CN111872021A - Environment-friendly waste lithium battery recovery processing system - Google Patents
Environment-friendly waste lithium battery recovery processing system Download PDFInfo
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- CN111872021A CN111872021A CN202010651394.2A CN202010651394A CN111872021A CN 111872021 A CN111872021 A CN 111872021A CN 202010651394 A CN202010651394 A CN 202010651394A CN 111872021 A CN111872021 A CN 111872021A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B5/00—Operations not covered by a single other subclass or by a single other group in this subclass
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B2101/00—Type of solid waste
- B09B2101/02—Gases or liquids enclosed in discarded articles, e.g. aerosol cans or cooling systems of refrigerators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses an environment-friendly waste lithium battery recovery processing system, which comprises a battery crushing device, wherein the battery crushing device is connected with a vacuum heating/hydrolysis liquid removing device; a fragment discharge port of the vacuum heating/hydrolysis liquid removal device is connected with a secondary crushing device, the secondary crushing device is connected with an airflow sorting machine, and the airflow sorting machine is connected with a diaphragm recovery device; the air flow separator is connected with a shell separation and conveying device, a crusher is arranged behind the shell separation and conveying device, the discharge end of the crusher is connected with an analyzer, and the discharge end of pole piece particles of the analyzer is connected with a swing sieve; the middle outlet of the swing sieve is connected with a grinder, the discharge port of the grinder is connected with a grinding material collector, and the bottom end opening of the grinding material collector is connected with a rotary vibration sieve; the lithium battery recovery processing system has the advantages of small pollution, high efficiency, reasonable processing technology, small environmental pollution in the processing process and high recovery rate.
Description
Technical Field
The invention relates to the field of waste battery treatment, in particular to a waste lithium battery recovery treatment system without waste gas discharge.
Background
The lithium battery mainly comprises a shell, a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the positive electrode is formed by coating lithium cobaltate powder on two sides of an aluminum foil current collector through PVDF (polyvinylidene fluoride) which plays a role in bonding; the negative electrode structure is similar to the positive electrode and is formed by bonding carbon powder on two sides of a copper foil current collector. The lithium ion battery has the obvious advantages of high voltage, large specific capacity, long service life, no memory effect and the like, so that the lithium ion battery can quickly occupy the market of power sources of portable electronic and electric equipment since the lithium ion battery is commercialized, and the yield is increased year by year. The service life is about 3-8 years, and if the discarded lithium battery is not properly treated, lithium hexafluorophosphate and carbonate organic solvents contained in the discarded lithium battery are toxic in air with certain humidity. On the other hand, cobalt, lithium, copper, metal shells, nickel sheets, lithium-containing compounds, plastic diaphragms and the like in the waste lithium batteries are valuable resources and have extremely high recovery value. Therefore, the waste lithium batteries are scientifically and effectively treated, and the method has remarkable environmental benefit and good economic benefit. Common methods for recycling waste lithium batteries include hydrometallurgy, pyrometallurgy and mechanical and physical methods. Compared with a wet method and a fire method, the mechanical and physical method does not need to use chemical reagents, has lower energy consumption and is an environment-friendly and efficient method.
However, the existing processing system is not perfect enough for crushing the lithium battery, and in the process of shredding, crushing and separating the battery, because lithium hexafluorophosphate and moisture in the air are subjected to decomposition reaction, harmful gas can be generated, and absolute sealing cannot be guaranteed through a conventional induced draft pipeline, so that certain phosphorus pentafluoride and hydrogen fluoride gas leak out in the operation process of the equipment, and the environment and the human health are harmed.
At present, the collection of the battery shell adopts a mode of additionally arranging a magnetic roller at the end part of a conveyor belt, and an iron shell is sucked out from a crushed mixture by utilizing magnetic force, but the mode has no function on the battery with the non-magnetic stainless steel shell because the shell is not magnetic. And the copper-aluminum particles obtained by the separation equipment are mixed materials, are not further separated, and bring certain difficulty for subsequent utilization.
Disclosure of Invention
The invention aims to solve the technical problem of providing an environment-friendly waste lithium battery recycling system without harmful gas emission.
