CN113161640A - System and method for recycling black powder through multistage pyrolysis of waste lithium batteries - Google Patents
System and method for recycling black powder through multistage pyrolysis of waste lithium batteries Download PDFInfo
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- CN113161640A CN113161640A CN202110147720.0A CN202110147720A CN113161640A CN 113161640 A CN113161640 A CN 113161640A CN 202110147720 A CN202110147720 A CN 202110147720A CN 113161640 A CN113161640 A CN 113161640A
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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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0038—Obtaining aluminium by other processes
- C22B21/0069—Obtaining aluminium by other processes from scrap, skimmings or any secondary source aluminium, e.g. recovery of alloy constituents
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to a system and a method for recycling black powder by multistage pyrolysis of waste lithium batteries, wherein the system comprises the following steps: the system comprises a disassembling system, a crushing and screening system, a primary pyrolysis system, a sorting system, a secondary pyrolysis system, a condensation and recovery system, a waste gas treatment system, a dust removal system and an inert gas system. The crushing and screening system is connected with the disassembling system and the primary pyrolysis system, the primary pyrolysis system is connected with the sorting system and the condensation recovery system, the sorting system is connected with the secondary pyrolysis system, and the dust removal system is connected with the crushing and screening system and the sorting system; exhaust gas treatment system and condensationThe recovery system is connected with the secondary pyrolysis system. The invention has small floor area, the recovery rate of black powder is more than 98 percent, the recovery rates of copper and aluminum are more than 98 percent, the removal rate of electrolyte is more than 99 percent, and the VOC (volatile organic compounds) discharged from waste gas is discharged<50mg/m3And no dioxin is generated. The device can avoid fire or explosion in the operation process. The electrolyte is separated under the low temperature condition, the energy consumption is reduced, and a large amount of waste gas is avoided.
Description
Technical Field
The invention belongs to the technical field of waste lithium battery recovery, and particularly relates to a system and a method for recovering black powder from waste lithium batteries through multistage pyrolysis.
Background
In 2020, the accumulated scrappage of the power lithium battery in China can reach 12-17 ten thousand tons, the theoretical scrappage of the power lithium battery is increased from 18.91Gwh in 2020 to 105.3Gwh in 2025, the waste lithium battery contains metals and organic matters such as cobalt, nickel, manganese, lithium, iron, aluminum and the like, the average content of lithium in the ternary battery is 1.9%, the content of nickel is 9%, the content of cobalt is 3%, the content of manganese is 4%, the content of copper is 13.3%, the content of aluminum is 12.7%, and the like. The waste lithium batteries can cause huge threat and pollution to the environment if not recycled, and simultaneously are also a waste to resources.
At present, the recovery technology of waste lithium batteries mainly comprises three types: (1) a pyrogenic recovery process; (2) a wet recovery process; (3) a combined treatment process of fire method and wet method.
The pyrogenic process recovery process is to treat the waste lithium ion battery by a reduction roasting mode, and a special smelting furnace is usually adopted to treat organic components such as electrolyte, plastics, binders and the like. The battery and the package are put into a smelting furnace for roasting, and pretreatment is not needed before roasting. Meanwhile, energy released by combustion of the graphite and the organic solvent can be utilized to obtain a mixture of metals such as cobalt, nickel and the like, so that the recycling of the metals is realized. The disadvantages of the pyrogenic process are: the energy consumption is large, other components in the electrolyte solution and the electrode can be converted into harmful components such as hydrofluoric acid or phosphorus pentoxide after being combusted, a large amount of waste gas is generated, the tail gas treatment cost is increased, and simultaneously, the air pollution is easily caused.
The wet recovery process is to disassemble and pretreat the waste batteries, dissolve the waste batteries in an acid-base solution, extract part of valuable metal elements, and extract the rest valuable metals by means of an ion exchange method, electrodeposition and the like. The disadvantages are as follows: low reaction speed, small throughput, complex process, high cost and low value of recovered products.
