.
Further, deduster is additionally provided with the outlet of dirt slag, and processing system further includes melting furnace, and melting furnace is exported with dirt slag
It is connected, melting harmless treatment is carried out for the dirt slag to dirt slag outlet discharge.
Further, apparatus for recovering metal is concentration equipment, gravity concentration apparatus or pneumatic separation device.
Further, processing system further includes flotation unit, and flotation unit is arranged between powder outlet and acidleach device
Pipeline on, for powder carry out flotation remove carbon.
Further, acidleach device is additionally provided with carbon dust outlet；Processing system further includes melting furnace, and melting furnace is provided with combustion
Expect import, fuel inlet is connected with carbon dust outlet.
Further, positive electrode material precursor preparation facilities includes：First settler, the first settler are provided with filter
Liquid import, compressed air inlet and secondary filtrate (liquid, filtrate import are connected with the filtrate (liquid of acidleach device, the first precipitation dress
It puts to carry out except iron filtrate；Second settler, the second settler be provided with secondary filtrate import, precipitating reagent import and
Persursor material exports, and secondary filtrate import is connected with secondary filtrate (liquid, and the second settler is used for secondary filtrate import
The secondary filtrate of discharge carries out precipitation reaction generation persursor material；And precipitating reagent feeding mechanism, it is connected with precipitating reagent import,
Precipitation reaction is carried out for supplying precipitating reagent into the second settler.
Further, the first settler is additionally provided with scum outlet, and processing system further includes melting furnace, melting furnace and iron
Slag outlet is connected, and melting harmless treatment is carried out for the scum to scum outlet discharge.
Further, processing system further includes electric discharge device, electric discharge device be used for the battery core of waste and old lithium ion battery into
Row discharge treatment, electric discharge device are connected with breaker, for the battery core after discharge treatment to be delivered in breaker.
Using the technical solution of the utility model, a kind of processing system of waste and old lithium ion battery is provided.Utilize this reality
With the above-mentioned processing system of new offer, some volatile organic compounds can be generated when being crushed using breaker to battery core, it will
Battery core particle carries out low temperature gasification cracking in low temperature gasification pyrolysis furnace organic matter therein can occur cracking gasification reaction,
Generate cracking gas (mainly some cracking paraffin gas and olefin gas) and solid residue (predominantly positive electrode, graphite
Powder and metal) so that the organic matter in waste and old lithium ion battery is converted into gaseous state and solid matter etc. and is completely separated, and has
Effect avoids subsequent contamination of the organic electrolyte to positive electrode etc..Then, the utility model is by volatile organic compounds and cracking gas
It burns in burner, the flue gas of generation enters smoke eliminator, using milk of lime injection apparatus to the cigarette of purification furnace
Milk of lime is sprayed into gas and carries out depickling reaction, the phosphorous sour gas in flue gas is changed into calcium phosphate, fluorine-containing sour gas
Change into calcirm-fluoride；After flue gas after being reacted using deduster depickling carries out dedusting, discharge.In addition, it is filled using grinding and sieving
It puts and the solid product after cracking is subjected to grinding and sieving, can positive electrode therein and graphite be subjected to formation powder fine crushing,
And it is separated with sheet metal.Secondly, carrying out acidleach to powder using acidleach device can react positive electrode and acid, will be therein
The metals such as lithium, nickel, cobalt are converted into ion and enter filtrate, and then are prepared into lithium-ion electric in positive electrode material precursor preparation facilities
The persursor material of pond positive electrode.Iron, aluminium and the copper in sheet metal can also be recycled by apparatus for recovering metal simultaneously.
The utility model provides the processing system of complete set for waste and old lithium ion battery, and metals resources therein (can be come from
Positive electrode, organic electrolyte etc.) effective recycling has been carried out, and by the organic matter in waste and old lithium ion battery and can have
Evil substance is innoxious, is recycling, environmentally protective processing system for waste and old lithium ion battery.In addition, above-mentioned system
System, which also has, is easy to engineering, the advantage of advanced economy, is very suitable for industrialization large-scale application.
Description of the drawings
The accompanying drawings which form a part of this application are used to provide a further understanding of the present invention, this practicality
New schematic description and description does not form the improper restriction to the utility model for explaining the utility model.
In the accompanying drawings：
Fig. 1 shows a kind of schematic diagram of the processing system of waste and old lithium ion battery according to the present utility model.
Wherein, above-mentioned attached drawing is marked including the following drawings：
10th, breaker；20th, low temperature gasification pyrolysis furnace；30th, burner；31st, heating generator；40th, gas cleaning fills
It puts；41st, purification furnace；42nd, activated carbon injection apparatus；43rd, milk of lime injection apparatus；44th, deduster；50th, grinding and sieving device；
60th, apparatus for recovering metal；70th, acidleach device；80th, positive electrode material precursor preparation facilities；81st, the first settler；82nd, second
Settler；83rd, precipitating reagent feeding mechanism；90th, inert gas feeding mechanism；100th, flotation unit；110th, melting furnace；120th, put
Electric installation.