In order to solve the technical problems, the technical scheme of the invention is as follows: an environment-friendly waste lithium battery recovery processing system comprises a battery crushing device, wherein the battery crushing device is connected with a vacuum heating/hydrolysis liquid removing device, and the battery crushing device and the vacuum heating/hydrolysis liquid removing device are connected with a harmful gas processing device;
a fragment discharge port of the vacuum heating/hydrolysis liquid removal device is connected with a secondary crushing device, the secondary crushing device is connected with an airflow separator, the airflow separator is connected with a diaphragm recovery device, and the secondary crushing device, the airflow separator and the diaphragm recovery device are all connected with a first dust removal device;
the air flow separator is connected with a shell separation conveying device, a crusher is installed behind the shell separation conveying device, the discharge end of the crusher is connected with an analyzer, the discharge end of pole piece particles of the analyzer is connected with a swing sieve, and a powder outlet of the analyzer is connected with a second dust removal device; the middle outlet of the swing sieve is connected with a grinding machine, a discharge port of the grinding machine is connected with a grinding material collector, a powder outlet at the top end of the grinding material collector is connected with a third dust removal device, and an opening at the bottom end of the grinding material collector is connected with a rotary vibration sieve.
As a preferred technical scheme, the battery crushing device comprises a battery feeding machine, and the discharge end of the battery feeding machine is connected with a shredder.
As a preferable technical scheme, the vacuum heating/hydrolysis liquid-removing device comprises a vacuum heating/hydrolysis liquid-removing tank body, a heating device and a temperature/pressure/humidity detection device are installed in the vacuum heating/hydrolysis liquid-removing tank body, and a liquid spraying device and a spiral stirring device are also installed in the vacuum heating/hydrolysis liquid-removing tank body;
the liquid spraying device comprises a liquid tank arranged on one side of the vacuum heating/hydrolysis liquid removal tank body, the liquid tank is connected with a liquid pipe extending into the vacuum heating/hydrolysis liquid removal tank body, a spraying pipe connected with the liquid pipe is arranged in the vacuum heating/hydrolysis liquid removal tank body, and a plurality of spraying heads are arranged on the spraying pipe.
As a preferred technical scheme, the harmful gas treatment device comprises a gas filter connected with an air outlet port of the battery crushing device and an air outlet port of the vacuum heating/hydrolysis liquid removal device, the gas filter is connected with a gas condenser, the gas condenser is connected with an alkali liquor spraying device through a vacuum pump, the air outlet port of the alkali liquor spraying device is connected with an activated carbon adsorption tank, and the activated carbon adsorption tank is connected with a purified gas discharge pipe; a spray liquid condenser is arranged on the alkali liquor spray device; the spraying liquid condenser and the gas condenser are both connected with a refrigerating machine.
As a preferred technical scheme, the alkali liquor spraying device comprises an alkali liquor spraying tower, the bottom end of the alkali liquor spraying tower is communicated with an alkali liquor circulating box, the spraying liquid condenser is arranged between the alkali liquor circulating box and the alkali liquor spraying tower, and the alkali liquor spraying tower is connected with a gas circulating device;
the gas circulating device comprises gas circulating pipes which are respectively communicated with the top end and the bottom end of the alkali liquor spraying tower, and a pipeline fan is arranged on each gas circulating pipe.
As a preferable technical scheme, the secondary crushing device comprises a crusher, and a spiral feeding machine is arranged between the crusher and a fragment discharging port of the vacuum heating/hydrolysis liquid-removing device.
As an optimal technical scheme, the diaphragm recovery device comprises a diaphragm recovery box, a diaphragm discharge port is arranged at the top end of the air flow separator, the diaphragm discharge port is communicated with the diaphragm recovery box through a diaphragm induced air pipeline, and a diaphragm induced air fan is installed on the diaphragm induced air pipeline.
As an optimal technical scheme, first dust collector include with the first loading head that secondary crushing device connects, there is first pulse dust remover top export of first loading head through the pipe connection, install first draught fan on the first pulse dust remover, the bottom discharge gate of first loading head with the air current sorter intercommunication, the top discharge gate of diaphragm collection box pass through the pipeline with first pulse dust remover is connected.
As a preferable technical scheme, the shell sorting and conveying device comprises a conveyor, a magnetic roller is installed at a discharge port of the conveyor, a blower for blowing light fragments into the pulverizer is installed below the discharge port of the conveyor, and a blanking collecting hopper is installed below the discharge port of the conveyor.
