CN114388920A - Recycling system and recycling method for electrolyte of retired lithium battery - Google Patents

Recycling system and recycling method for electrolyte of retired lithium battery Download PDF

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Publication number
CN114388920A
CN114388920A CN202111558067.3A CN202111558067A CN114388920A CN 114388920 A CN114388920 A CN 114388920A CN 202111558067 A CN202111558067 A CN 202111558067A CN 114388920 A CN114388920 A CN 114388920A
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gas
volatile gas
condenser
crusher
heat exchanger
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CN202111558067.3A
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Chinese (zh)
Inventor
辛国伟
池子翔
王向辉
刘威
蔡振宇
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Sunertz Environmental Protection Beijing Co ltd
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Sunertz Environmental Protection Beijing Co ltd
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Priority to CN202111558067.3A priority Critical patent/CN114388920A/en
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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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
    • F27D17/004—Systems for reclaiming waste heat
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D17/00—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases
    • F27D17/008—Arrangements for using waste heat; Arrangements for using, or disposing of, waste gases cleaning gases
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D9/00—Heat-exchange apparatus having stationary plate-like or laminated conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
    • 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 belongs to the technical field of retired lithium battery recovery, and relates to a retired lithium battery electrolyte recovery system and a retired lithium battery electrolyte recovery method, wherein the recovery system comprises: a crushing and volatilizing subsystem, a dust collecting and heat exchanging subsystem, a condensing subsystem and a plurality of sets of absorbing and preparing subsystems; the crushing and volatilizing subsystem is connected with the dust collecting and heat exchanging subsystem; the dust collection and heat exchange subsystem is connected with the condensation subsystem; the condensing subsystem is connected with a plurality of sets of absorbing and preparing subsystems; by adopting the technical scheme of the application, the electrolyte product is recovered and produced, and the method has better economic benefit; the heat exchanger is arranged, so that heat is reasonably utilized, and energy consumption is reduced; recycling the recycle gas, reducing the consumption of inert gas, improving the yield of F, P and organic solvent, and simultaneously reducing the generation and discharge of three wastes; the flow, the equipment and the process are simple to control, and the industrial application is easy.

Description

Recycling system and recycling method for electrolyte of retired lithium battery
Technical Field
The invention belongs to the technical field of retired lithium battery recovery, and relates to a retired lithium battery electrolyte recovery system and a retired lithium battery electrolyte recovery method.
Background
The rapid development of new energy sources brings a large number of retired lithium batteries, the comprehensive utilization of resources in the retired lithium batteries is determined by the era background, and particularly under the background of double carbon, the recovery of the retired lithium batteries also urgently needs a low-energy-consumption, low-emission and high-efficiency recovery process. Lithium batteries are mainly classified into lithium iron phosphate series, lithium cobaltate series, ternary nickel cobalt manganese series, lithium manganate series, and the like. Although the variety is wide, the structure is substantially the same as the components except for the positive electrode powder. The lithium battery mainly comprises the following structural components: the battery comprises a shell, a positive electrode, a negative electrode, a diaphragm and electrolyte. The main stream recycling process is to discharge the retired lithium battery, then carry out nitrogen protection crushing and low-temperature drying (or high-temperature pyrolysis) on the electrolyte waste gas, then carry out multi-stage separation, and respectively select out a shell, a diaphragm, positive copper particles (or powder), negative aluminum particles (or powder), positive and negative black powder and the like, wherein the high-value components such as the positive electrode, the negative electrode and the black powder, and the easily separated components such as the shell and the diaphragm can be well recycled, but the electrolyte recycling process which is suitable for industrialization is fresh.
The biggest problems in recycling the electrolyte are: h in the air is difficult to isolate in the stages of crushing, sorting and the like of the retired lithium battery2O and O2Etc., so that the organic solvent is easily decomposed and a large amount of POF is produced from F and P3HF and H3PO4And the waste can be only collected and treated as hazardous waste, but cannot be effectively recycled.
At present, the common method is that low-temperature volatilization or high-temperature pyrolysis is carried out on a crushed lithium battery, then volatile gas is condensed to obtain an electrolyte solvent which is used as hazardous waste for disposal, F and P elements in the electrolyte are sprayed by an alkaline solution, almost all the F and P elements enter a spraying liquid (or spraying slag), and the spraying liquid (or spraying slag) is used as hazardous waste for disposal; or to volatilizing the gas and burning, then handle burning waste gas, F and P still get into and spray liquid (or spray the sediment), need carry out the useless processing of danger, and high temperature burning not only brings a large amount of carbon emissions, has the risk that certain dioxin produced moreover. The invention is provided in view of the above.