Specific embodiment
It should be noted that in the case where there is no conflict, the feature in embodiment and embodiment in the application can phase
Mutually combination.The utility model will be described in detail below with reference to the accompanying drawings and embodiments.
The application is described in further detail below in conjunction with specific embodiment, these embodiments are it is not intended that limit this
Apply for scope claimed.
As background section is described, in the prior art the recycling of waste and old lithium ion battery there are recycling it is poor,
The problem of not environmentally friendly enough.
In order to solve the problems, such as this, the utility model provides a kind of processing system of waste and old lithium ion battery, such as Fig. 1 institutes
Show, including breaker 10, low temperature gasification pyrolysis furnace 20, burner 30, smoke eliminator 40, grinding and sieving device
50, apparatus for recovering metal 60, acidleach device 70 and positive electrode material precursor preparation facilities 80；Breaker 10 is provided with battery core
Particle exports and volatile organic compounds outlet, breaker 10 are used to be crushed to obtain battery core by the battery core of waste and old lithium ion battery
Particle and volatile organic compounds；Low temperature gasification pyrolysis furnace 20 is provided with the import of battery core particle, cracking gas outlet and solid residue and goes out
Mouthful, the import of battery core particle is connected with the outlet of battery core particle, and low temperature gasification pyrolysis furnace 20 is used to battery core particle carrying out low temperature gasification
Cracking obtains cracking gas and solid residue；Burner 30 is provided with air inlet and exhanst gas outlet, air inlet respectively with cracking
Gas is exported to be connected with volatile organic compounds outlet；Smoke eliminator 40 includes purification furnace 41, milk of lime injection apparatus 43 and dedusting
Device 44, purification furnace 41 are provided with gas inlet and depickling exhanst gas outlet, and gas inlet is connected with exhanst gas outlet；Milk of lime injection dress
43 are put for spraying milk of lime into purification furnace 41 so that the phosphorous sour gas in flue gas changed into calcium phosphate, and by fluoric-containing acid
Property gas changes into calcirm-fluoride；Deduster 44 is connected with depickling exhanst gas outlet；Grinding and sieving device 50 is provided with solid residue
Import, sheet metal outlet and powder outlet, grinding and sieving device 50 are used to obtain powder to solid residue progress grinding and sieving
And sheet metal；Apparatus for recovering metal 60 is connected with sheet metal outlet, for recycling the iron in sheet metal, aluminium and copper；Acidleach device
70 are connected with powder outlet, and filtrate is obtained for carrying out acidleach to powder；Positive electrode material precursor preparation facilities 80 is filled with acidleach
It puts 70 to be connected, for preparing the persursor material of anode material for lithium-ion batteries using filtrate.
Using above-mentioned processing system provided by the utility model, can be generated when being crushed using breaker 10 to battery core
Some volatile organic compounds, battery core particle is carried out in low temperature gasification pyrolysis furnace 20 to low temperature gasification cracking can will be therein organic
Cracking gasification reaction occurs for object, generates cracking gas (mainly some cracking paraffin gas and olefin gas) and solid residue
(predominantly positive electrode, graphite powder and metal) so that the organic matter in waste and old lithium ion battery be converted into gaseous state with
Solid matter etc. is completely separated, and effectively prevents subsequent contamination of the organic electrolyte to positive electrode etc..Then, the utility model
Volatile organic compounds and cracking gas are burnt in burner 30, the flue gas of generation enters smoke eliminator 40, utilizes stone
Grey breast injection apparatus 43 sprays into milk of lime into the flue gas of purification furnace 41 and carries out depickling reaction, by the phosphorous sour gas in flue gas
Body changes into calcium phosphate, and fluorine-containing sour gas changes into calcirm-fluoride；Flue gas after being reacted using deduster 44 depickling is removed
After dirt, discharge.In addition, the solid product after cracking is subjected to grinding and sieving using grinding and sieving device 50, it can will be therein
Positive electrode and graphite carry out formation powder fine crushing, and are separated with sheet metal.Secondly, acid is carried out to powder using acidleach device 70
Leaching can react positive electrode and acid, and the metals such as lithium therein, nickel, cobalt are converted into ion and enter filtrate, and then in anode
The persursor material of anode material for lithium-ion batteries is prepared into material precursor preparation facilities 80.Simultaneously the iron in sheet metal,
Aluminium and copper can also be recycled by apparatus for recovering metal 60.The utility model provides a set of complete for waste and old lithium ion battery
Whole processing system (from positive electrode, organic electrolyte etc.) can effectively return to metals resources therein
It receives, and can be innoxious by the organic matter in waste and old lithium ion battery and harmful substance, it is the money for waste and old lithium ion battery
Source, environmentally protective processing system.In addition, above system, which also has, is easy to engineering, the advantage of advanced economy, very
It is suitble to industrialization large-scale application.