As a preferred technical scheme, the second dust removal device comprises a second collector connected with the analyzer, an outlet at the top end of the second collector is connected with a second pulse dust collector, and a second induced draft fan is installed on the second pulse dust collector;
the third dust collector include with grind the third loading head that the loading head is connected, the top exit linkage of third loading head has the third pulse dust collector, install the third draught fan on the third pulse dust collector.
Due to the adoption of the technical scheme, the environment-friendly waste lithium battery recovery processing system comprises a battery crushing device, wherein the battery crushing device is connected with a vacuum heating/hydrolysis liquid removing device, and the battery crushing device and the vacuum heating/hydrolysis liquid removing device are connected with a harmful gas processing device; a fragment discharge port of the vacuum heating/hydrolysis liquid removal device is connected with a secondary crushing device, the secondary crushing device is connected with an airflow separator, the airflow separator is connected with a diaphragm recovery device, and the secondary crushing device, the airflow separator and the diaphragm recovery device are all connected with a first dust removal device; the air flow separator is connected with a shell separation conveying device, a crusher is installed behind the shell separation conveying device, the discharge end of the crusher is connected with an analyzer, the discharge end of pole piece particles of the analyzer is connected with a swing sieve, and a powder outlet of the analyzer is connected with a second dust removal device; the middle outlet of the swing sieve is connected with a grinder, the discharge port of the grinder is connected with a grinding material collector, the powder outlet at the top end of the grinding material collector is connected with a third dust removal device, and the bottom end opening of the grinding material collector is connected with a rotary vibration sieve; the invention realizes the waste lithium battery no-waste gas crushing recovery, solves the problem of harmful gas leakage caused by the decomposition of lithium hexafluorophosphate in the existing lithium battery recovery technology, cleans up the carbonate electrolyte solvent at the front end of the pole piece treatment, and is more beneficial to the crushing and the pure separation of the subsequent pole pieces; the problem of sorting the stainless steel shells of the batteries in the prior art is solved, and the stainless steel shells are separated by adopting a specific gravity sorting mode; completely separating the copper and aluminum particles by using specific gravity liquid; the lithium battery recovery processing system has the advantages of small pollution, high efficiency, reasonable processing technology, small environmental pollution in the processing process and high recovery rate.
Drawings
The drawings are only for purposes of illustrating and explaining the present invention and are not to be construed as limiting the scope of the present invention. Wherein:
FIG. 1 is a schematic structural diagram of a device related to a debris screening and separating part in an embodiment of the invention;
FIG. 2 is a first schematic structural view of a harmless removal apparatus for an electrolyte according to an embodiment of the present invention;
FIG. 3 is a schematic structural view II of a harmless removal device for the electrolyte according to an embodiment of the invention;
FIG. 4 is a schematic structural diagram of a shell sorting and conveying device in an embodiment of the invention;
FIG. 5 is a flow chart of an embodiment of the present invention;
in the figure: 11-a crusher; 12-a spiral feeder; 13-an air flow separator; 14-a pulverizer; 15-an analyzer; 16-a rocking screen; 17-a grinder; 18-grinding the collector; 19-rotating and vibrating the sieve; 21-a shredder; 22-a vacuum heating/hydrolysis liquid-removing tank body; 23-a gas filter; 24-a gas condenser; 25-a refrigerator; 26-spray liquid condenser; 27-a vacuum pump; 28-clean gas discharge pipe; 29-battery feeder; 31-a liquid tank; 32-a liquid tube; 41-alkali liquor spray tower; 42-an alkali liquor circulation box; 51-gas circulation pipe; 52-pipeline fan; 6-activated carbon adsorption tank; 71-a membrane recovery tank; 72-diaphragm induced draft fan; 73-first collector; 74-a first pulse precipitator; 75-a first induced draft fan; 81-a conveyor; 82-a magnetic roller; 83-a blower; 84-blanking collection bin; 91-a second collector; 92-a second pulse precipitator; 93-a second induced draft fan; 94-third collector; 95-a third pulse precipitator; 96-a third induced draft fan; 97-Black powder storage bin.
Detailed Description
The invention is further illustrated below with reference to the figures and examples. In the following detailed description, certain exemplary embodiments of the present invention are described by way of illustration only. Needless to say, a person skilled in the art realizes that the described embodiments can be modified in various different ways without departing from the spirit and scope of the present invention. Accordingly, the drawings and description are illustrative in nature and not intended to limit the scope of the claims.