The combined fire-wet process includes smelting furnace to eliminate electrolyte, plastic, adhesive and other organic components to obtain mixture of Co, Ni and other metals, and wet separation to extract residual valuable metals. The disadvantages are as follows: large energy consumption, large amount of waste gas, high investment cost and operation cost and low recovery rate.
Disclosure of Invention
The invention aims to provide a system and a method for recycling black powder through multistage pyrolysis of waste lithium batteries, and the system and the method overcome the defects in the prior art.
In order to achieve the above purposes, the technical scheme adopted by the invention is as follows:
a system for recovering black powder by multistage pyrolysis of waste lithium batteries comprises: the system comprises a disassembling system, a crushing and screening system, a primary pyrolysis system, a sorting system, a secondary pyrolysis system, a condensation and recovery system, a waste gas treatment system, a dust removal system and an inert gas system;
the disassembling system is connected with the crushing and screening system, the crushing and screening system is connected with the primary pyrolysis system, the primary pyrolysis system is respectively connected with the sorting system and the condensation recovery system, the sorting system is connected with the secondary pyrolysis system, the dust removal system is respectively connected with the crushing and screening system and the sorting system, and the inert gas system is respectively connected with the crushing and screening system, the primary pyrolysis system and the condensation recovery system; the waste gas treatment system is respectively connected with the condensation recovery system and the secondary pyrolysis system;
the disassembling system is used for disassembling the waste lithium battery, separating plastic and a shell to obtain a module or a battery cell;
the crushing and screening system comprises a primary crushing system, a primary screening system, a secondary crushing system and a secondary screening system; the primary screening system is respectively connected with the primary crushing system and the secondary crushing system, and the secondary screening system is connected with the secondary crushing system; the primary crushing system is used for crushing the module, the primary screening system is used for separating the plastic and the shell, the secondary crushing system is used for crushing the material subjected to primary screening in a smaller particle size, and the secondary screening system is used for further removing the plastic and the shell;
the primary pyrolysis system comprises a low-temperature pyrolysis furnace and a heat-conducting oil heating system; the heat conducting oil heating system comprises a heat conducting oil heater for providing a heat source;
the sorting system comprises a tertiary screening device, a grinding device, a quaternary screening device, a winnowing device, a magnetic separation device and an eddy current separation device;
the secondary pyrolysis system comprises a rotary kiln pyrolysis furnace and a natural gas heating system;
the condensation recovery system comprises a condenser and a washing tower, wherein the condenser is connected with the washing tower through a pipeline; the condenser is used for condensing the condensable waste gas, part of electrolyte solvent is recovered after the condensable waste gas is condensed, other uncondensed waste gas enters the washing tower, and the washing tower is used for absorbing HF gas in the uncondensed waste gas;
the waste gas treatment system comprises an incinerator and a waste gas purification system.
The dust removal system includes: the device comprises an induced draft fan, a cloth bag dust removing device and a chimney, wherein the induced draft fan is connected with the cloth bag dust removing device through a pipeline, the cloth bag dust removing device is connected with the chimney through a pipeline, the cloth bag dust removing device is used for removing dust generated by a crushing and screening system and a sorting system, and the dust generated by the crushing and screening system and the sorting system is introduced into the dust removing system through the induced draft fan. The cloth bag dust removing device has the functions of water and oil resistance, and prevents water and oil from blocking the cloth bag.
On the basis of the scheme, nitrogen is selected as inert gas in the inert gas system, and the inert gas system is respectively connected with the crushing and screening system, the primary pyrolysis system and the condensation recovery system through pipelines. The inert gas is used to prevent ignition and explosion of the material.
On the basis of the scheme, the system for recycling black powder by multistage pyrolysis of the waste lithium batteries further comprises a waste heat recovery system, a second dust removal system and a third dust removal system, wherein the second dust removal system is respectively connected with the primary pyrolysis system and the condensation recovery system; the waste heat recovery system is respectively connected with the secondary pyrolysis system and the third dust removal system, and the third dust removal system is connected with the waste gas treatment system. The top of the low-temperature pyrolysis furnace of the primary pyrolysis system is connected with a dust removal system.