Disclosure of Invention
The technical problems to be solved by the invention are as follows:
(1) recycling electrolyte of the retired lithium battery;
(2) an inert gas protective cover is arranged to isolate H in the air2O and O2Guarantee is provided for qualified electrolyte products;
(3) the heat exchanger is arranged, so that heat is reasonably utilized, and energy consumption is reduced;
(4) recycling the circulating gas to reduce the consumption of inert gas;
(5) the yield of fluorine, phosphorus and electrolyte solvent is improved;
(6) and simultaneously reduces the generation and discharge of three wastes.
Aiming at the technical problems, the technical scheme is as follows:
a retired lithium battery electrolyte recovery system comprising: a crushing and volatilizing subsystem, a dust collecting and heat exchanging subsystem, a condensing subsystem and a plurality of sets of absorbing and preparing subsystems;
the crushing and volatilization subsystem comprises: a storage bin, a crusher and a volatilization furnace kiln;
the dust collection and heat exchange subsystem comprises: a heat exchanger and a dust collector;
the condensing subsystem includes: a condenser;
each set of absorption and deployment subsystems includes: an absorption tower and a blending tank;
the storage bin is connected with a crusher, and the crusher is connected with the volatilization furnace kiln;
the volatilization furnace kiln is connected with a dust collector, and the dust collector is connected with a heat exchanger;
the heat exchanger is connected with the condenser; the condenser is connected with a plurality of sets of absorption and allocation subsystems through valves;
in each set of absorption and allocation subsystem, the absorption tower is connected with the allocation tank;
dry inert gas is introduced into the crusher, the volatilization furnace kiln and the blending tank;
micro negative pressure is kept in the crusher, the volatilization furnace kiln and the blending tank;
the feed bin is used for: adding a retired lithium battery;
the crusher is used for: crushing the retired lithium battery in the storage bin;
the volatilization furnace kiln is used for: volatilizing the materials crushed by the crusher to generate volatilized materials and hot volatilized gas;
the volatilized materials enter a subsequent lithium battery recovery process;
the dust collector is used for: receiving hot volatile gas generated by the volatilization furnace kiln, and collecting dust for the hot volatile gas;
the heat exchanger is used for: receiving the hot volatile gas after dust collection, and carrying out temperature reduction and precooling on the hot volatile gas to form precooled volatile gas;
the condenser is used for: receiving the precooled volatile gas, condensing out the organic solvent, and outputting uncondensed volatile gas;
the non-condensed volatile gas comprises: PF (particle Filter)5And a small amount of organic gases that are not condensed;
the organic solvent includes: dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), and the like;
the absorption tower is used for: receiving the organic solvent condensed by the condenser, adding LiF (lithium fluoride) into the absorption tower, and absorbing uncondensed volatile gas;
the PF5React with LiF to generate LiPF6；
LiPF6Mixing the electrolyte in an organic solvent to form an electrolyte;
the blending tank is used for: receiving the electrolyte which is analyzed to reach the standard in the absorption tower, and adding an additive to produce an electrolyte product;
the electrolyte after reaching the standard meets the industrial standard: SJ/T11568-2016;
and the qualified electrolyte contains LiPF6The content of (A) is as follows: 0.9-1.5 mol/L;
with addition of LiF in the absorption columnThe amount is also determined according to LiPF in the electrolyte after reaching the standard6Determining the content of (A);
the additive is used for: the performance of various aspects of the electrolyte product is improved.
On the basis of the technical scheme, the additive comprises: EC additives and PC additives, etc.
On the basis of the technical scheme, the crusher, the volatilization furnace kiln and the absorption tower are all connected with a heat exchanger;
the volatile gas which is not absorbed in the absorption tower flows back to the heat exchanger again to exchange heat with the hot volatile gas in the heat exchanger, and the heat exchanger outputs hot circulating gas;
the uncondensed volatile gas is sent into an absorption tower to be absorbed or reflows to a heat exchanger again, and exchanges heat with hot volatile gas in the heat exchanger, and the heat exchanger outputs hot circulating gas;
PF in the uncondensed volatile gas5When the content of the volatile gas is low, the volatile gas which is not condensed flows back to the heat exchanger again to exchange heat with the hot volatile gas in the heat exchanger, and the heat exchanger outputs hot circulating gas;
PF in the uncondensed volatile gas5When the content of the volatile gas is high, the volatile gas which is not condensed is sent into an absorption tower to be absorbed;
hot circulating gas is introduced into the crusher and the volatilization furnace kiln to reduce the use amount of inert gas;
and micro negative pressure is kept in the crusher and the volatilization furnace kiln.
On the basis of the above technical solution, the uncondensed volatile gas further includes: inert gas (mixed in by the inert gas in the crusher and the volatilization furnace).
Since the hot volatile gas and the hot circulating gas contain a large amount of organic solvent gas, and environmentally harmful substances such as F and P, the slight negative pressure is maintained to prevent the above harmful substances from escaping in an unorganized manner.