As shown in fig. 1 and 2, an environment-friendly waste lithium battery recycling system comprises a battery crushing device, wherein the battery crushing device is connected with a vacuum heating/hydrolysis liquid removing device, and the battery crushing device and the vacuum heating/hydrolysis liquid removing device are connected with a harmful gas treatment device; a fragment discharge port of the vacuum heating/hydrolysis liquid removal device is connected with a secondary crushing device, the secondary crushing device is connected with an airflow separator 13, the airflow separator 13 is connected with a diaphragm recovery device, and the secondary crushing device, the airflow separator 13 and the diaphragm recovery device are all connected with a first dust removal device; the air flow separator 13 is connected with a shell separation conveying device, a crusher 14 is installed behind the shell separation conveying device, the discharge end of the crusher 14 is connected with an analyzer 15, the discharge end of pole piece particles of the analyzer 15 is connected with a swing sieve 16, and a powder outlet of the analyzer 15 is connected with a second dust removal device; the middle outlet of the swing sieve 16 is connected with a grinder 17, the discharge port of the grinder 17 is connected with a grinding collector 18, the top powder outlet of the grinding collector 18 is connected with a third dust removal device, and the bottom end opening of the grinding collector 18 is connected with a rotary vibration sieve 19. The swing sieve 16 comprises three discharge ports, a top discharge port is used for sieving large-particle copper-aluminum particles, a bottom discharge port is used for sieving black powder, and a middle discharge port is used for sieving materials which can not be separated through specific gravity.
Black powder generated in the lithium battery recovery processing process is collected into the black powder collecting bin through a pipeline, and black powder discharge ports of the first dust removal device, the second dust removal device, the third dust removal device, the swing sieve 16 and the rotary vibration sieve 19 are communicated with the black powder collecting bin through pipelines.
As shown in fig. 3, the battery crushing device comprises a battery feeder 29, and a shredder 21 is connected to a discharge end of the battery feeder 29. The vacuum heating/hydrolysis liquid-removing device comprises a vacuum heating/hydrolysis liquid-removing tank 22, a heating device and a temperature/pressure/humidity detection device are installed in the vacuum heating/hydrolysis liquid-removing tank 22, and a liquid spraying device and a spiral stirring device are further installed in the vacuum heating/hydrolysis liquid-removing tank 22; the liquid spraying device comprises a liquid tank 31 arranged on one side of the vacuum heating/hydrolysis liquid-removing tank body 22, the liquid tank 31 is connected with a liquid pipe 32 extending into the vacuum heating/hydrolysis liquid-removing tank body 22, a spraying pipe connected with the liquid pipe 32 is arranged in the vacuum heating/hydrolysis liquid-removing tank body 22, and a plurality of spraying heads are arranged on the spraying pipe. The heating device, the temperature/pressure/humidity detecting device and the spiral stirring device are all devices commonly used in the field, and the working principle and structure thereof are common knowledge to those skilled in the art, and are not described herein again.
As shown in fig. 3, the harmful gas treatment device comprises a gas filter 23 connected with the gas outlet port of the battery crushing device and the gas outlet port of the vacuum heating/hydrolysis liquid removal device, negative pressure adsorption valves are respectively installed on the gas outlet port of the battery crushing device and the gas outlet port of the vacuum heating/hydrolysis liquid removal device, the gas filter 23 is connected with a gas condenser 24, the gas condenser 24 is connected with an alkali liquor spraying device through a vacuum pump 27, the gas outlet port of the alkali liquor spraying device is connected with an activated carbon adsorption tank 6, and the activated carbon adsorption tank 6 is connected with a clean gas discharge pipe 28; a spray liquid condenser 26 is arranged on the alkali liquor spray device; a refrigerator 25 is connected to both the spray liquid condenser 26 and the gas condenser 24.
As shown in fig. 3, the alkali liquor spray device comprises an alkali liquor spray tower 41, the bottom end of the alkali liquor spray tower 41 is communicated with an alkali liquor circulation box 42, the spray liquor condenser 26 is installed between the alkali liquor circulation box 42 and the alkali liquor spray tower 41, and the alkali liquor spray tower 41 is connected with a gas circulation device; the gas circulating device comprises gas circulating pipes 51 respectively communicated with the top end and the bottom end of the alkali liquor spraying tower 41, and a pipeline fan 52 is installed on the gas circulating pipes 51.