On the basis of the scheme, the crushing and screening system further comprises a buffer box and a quantitative feeder, and the quantitative feeder is arranged at the bottom of the buffer box.
On the basis of the scheme, the waste gas purification system comprises a waste heat recovery device, a cloth bag dust removal device, a multi-stage washing device, an activated carbon adsorption device and a chimney. Burn burning furnace and pass through the pipeline and be connected with waste heat recovery device, waste heat recovery device passes through the pipeline and is connected with sack dust collector, and sack dust collector passes through the pipeline and is connected with multistage washing device, and multistage washing device passes through the pipeline and is connected with active carbon adsorption device, and active carbon device passes through the pipeline and is connected with the chimney. The incinerator is used for carrying out incineration treatment on gas entering the incinerator; the activated carbon adsorption device is used for carrying out adsorption treatment on the uncondensed waste gas treated by the washing tower. And discharging the gas after adsorption treatment into the atmosphere through a chimney.
On the basis of the scheme, the rotary kiln pyrolysis furnace adopts indirect outer wall heating, and high-temperature flue gas generated by a natural gas heating system and the rotary kiln pyrolysis furnace are reversely heated.
A method for recycling black powder from waste lithium batteries through multistage pyrolysis comprises the following steps of:
step 1, firstly, disassembling a waste lithium battery by utilizing a disassembling system, and separating plastics and a shell to obtain a module or a battery cell;
step 2, the module or the battery cell enters the crushing and screening system through the belt conveyor, a rainproof cover is arranged above the belt conveyor, and the belt conveyor is provided with a stay wire protection device. A primary crushing system of the crushing and screening system is used for crushing the module, the materials after primary crushing enter the primary screening system, and the primary screening system is used for separating the plastic and the shell; the materials after primary screening enter a secondary crushing system to crush incoming materials with smaller particle sizes, and then the plastics and the shells are further removed through the secondary screening system. If the battery cell obtained in the step 1 is the battery cell, directly entering a secondary crushing system; the material after secondary screening enters a buffer tank;
and 3, conveying the materials processed by the crushing and screening system to the low-temperature pyrolysis furnace through a screw conveyor, wherein the screw conveyor is in a fully-sealed state. The material is dried, evaporated at low temperature and pyrolyzed at low temperature in a low-temperature pyrolysis furnace in sequence. The internal parts of the low-temperature pyrolysis furnace are of special structures, so that materials can be uniformly heated in a drying system, and black powder can fall off in the pyrolysis process. The heat conducting oil heating system provides a heat source for the low-temperature pyrolysis furnace.
The heat conduction oil is adopted for heating: the first heat conducting oil can be recycled, the second is convenient for temperature control, and the third is free of pollution. The primary pyrolysis system is used for recovering the low-boiling-point solvent and removing lithium hexafluorophosphate so as to ensure the safety of the subsequent working section and ensure that the subsequent working section achieves effective mechanical separation. The material of the low-temperature pyrolysis furnace and the heat conducting oil are reversely heated.
And 4, conveying the material subjected to primary pyrolysis to a tertiary screening device through a screw conveyor, and separating out heavy components and light components. Magnetic separation is carried out on the recombined materials to separate out magnetic materials and nonmagnetic materials, and eddy current separation is carried out on the nonmagnetic materials to separate out copper and aluminum. The light component enters a grinding device, the internal parts of the grinding device are of a special structure, black powder is stripped under the action of shearing force in the grinding device, a mixture of the black powder and copper and aluminum is separated out through screening for four times, and copper, aluminum and a small amount of black powder are separated out from the mixture of the copper and aluminum through a winnowing device.
And 5, allowing the black powder to enter a secondary pyrolysis system, further removing the electrolyte, and decomposing the electrolyte.