In a preferred embodiment, low temperature gasification pyrolysis furnace 20 includes housing and chuck, and housing is provided with battery core
Particle import, cracking gas outlet, solid residue outlet and superheated steam import, housing are used to provide for low temperature gasification cracking anti-
Answer place；Chuck is arranged on the outside of housing, and chuck is provided with heat smoke import, and heat smoke import is used to be passed through heat into chuck
Flue gas carries out concurrent heating to be cracked to low temperature gasification.In this way, superheated steam reacts in the housing with battery core particle, battery core can be made broken
Alkane, the olefin gas that low temperature gasification cracking is converted into small molecule occur for the organic matter in material, can effectively avoid coking.With this
Meanwhile by the use of superheated steam as heat source and heat smoke chuck concurrent heating, compared to other heat forms, (for example fuel nozzle is mended
Heat), the cracking gas purity height obtained after cracking gasification reaction occurs for organic matter, does not add in additional other gases, drops significantly
The treatment quantity of low cracking gas processing system, investment is low, bioxin removes more thorough, and under an inert atmosphere, cracking is anti-
It should be safer.
Preferably, processing system further includes heat smoke feeding mechanism, and heat smoke feeding mechanism is connected with heat smoke import, uses
In the heat smoke that the aftercombustion fuel oil into chuck and/or natural gas generate.It so can be in the feelings of superheated steam shortage of heat
By chuck to cracking reaction concurrent heating under condition.
In a preferred embodiment, the battery core particle entrance of low temperature gasification pyrolysis furnace 20 is provided with the first sealing
Portion, cracking gas outlet are provided with the second sealing, and solid residue exit is provided with the 3rd sealing；Processing system is also wrapped
Inert gas feeding mechanism 90 is included, inert gas feeding mechanism 90 is respectively at the first sealing, the second sealing and the 3rd sealing
Portion is connected.Low temperature gasification cracking process can be protected using inert gas feeding mechanism 90, improve the security of processing.
Preferably, above-mentioned inert gas feeding mechanism 90 is also connected with breaker 10, makes the protection crushed in inert gas of battery core
Lower progress further improves the security of processing system.
In a preferred embodiment, burner 30 is waste heat boiler, and burner 30 is additionally provided with steam and goes out
Mouthful, processing system further includes heating generator 31, and the entrance of heating generator 31 is connected with steam (vapor) outlet, heating generator 31
Outlet is connected with superheated steam outlet.The heat water that so can be directly generated using cracking gas and volatile organic compounds burning
Steam is generated, and then steam is heated to be by superheated steam by heating generator and returns to low temperature gasification cleavage stages.So can
The energy of further recycling waste and old lithium ion battery, reduces energy consumption.
In a preferred embodiment, smoke eliminator 40 further includes activated carbon injection apparatus 42, activated carbon spray
Injection device 42 is used to spray activated carbon into purification furnace 41 with bioxin and peculiar smell in flue gas described in adsorbing and removing.It can during discharge
It is discharged so that purified flue gas is concentrated by chimney.
The common type in flue gas ash removal field, such as sack cleaner may be employed in above-mentioned 44 type of deduster.
In a preferred embodiment, deduster 44 is additionally provided with the outlet of dirt slag, and processing system further includes melting furnace
110, melting furnace 110 is connected with the outlet of dirt slag, and melting harmless treatment is carried out for the dirt slag to dirt slag outlet discharge.Deduster
The dirt slag obtained in 44 dust removal processes, main component are calcium phosphate, calcirm-fluoride and waste active carbon, can be with using melting furnace 110
Melting harmless treatment is carried out, is conducive to further improve the feature of environmental protection of technique, and this part resource is converted into harmless
Solid waste is recycled.
In a preferred embodiment, apparatus for recovering metal 60 is concentration equipment, gravity concentration apparatus or pneumatic separation device.It is logical
Cross these types of processing unit, can by sheet metal iron, aluminium and and copper be separately recovered, related neck may be employed in specific equipment
The commonly used equipment in domain, details are not described herein.
In a preferred embodiment, processing system further includes flotation unit 100, and flotation unit 100 is arranged on powder
Body is exported on the pipeline between acidleach device 70, and carbon is removed for carrying out flotation to powder.Based between carbon dust and positive electrode
Density variation, using flotation unit 100 can to powder carry out pre-separation, so as to improve between carbon dust and positive electrode
Separating effect.
In a preferred embodiment, acidleach device 70 is additionally provided with carbon dust outlet；Processing system further includes melting
Stove 110, melting furnace 110 are provided with fuel inlet, and fuel inlet is connected with carbon dust outlet.So this can be partially separated out
Fuel of the carbon dust as melting innocent treatment procedure, so as to further improve resource utilization rate, reduce energy consumption.
In a preferred embodiment, positive electrode material precursor preparation facilities 80 includes the first settler 81, the
Two settlers 82 and precipitating reagent feeding mechanism 83, the first settler 81 be provided with filtrate import, compressed air inlet and
Secondary filtrate (liquid, filtrate import are connected with the filtrate (liquid of acidleach device 70, and the first settler 81 is used to carry out filtrate
Except iron；Second settler 82 is provided with secondary filtrate import, precipitating reagent import and persursor material outlet, secondary filtrate import
It is connected with secondary filtrate (liquid, the second settler 82 is used to the secondary filtrate of secondary filtrate import discharge carrying out precipitation reaction
Generate persursor material；Precipitating reagent feeding mechanism 83 is connected with precipitating reagent import, heavy for being supplied into the second settler 82
Shallow lake agent carries out precipitation reaction.Filtrate can be carried out by the first settler 81 except iron under conditions of compressed air is passed through.