As shown in fig. 1, the secondary crushing device comprises a crusher 11, and a spiral feeder 12 is installed between the crusher 11 and a fragment discharging port of the vacuum heating/hydrolysis liquid removing device.
The diaphragm recovery unit includes diaphragm collection box 71, the top of air current sorter 13 is provided with the diaphragm bin outlet, the diaphragm bin outlet pass through the diaphragm induced air pipeline with diaphragm collection box 71 intercommunication, install diaphragm draught fan 72 on the diaphragm induced air pipeline.
First dust collector include with first loading head 73 that secondary crushing device connects, there is first pulse dust remover 74 in the top export of first loading head 73 through the pipe connection, install first draught fan 75 on the first pulse dust remover 74, the bottom discharge gate of first loading head 73 with air current sorter 13 intercommunication, the top discharge gate of diaphragm collection box 71 pass through the pipeline with first pulse dust remover 74 is connected.
As shown in fig. 4, the housing sorting conveyor includes a conveyor 81, a magnetic roller 82 is installed at a discharge port of the conveyor 81, a blower 83 for blowing light chips into the pulverizer 14 is installed below the discharge port of the conveyor 81, and a blanking collecting hopper is installed below the discharge port of the conveyor 81.
The second dust removal device comprises a second material collector 91 connected with the analyzer 15, an outlet at the top end of the second material collector 91 is connected with a second pulse dust collector 92, and a second induced draft fan 93 is installed on the second pulse dust collector 92; the third dust collector includes with grind the third loading head 94 that loading head 18 is connected, the top exit linkage of third loading head 94 has third pulse dust collector 95, install third draught fan 96 on the third pulse dust collector 95. The second material collector 91 is connected with the bottom discharge port of the third material collector 94 through a spiral reamer, and the discharge port of the spiral reamer is communicated with the black powder collecting bin.
The whole waste lithium battery recovery process has no harmful waste gas emission, the environment-friendly waste lithium battery recovery is realized, and the following technical measures are mainly taken for realizing no waste gas emission:
1. a vacuum heating/hydrolysis liquid removing device is arranged, the liquid removing device has the prominent functions of water spraying, hydration decomposition and heating pyrolysis of lithium hexafluorophosphate, and the functions of uniform stirring, drying dehydration and vacuum degassing can be realized in the vacuum heating/hydrolysis liquid removing tank body 22. And (3) spraying alkali liquor (such as NaOH solution) or pure water on the shredded lithium battery fragments for cleaning, stirring, drying and vacuum degassing. Reacting lithium hexafluorophosphate with water, hydrolyzing and pyrolyzing at high temperature (60-80 ℃) to form phosphorus pentafluoride and hydrogen fluoride gas, sending gas containing phosphorus pentafluoride and hydrogen fluoride pumped from the vacuum heating/hydrolysis liquid-removing tank 22 and the battery shredder 21 to an alkali liquor spray tower 41 for gas-water exchange through a vacuum pump 27, repeatedly absorbing sodium hydroxide alkali liquor to generate harmless sodium fluoride and phosphate products, and enabling air-containing components to pass through an active carbon adsorption box 6 and then be discharged in a non-toxic manner. Through adjusting pyrolysis and hydrolysis number of times and stirring time, reach complete decomposition, the absorption to lithium hexafluorophosphate, to the tail gas that does not totally absorb in vacuum heating/hydrolysis deliquoring device, through the alkali lye spray set of follow-up configuration, absorb the harmful component in the tail gas totally, air wherein passes through active carbon adsorption box 6 again, discharges into the atmosphere with clean air.
The reaction equation of the electrolyte in the vacuum heating/hydrolysis liquid-removing tank 22 is:
2. under the condition that the temperature in the vacuum pumping system, namely the vacuum pump 27 and the vacuum heating/hydrolysis liquid removal tank 22 is 60-80 ℃, the water vapor and the low-boiling-point carbonate solvent pass through the gas filter 23 to filter solid particles, and then pass through the gas condenser 24 to become liquid, and flow to the lower liquid container, so that most of the low-melting-point carbonate oily solvent is removed, and the subsequent solid separation is convenient.
3. More clear water is sprayed in the vacuum heating/hydrolysis liquid-removing tank body 22, lithium fluoride in the battery fragments is dissolved in the aqueous solution by stirring, and the aqueous solution of lithium fluoride is discharged and collected from a tank bottom valve.