On the basis of the scheme, the waste gas generated by the primary pyrolysis system is condensed by a condenser after being dedusted, and part of the electrolyte solvent is condensed. The non-condensable gas passes through a washing tower to remove HF gas, then enters an incinerator for incineration treatment, the incinerated gas is subjected to waste heat recovery, cloth bag dust removal and multi-stage washing, activated carbon is adsorbed and then is discharged to the atmosphere, and VOC in the treated waste gas<50mg/m3. And waste gas generated by the secondary pyrolysis system enters an incinerator for incineration treatment after waste heat recovery and dust removal. The temperature of the incinerator is 850-900 ℃.
In the step 3, the low-temperature pyrolysis temperature is 80-150 ℃;
in the step 5, the rotary kiln pyrolysis furnace adopts indirect outer wall heating, high-temperature flue gas generated by a natural gas heating system and the rotary kiln pyrolysis furnace are reversely heated, and the secondary pyrolysis temperature is 300-400 ℃.
In the step 2, the grain diameter of the material after the secondary crushing is less than 20 mm.
The operation environment of the primary pyrolysis system and the secondary pyrolysis system is micro-negative pressure operation.
The invention has the beneficial effects that:
(1) the occupied area is small;
(2) mechanically stripping black powder and a binder; the recovery rate of the black powder is improved and is more than 98 percent.
(3) The recovery rates of copper and aluminum are > 98%.
(4) VOC in exhaust gas<50mg/m3。
(5) No dioxin is generated.
(6) The device can avoid fire or explosion in the operation process.
(7) The electrolyte removal rate is more than 99 percent.
(8) The electrolyte is separated under the low-temperature condition, so that the energy consumption is reduced, and a large amount of waste gas is avoided;
drawings
The invention has the following drawings:
FIG. 1 is a block diagram of the system of the present invention.
Figure 2 is a schematic view of the crushing and screening system of the present invention.
FIG. 3 is a flow chart of a method according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1 to 3, the system for recycling black powder by multistage pyrolysis of waste lithium batteries according to the present invention includes: the system comprises a disassembling system, a crushing and screening system, a primary pyrolysis system, a sorting system, a secondary pyrolysis system, a condensation and recovery system, a waste gas treatment system, a dust removal system and an inert gas system.
The disassembling system is connected with the crushing and screening system, the crushing and screening system is connected with the primary pyrolysis system, the primary pyrolysis system is respectively connected with the sorting system and the condensation recovery system, the sorting system is connected with the secondary pyrolysis system, the dust removal system is respectively connected with the crushing and screening system and the sorting system, and the inert gas system is respectively connected with the crushing and screening system, the primary pyrolysis system and the condensation recovery system; the waste gas treatment system is respectively connected with the condensation recovery system and the secondary pyrolysis system;
the disassembling system is used for disassembling the waste lithium battery, separating plastic and a shell to obtain a module or a battery cell;
the crushing and screening system comprises a primary crushing system, a primary screening system, a secondary crushing system and a secondary screening system; the primary screening system is respectively connected with the primary crushing system and the secondary crushing system, and the secondary screening system is connected with the secondary crushing system; the primary crushing system is used for crushing the module, the primary screening system is used for separating plastic and the shell, the secondary crushing system is used for crushing the materials after primary screening in a smaller grain size, and the secondary screening system is used for further removing the plastic and the shell.
The crushing and screening system further comprises a buffer box and a quantitative feeder, and the quantitative feeder is arranged at the bottom of the buffer box.
The primary pyrolysis system is used for recovering the low-boiling-point solvent and removing lithium hexafluorophosphate so as to ensure the safety of the subsequent working section. The primary pyrolysis system comprises a low-temperature pyrolysis furnace and a heat-conducting oil heating system. The top of the low-temperature pyrolysis furnace is connected with a dust removal system. The main equipment of the heat-conducting oil heating system is a heat-conducting oil heater which is mainly used for providing a heat source.