Using the second settler 82 can with when secondary filtrate precipitation reaction is carried out under the action of precipitating reagent, with further by secondary filter
The cycling of elements hydrates such as nickel, cobalt, manganese in liquid precipitate, and form the ternary precursor of anode material for lithium-ion batteries.It is heavy
Shallow lake agent preferably uses sodium hydroxide solution and/or ammonium hydroxide.
In a preferred embodiment, the first settler 81 is additionally provided with scum outlet, and processing system further includes
Melting furnace 110, melting furnace 110 are connected with scum outlet, and melting harmless treatment is carried out for the scum to scum outlet discharge.
Scum can be so converted into harmless solid waste to be used, to further improve the recycling degree of technique.
Preferably, melting furnace 110 is side-blown submerged combustion stove, and liquid molten molten bath, side-blown spray gun submergence are provided in stove
Below molten bath.Solid waste entered by charge door in high-temperature slag decomposed, the smelting processes such as slag making, wherein most
Harmful substance cure in slag, particularly calcirm-fluoride and calcium phosphate, be melted at high temperature in iron silico-calcium ternary slag system,
Polynary slag system glass slugging is formed, so as to which dangerous waste is converted into general solid waste.
In a preferred embodiment, processing system further includes electric discharge device 120, and electric discharge device 120 is used for useless
The battery core of old lithium ion battery carries out discharge treatment, and electric discharge device 120 is connected with breaker 10, for will be after discharge treatment
Battery core is delivered in breaker 10.
Another aspect according to the present utility model, the utility model additionally provide a kind of processing side of waste and old lithium ion battery
Method comprises the following steps：S1 crushes the battery core of waste and old lithium ion battery, obtains battery core particle and volatile organic compounds；
Battery core particle is carried out low temperature gasification cracking, obtains cracking gas and solid residue by S2；S3 has cracking gas and the volatilization
Machine object burns, and obtains flue gas；S4 sprays into milk of lime progress depickling reaction into flue gas, by the phosphorous acidity in flue gas
Gas changes into calcium phosphate, and fluorine-containing sour gas changes into calcirm-fluoride；After flue gas after reacting depickling carries out dedusting, discharge；
Solid residue is carried out grinding and sieving, obtains powder and sheet metal by S5；S6 recycles iron, aluminium and copper in sheet metal；S7 is right
Powder carries out acidleach, and filtrate is then obtained by filtration；The persursor material of anode material for lithium-ion batteries is prepared using filtrate.
Waste and old lithium ion battery is recycled using above-mentioned processing method, it is organic that some volatilizations can be generated when being crushed to battery core
Object, battery core particle is carried out low temperature gasification cracking organic matter therein can occur cracking gasification reaction, and it is (main to generate cracking gas
If some cracking paraffin gas and olefin gas) and solid residue (predominantly positive electrode, graphite powder and metal), make
Organic matter in waste and old lithium ion battery is converted into gaseous state and solid matter etc. and is completely separated, effectively prevent Organic Electricity
Solve subsequent contamination of the liquid to positive electrode etc..Then, volatile organic compounds and cracking gas are burnt, is sprayed into obtained flue gas
Milk of lime can make phosphorous, the fluorine-containing sour gas generation depickling reaction in flue gas be converted into calcium phosphate and calcirm-fluoride (process
Middle flue gas can also be quenched), the innoxious of flue gas is then realized by dust removal process.In addition, by the solid product object after cracking
Grinding and sieving is carried out, can positive electrode therein and graphite formation powder fine crushing be subjected to, and be separated with sheet metal.Secondly,
Acidleach is carried out to powder can react positive electrode and acid, and the metals such as lithium therein, nickel, cobalt, manganese are converted into ion enters
Filtrate, and then it is prepared into the persursor material of anode material for lithium-ion batteries.Iron, aluminium and the copper in sheet metal also obtain simultaneously
Recycling.The utility model provides a complete processing route for waste and old lithium ion battery, (comes for metals resources therein
From positive electrode, organic electrolyte etc.) carried out effective recycling, and can by the organic matter in waste and old lithium ion battery and
Harmful substance is innoxious, is recycling, environmentally protective treatment process for waste and old lithium ion battery.In addition, it is above-mentioned
Method, which also has, is easy to engineering, the advantage of advanced economy, is very suitable for industrialization large-scale application.
In order to improve the efficiency of low temperature gasification cracking process, while the security of shattering process is improved, a kind of preferred
In embodiment, above-mentioned shattering process includes：Carried out under the protection of inert gas it is above-mentioned broken, particle size after cracking control 2~
3cm, temperature is maintained at less than 25 DEG C when broken.