4. At the earlier stage of the treatment process, in order to prevent the feeding of the shredder 21, a small amount of waste gas generated in the process of shredding the battery is discharged, a negative pressure adsorption pipeline is arranged at the top of the feeding of the shredder 21, the generated small amount of waste gas is absorbed, and the waste gas is directly sent into the alkali liquor spraying device through the gas filter 23, the gas condenser 24 and the vacuum pump 27, so that the subsequent treatment is carried out. The shredder 21 and the vacuum heating/hydrolysis liquid removing device adopt sealing measures to ensure that the pressure above 2kg is airtight after the inlet and the outlet are sealed.
5. And sending the clean waste lithium battery fragments subjected to liquid removal into a crusher 11 for subsequent treatment. Because the pole piece is subjected to liquid removal and baking, no residual electrolyte and lipid organic matters exist, and finally, the particles such as copper, aluminum and the like obtained through separation are cleaner.
6. And a magnetic separation and air separation mode is adopted when the battery shells are separated. The magnetic roller 82 is added on the conveyor 81, and simultaneously, a proportion winnowing device, namely a blower 83 is arranged, so that the ferromagnetic battery shell or the nonmagnetic battery shell can be separated. For the ferromagnetic battery shell, the iron shell is adsorbed by the magnetic force of the magnetic roller 82, and the ferromagnetic shell falls into the blanking collecting hopper along with the separation of the belt from the magnetic roller 82;
7. for the non-magnetic shell, a specific gravity air separation mode is adopted, a blower 83 is arranged at the bottom of the conveying belt, in the falling process of the fragments, the light pole pieces are blown into the rear crusher 14, and the shell with higher specific gravity falls into the blanking collecting hopper.
8. And subdividing the obtained copper-aluminum particles by utilizing the specific gravity liquid of the centrifugal rotation saturated saline water to obtain copper-aluminum element particles with higher purity.
As shown in fig. 5, the main process flow based on the system is as follows:
1. vacuum heating and liquid removing: and separating the crushed electrolyte remained in the pole piece to obtain the clean lithium electrode piece. The waste lithium batteries enter the shredder 21 through the battery feeding machine 29, are shredded into large fragments or strips, and are sent into the vacuum heating/hydrolysis liquid-removing tank 22 with the functions of heating, spraying and stirring at the lower part. During feeding, a negative pressure adsorption valve connected with the top of the shredder 21 is opened, a small amount of powder generated during shredding and electrolyte volatile gas are pumped away and enter a gas filter 23 and a gas condenser 24, carbonic acid organic matters in waste gas are liquefied and separated out under the cooling effect, residual gas is sent into an alkali liquor spray tower 41 through a vacuum pump 27, residual harmful gas is eliminated, the harmful gas which is not completely eliminated is further adsorbed by active carbon, and finally clean gas is sent into and removed.
After the feeding is finished, the battery feeding machine 29 is closed, the negative pressure adsorption valve arranged at the air outlet at the top end of the shredder 21 is closed, the feed inlet of the shredder 21 is closed, the discharge outlet of the vacuum heating tank body is closed, the alkali liquor spraying valve in the vacuum heating/hydrolysis liquid-removing tank body 22 is opened at the same time, the spiral stirring device in the vacuum heating/hydrolysis liquid-removing tank body 22 is opened, the alkali liquor and the battery fragments are fully mixed, after the alkali liquor is stirred for a certain time or the pressure in the tank reaches a certain pressure, the negative pressure adsorption valve at the air outlet end of the vacuum heating/hydrolysis liquid-removing tank body 22 is opened, the waste gas generated in the vacuum heating/hydrolysis liquid-removing tank body 22 is discharged into the gas condenser 24 through a vacuum pipeline, the carbonic organic matters are separated out from the gas condenser 24 through liquefaction and are discharged, the residual tail gas enters the alkali liquor spraying, and discharging the filtered clean air. Through the effects of heating, spraying alkali liquor and vacuumizing, the electrolyte on the pole piece is removed, and a relatively clean lithium battery pole piece is obtained.