The sorting system comprises a tertiary screening device, a grinding device, a quaternary screening device, a winnowing device, a magnetic separation device and an eddy current separation device;
the secondary pyrolysis system is used for further removing electrolyte and decomposing electrolyte. The secondary pyrolysis system comprises a rotary kiln pyrolysis furnace and a natural gas heating system; the rotary kiln pyrolysis furnace adopts indirect outer wall heating, and high-temperature flue gas generated by a natural gas heating system and the rotary kiln pyrolysis furnace are reversely heated.
The condensation recovery system comprises a condenser and a washing tower, wherein the condenser is connected with the washing tower through a pipeline; the condenser is used for condensing the condensable waste gas, part of electrolyte solvent is recovered after the condensable waste gas is condensed, and other non-condensable waste gas enters the washing tower and is used for absorbing gases such as HF (hydrogen fluoride) in the non-condensable waste gas;
the waste gas treatment system comprises an incinerator and a waste gas purification system. The waste gas purification system comprises a waste heat recovery device, a cloth bag dust removal device, a multi-stage washing device, an active carbon adsorption device and a chimney. Burn burning furnace and pass through the pipeline and be connected with waste heat recovery device, waste heat recovery device passes through the pipeline and is connected with sack dust collector, and sack dust collector passes through the pipeline and is connected with multistage washing device, and multistage washing device passes through the pipeline and is connected with active carbon adsorption device, and active carbon device passes through the pipeline and is connected with the chimney. The incinerator is used for carrying out incineration treatment on gas entering the incinerator; the activated carbon adsorption device is used for carrying out adsorption treatment on the uncondensed waste gas treated by the washing tower. And discharging the gas after adsorption treatment into the atmosphere through a chimney.
The dust removal system includes: the device comprises an induced draft fan, a cloth bag dust removing device and a chimney, wherein the induced draft fan is connected with the cloth bag dust removing device through a pipeline, the cloth bag dust removing device is connected with the chimney through a pipeline, the cloth bag dust removing device is used for removing dust generated by a crushing and screening system and a sorting system, and the dust generated by the crushing and screening system and the sorting system is introduced into the dust removing system through the induced draft fan. The cloth bag dust removing device has the functions of water and oil resistance, and prevents water and oil from blocking the cloth bag.
An inert gas system: and the nitrogen is selected as inert gas, and the inert gas system is respectively connected with the crushing and screening system, the primary pyrolysis system and the condensation recovery system through pipelines. The inert gas is used to prevent ignition and explosion of the material.
On the basis of the scheme, the system for recycling black powder by multistage pyrolysis of the waste lithium batteries further comprises a waste heat recovery system, a second dust removal system and a third dust removal system, wherein the second dust removal system is respectively connected with the primary pyrolysis system and the condensation recovery system; the waste heat recovery system is respectively connected with the secondary pyrolysis system and the third dust removal system, and the third dust removal system is connected with the waste gas treatment system.
A method for recycling black powder from waste lithium batteries through multistage pyrolysis comprises the following steps of:
step 1, firstly, disassembling the waste lithium battery by utilizing a disassembling system, and separating plastic and a shell to obtain a module or a battery cell.
Step 2, the module or the battery cell enters the crushing and screening system through the belt conveyor, a rainproof cover is arranged above the belt conveyor, and the belt conveyor is provided with a stay wire protection device. The primary crushing system of the crushing and screening system is mainly used for crushing the module, materials after primary crushing enter the primary screening system, and the primary screening system is mainly used for separating plastics and shells. The materials after primary screening enter a secondary crushing system to crush incoming materials with smaller particle sizes, and then the plastics and the shells are further removed through the secondary screening system. And if the battery cell obtained in the step 1 is the battery cell, directly entering a secondary crushing system. And the material after secondary screening enters a buffer tank.