In a preferred embodiment, in above-mentioned steps S2, to battery core particle carry out low temperature gasification cracking the step of
Including：Under the protection of inert gas, into battery core particle being passed through superheated steam is reacted, so that organic in battery core particle
Cracking gasification reaction occurs for object, obtains cracking gas and solid residue.In this way, using the reaction of superheated steam and battery core particle,
It can make the organic matter in battery core particle that alkane, olefin gas that low temperature gasification cracking is converted into small molecule occur, it can be effective
Avoid coking.At the same time, by the use of superheated steam as heat source, compared to other heat forms (such as fuel nozzle concurrent heating),
The cracking gas purity height obtained after cracking gasification reaction occurs for organic matter, does not add in additional other gases, greatly reduces
The treatment quantity of gas processing system is cracked, investment is low, bioxin removing is more thorough, and under an inert atmosphere, cracking reaction is more
For safety.
Specific inert atmosphere can be nitrogen, argon gas, carbon dioxide etc..Preferably, the temperature for cracking gasification reaction is
400~600 DEG C.Preferably, with the heat water generated in combustion process in step S3, steam is obtained, high frequency is recycled to add
Hot device heats steam to form superheated steam；Energy consumption so can be further reduced, it is energy saving.Preferably, step
S2 is further included：Using heat smoke by chuck to cracking gasification reaction concurrent heating, combustion of the heat smoke from fuel oil and/or natural gas
It burns.The concurrent heating process can carry out concurrent heating in superheated steam shortage of heat by chuck, so on the one hand can ensure to crack
On the one hand the progress of gasification reaction will not enter other gases into cracking gas, will not increase the burden of follow-up gas cleaning.
Preferably, in the step of above-mentioned low temperature gasification cracking, the useless pole piece of outsourcing and battery core particle can be carried out together
Crack gasification reaction.
In order to further improve the clean-up effect of flue gas, in a preferred embodiment, in step S4, into flue gas
While spraying into milk of lime and carry out depickling reaction, activated carbon is sprayed into flue gas with bioxin in adsorbing and removing flue gas and different
Taste.
In a preferred embodiment, dirt slag has been obtained during dedusting in above-mentioned steps S3, processing method is also
The step of including dirt slag is carried out melting harmless treatment.The dirt slag obtained in above-mentioned dust removal process, main component for calcium phosphate,
Calcirm-fluoride and waste active carbon, are carried out high temperature harmless treatment, are converted into glassy state slag and are fixed harmful components, are converted into nothing
Evil solid waste is recycled.
In a preferred embodiment, in step S6, recycling the iron in sheet metal, aluminium and the step of copper includes：It will
Sheet metal carries out magnetic separation, gravity treatment or selection by winnowing, and iron, aluminium and and copper in sheet metal is separately recovered.It, can by these types of processing mode
With by sheet metal iron, aluminium and and copper be separately recovered, the common processing work of association area may be employed in specific processing mode
Skill, details are not described herein.
During solid residue is carried out grinding and sieving, the positive electrode and graphite of the inside all can be by formation powder fine crushing
Body, so as to be separated with sheet metal.In a preferred embodiment, in above-mentioned steps S7, to powder carry out acidleach the step of
In, the leaching agent used is hydrochloric acid, nitric acid or sulfuric acid.By the leaching of these reagents, can by positive electrode lithium, nickel,
The cycling of elements such as cobalt, manganese enter into ion in filtrate, and carbon dust is then separated as filter residue.Preferably, powder is carried out
Before the step of acidleach, step S7 is further included carries out the step of flotation removes carbon to powder.Based between carbon dust and positive electrode
Density variation can carry out pre-separation, so as to improve between carbon dust and positive electrode using the mode of flotation to powder
Separating effect.
In a preferred embodiment, in step S7, carbon dust has been obtained by filtration during acidleach, processing method is also
Including using carbon dust as the step of the fuel of above-mentioned melting innocent treatment procedure.Applying waste lithium ionic can so be further improved
The effective rate of utilization of resource in battery reduces energy consumption.
In a preferred embodiment, in step S7, the forerunner of anode material for lithium-ion batteries is prepared using filtrate
The step of body material, includes：The pH value of filtrate is adjusted to 4~6, compressed air is then passed through thereto and is reacted, obtain scum
With secondary filtrate；Ammonium hydroxide is added in into secondary filtrate and/or sodium hydroxide solution carries out precipitation reaction, obtains persursor material.
The acidity of the filtrate obtained after step of acid dipping is higher, and after its pH value to 4~6, will be passed through compressed air using alkali can incite somebody to action
Ferrous ion in filtrate is converted into ferric hydroxide precipitate removal, and the alkali of use can be sodium hydroxide etc..It then proceedes to think
Ammonium hydroxide and/or sodium hydroxide are added in secondary filtrate after filtering, converts further the nickel in secondary filtrate, cobalt, manganese
It precipitates for hydroxide, forms persursor material.