2. Crushing: the battery fragments which are subjected to vacuum liquid removal and are clean are sent into a crusher 11 through a spiral feeding machine 12 and are further crushed into smaller fragments;
3. air flow separation: screening out the diaphragm paper in the crushed lithium battery through an airflow sorting machine 13, and screening out other materials to enter a shell sorting conveyor 81;
4. shell sorting: the shell generally comprises an iron shell and a stainless steel shell, and adopts two modes:
1) the magnetic separation mode is that the magnetic conductivity of an iron shell is utilized, a magnetic roller 82 is arranged at a discharge port of the conveyor 81, and the iron shell falls into a blanking collecting hopper after being adsorbed by the magnetic roller 82;
2) a specific gravity winnowing mode: the non-magnetic stainless steel shell is winnowed by specific gravity, the lower part of the discharge hole of the conveyor 81 is provided with the blower 83, the wind power and the falling height of the blower 83 are adjusted, the blanking collecting hopper arranged at the lower part of the stainless steel shell with high specific gravity is used for blowing the pole pieces and plastics with lighter specific gravity into the next-stage crusher 14.
5. Crushing: the crushed material and the pole piece pieces separated from the casing are further crushed into fine particles and sent to an analyzer 15.
6. Selecting powder according to the specific weight: dispersing the materials entering the interior by using an analyzer 15, adjusting air quantity and air speed, collecting the pole piece particles from the bottom by using the dead weight of the particles, conveying the pole piece particles to the next stage, and feeding the powder into a second pulse dust removal device from the top;
7. copper and aluminum metal sorting: large-particle copper-aluminum particles are separated from an outlet at the top of the swing screen 16 by using the swing screen 16, powder with the lightest specific gravity is separated from the bottom and sent into a black powder collecting bin, and powder with the middle part which can not be separated by specific gravity is sent into a grinding machine 17 and a rotary vibration screen 19, so that copper-aluminum fine particles and powder are separated.
8. And (3) separating the aluminum specific gravity: the separated metal particles are copper-aluminum mixed particle powder, and specific gravity separation is carried out on copper and aluminum by using specific gravity liquid by utilizing the density difference between copper (with the density of 8.9g/cm3) and aluminum (with the density of 2.7g/cm 3).
The invention realizes the waste lithium battery no-waste gas crushing recovery, solves the problem of harmful gas leakage caused by the decomposition of lithium hexafluorophosphate in the existing lithium battery recovery technology, cleans up the carbonate electrolyte solvent at the front end of the pole piece treatment, and is more beneficial to the crushing and the pure separation of the subsequent pole pieces; the problem of sorting the stainless steel shells of the batteries in the prior art is solved, and the stainless steel shells are separated by adopting a specific gravity sorting mode; completely separating the copper and aluminum particles by using specific gravity liquid; the lithium battery recovery process and the treatment system have the advantages of small pollution, high efficiency, reasonable treatment process, small environmental pollution in the treatment process and high recovery rate.
In China, the harmless and resource recycling of waste lithium batteries is urgent, and many universities and research institutes currently only stay in the theoretical and laboratory test stages. The application provides a topic group uses waste lithium cell innoxious, resource and industrialization recycle to carry out actual research and development as the key, this production line adopts vacuum pyrolysis and hydrolysis to take off liquid (take off lithium hexafluorophosphate) and clean formula to smash the separation and be main technological means, can directly get into the production line with the waste lithium cell module after the discharge treatment, separate out battery case piece at last, the diaphragm piece, copper aluminium foil particle and positive and negative pole piece dusting (black powder), behind the production line installs waste lithium cell electrolyte innoxious desorption device additional, the production line does not have harmful water, gas and dust emission.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The utility model provides a useless lithium cell recovery processing system of environment-friendly which characterized in that: the device comprises a battery crushing device, wherein the battery crushing device is connected with a vacuum heating/hydrolysis liquid removing device, and the battery crushing device and the vacuum heating/hydrolysis liquid removing device are connected with a harmful gas treatment device;
a fragment discharge port of the vacuum heating/hydrolysis liquid removal device is connected with a secondary crushing device, the secondary crushing device is connected with an airflow separator, the airflow separator is connected with a diaphragm recovery device, and the secondary crushing device, the airflow separator and the diaphragm recovery device are all connected with a first dust removal device;
the air flow separator is connected with a shell separation conveying device, a crusher is installed behind the shell separation conveying device, the discharge end of the crusher is connected with an analyzer, the discharge end of pole piece particles of the analyzer is connected with a swing sieve, and a powder outlet of the analyzer is connected with a second dust removal device; the middle outlet of the swing sieve is connected with a grinding machine, a discharge port of the grinding machine is connected with a grinding material collector, a powder outlet at the top end of the grinding material collector is connected with a third dust removal device, and an opening at the bottom end of the grinding material collector is connected with a rotary vibration sieve.