And 3, conveying the materials processed by the crushing and screening system to the low-temperature pyrolysis furnace through a screw conveyor, wherein the screw conveyor is in a fully-sealed state. The material is dried, evaporated at low temperature and pyrolyzed at low temperature in a low-temperature pyrolysis furnace in sequence. The internal parts of the low-temperature pyrolysis furnace are of special structures, so that materials can be uniformly heated in a drying system, and black powder can fall off in the pyrolysis process. The heat conducting oil heating system provides a heat source for the low-temperature pyrolysis furnace.
The heat conduction oil is adopted for heating: the first heat conducting oil can be recycled, the second is convenient for temperature control, and the third is free of pollution. The primary pyrolysis system is used for recovering the low-boiling-point solvent and removing lithium hexafluorophosphate so as to ensure the safety of the subsequent working section and ensure that the subsequent working section achieves effective mechanical separation. The material of the low-temperature pyrolysis furnace and the heat conducting oil are reversely heated.
And 4, conveying the material subjected to primary pyrolysis to a tertiary screening device through a screw conveyor, and separating out heavy components and light components. Magnetic separation is carried out on the recombined materials to separate out magnetic materials and nonmagnetic materials, and eddy current separation is carried out on the nonmagnetic materials to separate out copper and aluminum. The light component enters a grinding device, the internal parts of the grinding device are of a special structure, black powder is stripped under the action of shearing force in the grinding device, a mixture of the black powder and copper and aluminum is separated out through screening for four times, and copper, aluminum and a small amount of black powder are separated out from the mixture of the copper and aluminum through a winnowing device.
And 5, allowing the black powder to enter a secondary pyrolysis system, further removing the electrolyte, and decomposing the electrolyte.
On the basis of the scheme, the waste gas generated by the primary pyrolysis system is condensed by a condenser after being dedusted, and part of the electrolyte solvent is condensed. The non-condensable gas passes through a washing tower to remove HF gas, then enters an incinerator for incineration treatment, the incinerated gas is subjected to waste heat recovery, cloth bag dust removal and multi-stage washing, activated carbon is adsorbed and then is discharged to the atmosphere, and VOC in the treated waste gas<50mg/m3. And waste gas generated by the secondary pyrolysis system enters an incinerator for incineration treatment after waste heat recovery and dust removal. The temperature of the incinerator is 850-900 ℃.
In the step 3, the low-temperature pyrolysis temperature is 80-150 ℃;
in the step 5, the rotary kiln pyrolysis furnace adopts indirect outer wall heating, high-temperature flue gas generated by a natural gas heating system and the rotary kiln pyrolysis furnace are reversely heated, and the secondary pyrolysis temperature is 300-400 ℃.
In the step 2, the grain diameter of the material after the secondary crushing is less than 20 mm.
The operation environment of the primary pyrolysis system and the secondary pyrolysis system is micro-negative pressure operation.
On the basis of the scheme, gas, dust and the like generated by the crushing and screening system and the sorting system are discharged to the atmosphere after being dedusted by the dedusting system.
The above embodiments are merely illustrative, and not restrictive, and those skilled in the relevant art can make various changes and modifications without departing from the spirit and scope of the invention, and therefore all equivalent technical solutions also belong to the scope of the invention.
Those not described in detail in this specification are within the skill of the art.