The process conditions of above-mentioned precipitation reaction can be adjusted, it is preferable that the temperature of precipitation reaction is 40~70 DEG C, pH
It is worth for 10~12, the reaction time is 6~20h.
Preferably, in step S7, processing method further includes the step of carrying out melting harmless treatment to scum.So can
Scum is converted into harmless solid waste to be used, to further improve the recycling degree of technique.
In a preferred embodiment, in step S1, the battery core of waste and old lithium ion battery is carried out to broken step
Before, processing method further includes the step of carrying out concentrating electric discharge to waste and old lithium ion battery.
It should be noted that in the processing procedure of above-mentioned waste and old lithium ion battery, the solid dangerous waste that each process generates is all
Side-blown submerged combustion stove can be sent into and carry out high temperature harmless treatment, 1300~1500 DEG C for the treatment of temperature.There is liquid molten in stove
Molten bath, side-blown spray gun are immersed in below molten bath.Solid waste entered by charge door in high-temperature slag decomposed, the smeltings such as slag making
Refining process, the harmful substance of wherein most cure in slag, particularly calcirm-fluoride and calcium phosphate, are melted at high temperature
In iron silico-calcium ternary slag system, polynary slag system glass slugging is formed, so as to which dangerous waste is converted into general solid waste.
Preferably, the flue gas generated in above-mentioned melting innocent treatment procedure goes out boiler by waste heat boiler recovery waste heat
Flue gas send exhaust treatment system collection China and foreign countries to arrange after quenching.By the flue dust of a small amount of high chlorine for cycling, it is preferred to use wet
It is after method leaches and dry, obtain chlorate take-away.
The beneficial effects of the utility model are further illustrated by the following examples：
Embodiment 1
After applying waste lithium ionic battery core concentrates electric discharge, be sent into nitrogen protection crushing system and carry out coarse crushing, granularity control 2~
3cm, temperature control is below 25 DEG C when crushing.The volatile organic gases generated when broken send cracking gas secondary combustion system.
Under broken battery core particle nitrogen atmosphere in closed addition low temperature gasification pyrolysis furnace, 550 DEG C of cracking temperature.Low temperature
The feed inlet and outlet of cracking furnace has double-deck nitrogen-sealed.The overheat saturated vapor being passed through in stove carries out low temperature gas with battery core particle
Change cracking and obtain cracking gas and solid residue, specifically：The generations such as electrolyte organic matter, binding agent PVDF crack gasified reverse
It answers, paraffin gas and some olefin gas such as generation methane, ethane, the lithium hexafluoro phosphate in electrolyte decomposes production in pyrolysis furnace
Raw LiF and PF5, solid residue is mainly positive electrode, graphite powder and metal.
Following processing is carried out for cracking gas：
Cracking gas enters waste heat boiler and carries out second-time burning, and the steam that waste heat boiler generates is heated by thermatron
It is back to after to 600 DEG C in the chuck of low temperature gasification pyrolysis furnace and is used as heat source.Smoke temperature at outlet of waste heat boiler control exists
300~500 DEG C, cooling system quenching is sent into, while sprays into milk of lime and the sour gas such as F, P in flue gas is neutralized, is passed through
Cloth bag dust-precipitator, and it is mainly N to spray into a small amount of active carbon adsorption residual bioxin and peculiar smell, final smoke components2、O2、
H2O、CO2, content of dioxin is less than 0.1ng-TEQ/Nm3, NOXContent is less than 50mg/m3, reached discharge standard.
The ash that bag collection obtains, main component are calcium phosphate, calcirm-fluoride and waste active carbon, send side-blown pyrogenic process high temperature melting
Melt processing, 1300~1500 DEG C of smelting temperature.There is liquid molten molten bath in stove.Side-blown spray gun fuel can spray waste active carbon or day
Right gas.Bag dust containing calcium phosphate, calcirm-fluoride and waste active carbon and flux are added in from charge door in side-blown converter slag
It is decomposed, the smelting processes such as slag making, when smelting utilizes CaO-SiO2-FeO-P2O5-CaF2Slag system controls CaF in slag2=
20%th, P2O5=10%, SiO2=15%, FeO=20%, CaO=35%.
Harmful substance F, P cures in slag, particularly calcirm-fluoride and calcium phosphate, is melted in iron silico-calcium three at high temperature
In first slag system, polynary slag system glass slugging is formed, so as to which dangerous waste is converted into general solid waste.It is generated during side-blown converter high melt
Flue gas goes out the control of boiler smoke temperature at 400~600 DEG C, vent gas treatment system is sent after quenching by waste heat boiler recovery waste heat
System collection China and foreign countries are arranged.It is after wet-leaching and dry by the flue dust of a small amount of high chlorine for cycling, obtain chlorate take-away.
Following processing is carried out for solid residue：
Solid residue is subjected to grinding and sieving, obtains powder and sheet metal, magnetic separation is carried out to sheet metal, it is separately recovered
In iron, aluminium and copper.