2. The environment-friendly waste lithium battery recycling system as set forth in claim 1, wherein: the battery crushing device comprises a battery feeding machine, and a discharging end of the battery feeding machine is connected with a shredder.
3. The environment-friendly waste lithium battery recycling system as set forth in claim 1, wherein: the vacuum heating/hydrolysis liquid-removing device comprises a vacuum heating/hydrolysis liquid-removing tank body, a heating device and a temperature/pressure/humidity detection device are installed in the vacuum heating/hydrolysis liquid-removing tank body, and a liquid spraying device and a spiral stirring device are further installed in the vacuum heating/hydrolysis liquid-removing tank body;
the liquid spraying device comprises a liquid tank arranged on one side of the vacuum heating/hydrolysis liquid removal tank body, the liquid tank is connected with a liquid pipe extending into the vacuum heating/hydrolysis liquid removal tank body, a spraying pipe connected with the liquid pipe is arranged in the vacuum heating/hydrolysis liquid removal tank body, and a plurality of spraying heads are arranged on the spraying pipe.
4. The environment-friendly waste lithium battery recycling system as set forth in claim 1, wherein: the harmful gas treatment device comprises a gas filter connected with a gas outlet port of the battery crushing device and a gas outlet port of the vacuum heating/hydrolysis liquid removal device, the gas filter is connected with a gas condenser, the gas condenser is connected with an alkali liquor spraying device through a vacuum pump, the gas outlet port of the alkali liquor spraying device is connected with an activated carbon adsorption tank, and the activated carbon adsorption tank is connected with a clean gas discharge pipe; a spray liquid condenser is arranged on the alkali liquor spray device; the spraying liquid condenser and the gas condenser are both connected with a refrigerating machine.
5. The environment-friendly waste lithium battery recycling system as set forth in claim 4, wherein: the alkali liquor spraying device comprises an alkali liquor spraying tower, the bottom end of the alkali liquor spraying tower is communicated with an alkali liquor circulating box, the spraying liquid condenser is arranged between the alkali liquor circulating box and the alkali liquor spraying tower, and the alkali liquor spraying tower is connected with a gas circulating device;
the gas circulating device comprises gas circulating pipes which are respectively communicated with the top end and the bottom end of the alkali liquor spraying tower, and a pipeline fan is arranged on each gas circulating pipe.
6. The environment-friendly waste lithium battery recycling system as set forth in claim 1, wherein: the secondary crushing device comprises a crusher, and a spiral feeding machine is arranged between the crusher and a fragment discharging port of the vacuum heating/hydrolysis liquid removing device.
7. The environment-friendly waste lithium battery recycling system as set forth in claim 1, wherein: the diaphragm recovery device comprises a diaphragm recovery box, a diaphragm discharge port is arranged at the top end of the air flow separator, the diaphragm discharge port is communicated with the diaphragm recovery box through a diaphragm induced air pipeline, and a diaphragm induced air is installed on the diaphragm induced air pipeline.
8. The environment-friendly waste lithium battery recycling system as set forth in claim 1, wherein: first dust collector include with the first loading head that secondary breaker connects, there is first pulse dust remover in the top export of first loading head through the pipe connection, install first draught fan on the first pulse dust remover, the bottom discharge gate of first loading head with the air current sorter intercommunication, the top discharge gate of diaphragm collection box pass through the pipeline with first pulse dust remover is connected.
9. The environment-friendly waste lithium battery recycling system as set forth in claim 1, wherein: the shell sorting and conveying device comprises a conveyor, a magnetic roller is installed at a discharge port of the conveyor, a blower for blowing light fragments into the crusher is installed below the discharge port of the conveyor, and a blanking collecting hopper is installed below the discharge port of the conveyor.
10. The environment-friendly waste lithium battery recycling system as set forth in claim 1, wherein: the second dust removal device comprises a second material collector connected with the analyzer, a second pulse dust collector is connected with an outlet at the top end of the second material collector, and a second induced draft fan is installed on the second pulse dust collector;
the third dust collector include with grind the third loading head that the loading head is connected, the top exit linkage of third loading head has the third pulse dust collector, install the third draught fan on the third pulse dust collector.
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