Claims (10)
1. The utility model provides a system for black powder is retrieved in multistage pyrolysis of old and useless lithium cell which characterized in that includes: the system comprises a disassembling system, a crushing and screening system, a primary pyrolysis system, a sorting system, a secondary pyrolysis system, a condensation and recovery system, a waste gas treatment system, a dust removal system and an inert gas system;
the disassembling system is connected with the crushing and screening system, the crushing and screening system is connected with the primary pyrolysis system, the primary pyrolysis system is respectively connected with the sorting system and the condensation recovery system, the sorting system is connected with the secondary pyrolysis system, the dust removal system is respectively connected with the crushing and screening system and the sorting system, and the inert gas system is respectively connected with the crushing and screening system, the primary pyrolysis system and the condensation recovery system; the waste gas treatment system is respectively connected with the condensation recovery system and the secondary pyrolysis system;
the disassembling system is used for disassembling the waste lithium battery, separating plastic and a shell to obtain a module or a battery cell;
the crushing and screening system comprises a primary crushing system, a primary screening system, a secondary crushing system and a secondary screening system; the primary screening system is respectively connected with the primary crushing system and the secondary crushing system, and the secondary screening system is connected with the secondary crushing system; the primary crushing system is used for crushing the module, the primary screening system is used for separating the plastic and the shell, the secondary crushing system is used for crushing the material subjected to primary screening in a smaller particle size, and the secondary screening system is used for further removing the plastic and the shell;
the primary pyrolysis system comprises a low-temperature pyrolysis furnace and a heat-conducting oil heating system; the heat conducting oil heating system comprises a heat conducting oil heater for providing a heat source;
the sorting system comprises a tertiary screening device, a grinding device, a quaternary screening device, a winnowing device, a magnetic separation device and an eddy current separation device;
the secondary pyrolysis system comprises a rotary kiln pyrolysis furnace and a natural gas heating system;
the condensation recovery system comprises a condenser and a washing tower, wherein the condenser is connected with the washing tower through a pipeline; the condenser is used for condensing the condensable waste gas, part of electrolyte solvent is recovered after the condensable waste gas is condensed, other uncondensed waste gas enters the washing tower, and the washing tower is used for absorbing HF gas in the uncondensed waste gas;
the waste gas treatment system comprises an incinerator and a waste gas purification system;
the dust removal system includes: the device comprises an induced draft fan, a cloth bag dust removal device and a chimney, wherein the induced draft fan is connected with the cloth bag dust removal device through a pipeline; the cloth bag dust removing device has the functions of water and oil resistance, and prevents water and oil from blocking the cloth bag.
2. The system for recycling black powder through multistage pyrolysis of waste lithium batteries as claimed in claim 1, wherein: in the inert gas system, nitrogen is selected as inert gas, and the inert gas system is respectively connected with the crushing and screening system, the primary pyrolysis system and the condensation recovery system through pipelines; the inert gas is used to prevent ignition and explosion of the material.
3. The system for recycling black powder through multistage pyrolysis of waste lithium batteries as claimed in claim 1, wherein: the system for recycling black powder by multistage pyrolysis of the waste lithium batteries further comprises a waste heat recovery system, a second dust removal system and a third dust removal system, wherein the second dust removal system is respectively connected with the primary pyrolysis system and the condensation recovery system; the waste heat recovery system is respectively connected with the secondary pyrolysis system and the third dust removal system, and the third dust removal system is connected with the waste gas treatment system; the top of the low-temperature pyrolysis furnace of the primary pyrolysis system is connected with a dust removal system.
4. The system for recycling black powder through multistage pyrolysis of waste lithium batteries as claimed in claim 1, wherein: the crushing and screening system further comprises a buffer box and a quantitative feeder, and the quantitative feeder is arranged at the bottom of the buffer box.
5. The system for recycling black powder through multistage pyrolysis of waste lithium batteries as claimed in claim 1, wherein: the waste gas purification system comprises a waste heat recovery device, a cloth bag dust removal device, a multi-stage washing device, an active carbon adsorption device and a chimney; the incinerator is connected with the waste heat recovery device through a pipeline, the waste heat recovery device is connected with the cloth bag dust removal device through a pipeline, the cloth bag dust removal device is connected with the multistage washing device through a pipeline, the multistage washing device is connected with the activated carbon adsorption device through a pipeline, and the activated carbon device is connected with the chimney through a pipeline; the incinerator is used for carrying out incineration treatment on gas entering the incinerator; the activated carbon adsorption device is used for carrying out adsorption treatment on the uncondensed waste gas treated by the washing tower; and discharging the gas after adsorption treatment into the atmosphere through a chimney.