Flotation is carried out to powder, is divided carbon dust therein in advance using the density variation between carbon dust and positive electrode
From.Using aqueous sulfuric acid to flotation except the powder after carbon carries out acidleach, by elements such as lithium, nickel, cobalt, the manganese in positive electrode
Ion is changed into enter in filtrate, and carbon dust is then separated as filter residue.The terminal pH controls of above-mentioned acidleach process exist
1.5, it carries out that carbon dust and filtrate is obtained by filtration after dissolving.
The pH value of above-mentioned filtrate is adjusted to 4.8, compressed air is passed through and removes iron, after filtration washing, in secondary filtrate
The sodium hydrate aqueous solution of the middle ammonium hydroxide and 4N for adding in 20wt% concentration, control system pH value are 11.0, and temperature is 70 DEG C, reaction
Time 15h obtains ternary precursor after final filtration washing.
The above-mentioned scum separated in melting furnace is subjected to melting harmless treatment, while is filtered out above-mentioned
Carbon dust burns as fuel in melting furnace provides heat, and the technique for melting harmless treatment is identical with preceding sections.
It can be seen from the above description that the above embodiments of the present invention achieve the following technical effects：
The utility model provides a complete processing route for waste and old lithium ion battery, for metals resources therein
(from positive electrode, organic electrolyte etc.) has carried out effective recycling, and can will be organic in waste and old lithium ion battery
Object and harmful substance are innoxious, are recycling, environmentally protective treatment process for waste and old lithium ion battery.In addition,
The above method, which also has, is easy to engineering, the advantage of advanced economy, is very suitable for industrialization large-scale application.
The above is only the preferred embodiment of the utility model only, 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 modifications, equivalent replacements and improvements are made should be included within the scope of protection of this utility model.
Claims (13)
1. a kind of processing system of waste and old lithium ion battery, which is characterized in that including：
Breaker (10), the breaker (10) is provided with the outlet of battery core particle and volatile organic compounds outlet, described broken
Device (10) is used to be crushed the battery core of the waste and old lithium ion battery to obtain battery core particle and volatile organic compounds；
Low temperature gasification pyrolysis furnace (20), the low temperature gasification pyrolysis furnace (20) be provided with the import of battery core particle, cracking gas outlet and
Solid residue exports, and the battery core particle import is connected with battery core particle outlet, the low temperature gasification pyrolysis furnace (20)
For battery core particle progress low temperature gasification to be cracked to obtain cracking gas and solid residue；
Burner (30), the burner (30) are provided with air inlet and exhanst gas outlet, the air inlet respectively with it is described
Cracking gas is exported to be connected with volatile organic compounds outlet；
Smoke eliminator (40), the smoke eliminator (40) include purification furnace (41), milk of lime injection apparatus (43) and
Deduster (44), the purification furnace (41) are provided with gas inlet and depickling exhanst gas outlet, the gas inlet and the flue gas
Outlet is connected；The milk of lime injection apparatus (43) is used for into the purification furnace (41) injection milk of lime with will be in the flue gas
Phosphorous sour gas change into calcium phosphate, and fluorine-containing sour gas is changed into calcirm-fluoride；The deduster (44) with it is described
Depickling exhanst gas outlet is connected；
Grinding and sieving device (50), the grinding and sieving device (50) are provided with solid residue import, sheet metal outlet and powder
Body exports, and the grinding and sieving device (50) is used to obtain powder and sheet metal to solid residue progress grinding and sieving；
Apparatus for recovering metal (60) is connected with sheet metal outlet, for recycling iron, aluminium and the copper in the sheet metal；
Acidleach device (70), the acidleach device (70) are connected with powder outlet, are obtained for carrying out acidleach to the powder
To filtrate；And
Positive electrode material precursor preparation facilities (80) is connected with the acidleach device (70), for preparing lithium using the filtrate
The persursor material of ion battery positive electrode.
2. processing system according to claim 1, which is characterized in that the low temperature gasification pyrolysis furnace (20) includes：
Housing, be provided with the battery core particle import, the cracking gas outlet, the solid residue outlet and superheated steam into
Mouthful, the housing is used to provide reacting environment for low temperature gasification cracking；
Chuck is arranged on the outside of the housing, and the chuck is provided with heat smoke import, and the heat smoke import is used for institute
It states and heat smoke is passed through in chuck to crack progress concurrent heating to the low temperature gasification.
3. processing system according to claim 2, which is characterized in that the processing system further includes heat smoke supply dress
It puts, the heat smoke feeding mechanism is connected with the heat smoke import, for aftercombustion fuel oil and/or day into the chuck
The heat smoke that right gas generates.
4. processing system according to claim 2, which is characterized in that the battery core of the low temperature gasification pyrolysis furnace (20)
Particle entrance is provided with the first sealing, and the cracking gas outlet is provided with the second sealing, and the solid residue goes out
The 3rd sealing is provided at mouthful；The processing system further includes inert gas feeding mechanism (90), the inert gas supply
Device (90) is connected respectively at first sealing, second sealing and the 3rd sealing.
5. processing system according to claim 2, which is characterized in that the burner (30) is waste heat boiler, described
Burner (30) is additionally provided with steam (vapor) outlet, and the processing system further includes heating generator (31), the heating generator
(31) entrance is connected with the steam (vapor) outlet, and the outlet of the heating generator (31) is connected with superheated steam outlet.
6. processing system according to any one of claim 1 to 5, which is characterized in that the smoke eliminator (40)
Activated carbon injection apparatus (42) is further included, the activated carbon injection apparatus (42) is used for the injection activity into the purification furnace (41)
Charcoal is with bioxin and peculiar smell in flue gas described in adsorbing and removing.
7. processing system according to claim 6, which is characterized in that the deduster (44) is additionally provided with the outlet of dirt slag,
The processing system further includes melting furnace (110), and the melting furnace (110) is connected with dirt slag outlet, for the dirt
The dirt slag of slag outlet discharge carries out melting harmless treatment.
8. processing system according to any one of claim 1 to 5, which is characterized in that the apparatus for recovering metal (60)
For concentration equipment, gravity concentration apparatus or pneumatic separation device.
9. processing system according to any one of claim 1 to 5, which is characterized in that the processing system further includes floating
Screening device (100), the flotation unit (100) are arranged on the pipeline between the powder outlet and the acidleach device (70)
On, remove carbon for carrying out flotation to the powder.
10. processing system according to claim 9, which is characterized in that the acidleach device (70) is additionally provided with carbon dust and goes out
Mouthful；The processing system further includes melting furnace (110), and the melting furnace (110) is provided with fuel inlet, the fuel inlet with
The carbon dust outlet is connected.
11. processing system according to any one of claim 1 to 5, which is characterized in that the positive electrode material precursor system
Standby device (80) includes：
First settler (81), first settler (81) are provided with filtrate import, compressed air inlet and secondary filter
Liquid exports, and the filtrate import is connected with the filtrate (liquid of the acidleach device (70), and first settler (81) is used for
The filtrate is carried out except iron；
Second settler (82), second settler (82) are provided with secondary filtrate import, precipitating reagent import and forerunner
Body material outlet, the secondary filtrate import are connected with the secondary filtrate (liquid, and second settler (82) is used for will
The secondary filtrate of the secondary filtrate import discharge carries out precipitation reaction and generates the persursor material；And
Precipitating reagent feeding mechanism (83) is connected with the precipitating reagent import, for the supply into second settler (82)
Precipitating reagent carries out the precipitation reaction.
12. processing system according to claim 11, which is characterized in that first settler (81) is additionally provided with iron
Slag exports, and the processing system further includes melting furnace (110), and the melting furnace (110) exports with the scum to be connected, for pair
The scum of scum outlet discharge carries out melting harmless treatment.
13. processing system according to any one of claim 1 to 5, which is characterized in that the processing system, which further includes, puts
Electric installation (120), the electric discharge device (120) is used to carry out discharge treatment to the battery core of the waste and old lithium ion battery, described
Electric discharge device (120) is connected with the breaker (10), described broken for the battery core after discharge treatment to be delivered to
In device (10).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108172923A (en) * | 2017-11-13 | 2018-06-15 | 中国恩菲工程技术有限公司 | The processing system of waste and old lithium ion battery |
| CN109088117A (en) * | 2018-08-03 | 2018-12-25 | 许成林 | A kind of new energy car battery material recovery system |
| CN109290339A (en) * | 2018-09-10 | 2019-02-01 | 湖南邦普循环科技有限公司 | A kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece |
| CN109550568A (en) * | 2018-10-31 | 2019-04-02 | 株洲鼎端装备股份有限公司 | A kind of used Li ion cell cracking and sorting technique |
| CN113924374A (en) * | 2019-04-15 | 2022-01-11 | 诺斯伏特公司 | Method for recovering cathode material in battery recycling |
| CN114122522A (en) * | 2020-08-26 | 2022-03-01 | 北京小米移动软件有限公司 | Battery manufacturing apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108172923A (en) * | 2017-11-13 | 2018-06-15 | 中国恩菲工程技术有限公司 | The processing system of waste and old lithium ion battery |
| CN109088117A (en) * | 2018-08-03 | 2018-12-25 | 许成林 | A kind of new energy car battery material recovery system |
| CN109088117B (en) * | 2018-08-03 | 2019-05-14 | 许成林 | A kind of new energy car battery material recovery system |
| CN109290339A (en) * | 2018-09-10 | 2019-02-01 | 湖南邦普循环科技有限公司 | A kind of method of positive pole powder and aluminium collector in separating waste, worn tertiary cathode piece |
| CN109550568A (en) * | 2018-10-31 | 2019-04-02 | 株洲鼎端装备股份有限公司 | A kind of used Li ion cell cracking and sorting technique |
| CN113924374A (en) * | 2019-04-15 | 2022-01-11 | 诺斯伏特公司 | Method for recovering cathode material in battery recycling |
| CN114122522A (en) * | 2020-08-26 | 2022-03-01 | 北京小米移动软件有限公司 | Battery manufacturing apparatus |
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