6. The system for recycling black powder through multistage pyrolysis of waste lithium batteries as claimed in claim 1, wherein: the rotary kiln pyrolysis furnace adopts indirect outer wall heating, and high-temperature flue gas generated by a natural gas heating system and the rotary kiln pyrolysis furnace are reversely heated.
7. A method for recycling black powder from waste lithium batteries through multistage pyrolysis by applying the system of any one of claims 1 to 6, which is characterized by comprising the following steps:
step 1, firstly, disassembling a waste lithium battery by utilizing a disassembling system, and separating plastics and a shell to obtain a module or a battery cell;
step 2, enabling the module or the battery cell to enter a crushing and screening system through a belt conveyor; a primary crushing system of the crushing and screening system is used for crushing the module, the materials after primary crushing enter the primary screening system, and the primary screening system is used for separating the plastic and the shell; the materials after primary screening enter a secondary crushing system, incoming materials are crushed into smaller particle sizes, and then plastics and shells are further removed through the secondary screening system; if the battery cell obtained in the step 1 is the battery cell, directly entering a secondary crushing system; the material after secondary screening enters a buffer tank;
3, conveying the materials processed by the crushing and screening system to a low-temperature pyrolysis furnace through a screw conveyor; the material is dried, evaporated at low temperature and pyrolyzed at low temperature in a low-temperature pyrolysis furnace in sequence; the material can be uniformly heated in the drying system in the low-temperature pyrolysis furnace, and the black powder can fall off in the pyrolysis process; the heat conducting oil heating system provides a heat source for the low-temperature pyrolysis furnace;
step 4, conveying the material subjected to primary pyrolysis to a tertiary screening device through a screw conveyor, and separating out heavy components and light components; separating the recombinant components by magnetic separation to obtain magnetic substances and non-magnetic substances, and separating copper and aluminum from the non-magnetic substances by eddy current separation; the light component enters a grinding device, the black powder is peeled off under the action of shearing force in the grinding device, the mixture of the black powder and copper and aluminum is separated out through four-time screening, and the copper and aluminum mixture is separated out of copper, aluminum and black powder through a winnowing device;
and 5, allowing the black powder to enter a secondary pyrolysis system, further removing the electrolyte, and decomposing the electrolyte.
8. The method for recycling black powder through multistage pyrolysis of waste lithium batteries as claimed in claim 7, wherein the method comprises the following steps: the waste gas generated by the primary pyrolysis system is dedusted and condensed by a condenser, and part of electrolyte solvent is condensed; the non-condensable gas passes through a washing tower to remove HF gas, then enters an incinerator for incineration treatment, the incinerated gas is discharged to the atmosphere after waste heat recovery, cloth bag dust removal, multi-stage washing and activated carbon adsorption, and VOC in the treated waste gas<50mg/m3(ii) a Waste gas generated by the secondary pyrolysis system enters an incinerator for incineration treatment after waste heat recovery and dust removal; the temperature of the incinerator is 850-900 ℃.
9. The method for recycling black powder through multistage pyrolysis of waste lithium batteries as claimed in claim 7, wherein the method comprises the following steps: in the step 2, a rain cover is arranged above the belt conveyor, and the belt conveyor is provided with a stay wire protection device; the grain diameter of the material after the secondary crushing is less than 20 mm.
10. The method for recycling black powder through multistage pyrolysis of waste lithium batteries as claimed in claim 7, wherein the method comprises the following steps: in step 3, the screw conveyor is in a fully sealed state; the low-temperature pyrolysis temperature is 80-150 ℃;
in the step 5, the rotary kiln pyrolysis furnace adopts indirect outer wall heating, high-temperature flue gas generated by a natural gas heating system and the rotary kiln pyrolysis furnace are reversely heated, and the secondary pyrolysis temperature is 300-400 ℃;
the operation environment of the primary pyrolysis system and the secondary pyrolysis system is micro-negative pressure operation.
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