The pressure control of the specific micro-negative pressure is adjusted according to the tightness of the equipment and the detection of the content of harmful gases in the process in the equipment.
On the basis of the technical scheme, the micro negative pressure is as follows: generally 5 to 400Pa below the atmospheric pressure.
On the basis of the technical scheme, the retired lithium battery electrolyte recovery system further comprises an induced draft fan;
the crusher, the volatilization furnace kiln and the blending tank are all connected with an induced draft fan;
the draught fan is used for: keeping the micro negative pressure in the crusher, the volatilization furnace kiln and the blending tank.
On the basis of the technical scheme, the air in the storage bin is replaced dry inert gas;
inert gas protective covers are arranged outside the crusher, the volatilization furnace kiln, the heat exchanger, the dust collector, the condenser, the absorption tower and the blending tank;
and introducing dry inert gas into the inert gas protective cover, and keeping the micro-positive pressure.
On the basis of the technical scheme, the micro-positive pressure is as follows: generally 5 to 400Pa higher than the atmospheric pressure.
On the basis of the technical scheme, the dust collector comprises: a high temperature bag collector;
the heat exchanger is as follows: a plate heat exchanger;
the condenser is as follows: a pipe condenser;
the condensing temperature of the condenser is as follows: -20 to 20 ℃;
the inert gas is: one of nitrogen, helium and argon or a mixture of the above gases.
On the basis of the technical scheme, the inert gas is as follows: nitrogen gas.
On the basis of the technical scheme, the condenser is sequentially divided into a front-section condenser, a middle-section condenser and a rear-section condenser;
the condensing temperature of the front-section condenser is as follows: 5-20 ℃;
the condensing temperature of the middle section condenser is as follows: -5 ℃ to 5 ℃;
the condensation temperature of the rear-section condenser is as follows: -20 ℃ to-5 ℃;
and the precooled volatile gas sequentially enters a front-section condenser, a middle-section condenser and a rear-section condenser.
On the basis of the technical scheme, the temperature of the volatilization furnace kiln for volatilizing the materials crushed by the crusher is as follows: 80-250 ℃; the temperature for absorbing the non-condensed volatile gas in the absorption tower is as follows: 0 to 50 ℃.
On the basis of the technical scheme, the temperature of the volatilization furnace kiln for volatilizing the materials crushed by the crusher is as follows: 180 ℃;
the temperature for absorbing the non-condensed volatile gas in the absorption tower is as follows: at 25 ℃.
On the basis of the technical scheme, the heat exchanger utilizes the non-condensed volatile gas or the non-absorbed volatile gas in the absorption tower to exchange heat, the temperature of the hot volatile gas is reduced and precooled, and the temperature of the non-condensed volatile gas or the non-absorbed volatile gas in the absorption tower is increased and preheated.
PF in the uncondensed volatile gas5When the concentration of the volatile gas is low, the uncondensed volatile gas is directly recycled, and hot circulating gas is formed by a heat exchanger and is introduced into a crusher and a volatilization furnace kiln; PF in the uncondensed volatile gas5When the concentration of the volatile gas is high, the volatile gas is absorbed by the absorption tower and then recycled, and hot circulating gas is formed by the heat exchanger and is introduced into the crusher and the volatilization furnace kiln; the specific operation can be flexibly controlled according to different raw materials and working conditions.
An electrolyte recovery method applying the electrolyte recovery system of the retired lithium battery comprises the following steps:
s1, adding the retired lithium battery into a bin;
s2, conveying the retired lithium battery in the bin into a crusher for crushing;
s3, conveying the material crushed by the crusher into a volatilization kiln;
s4, volatilizing the materials crushed by the crusher by a volatilizing kiln to generate volatilized materials and hot volatilized gas;
s5, receiving hot volatile gas generated by the volatilization furnace kiln by a dust collector, and collecting dust from the hot volatile gas;
s6, receiving the hot volatile gas after dust collection by a heat exchanger, and cooling and precooling the hot volatile gas to form precooled volatile gas;
s7, the condenser receives the precooled volatile gas, condenses out the organic solvent and outputs the non-condensed volatile gas;
s8, the absorption tower receives the organic solvent condensed by the condenser and the uncondensed volatile gas, lithium fluoride is added into the absorption tower, and the uncondensed volatile gas is absorbed;
and S9, the blending tank receives the electrolyte which is analyzed to reach the standard in the absorption tower, and the additive is added to produce an electrolyte product.
The invention has the following beneficial technical effects:
(1) electrolyte products are recovered and produced, and the method has better economic benefit;
(2) the heat exchanger is arranged, so that heat is reasonably utilized, and energy consumption is reduced;
(3) the recycling of the circulating gas (namely the hot circulating gas) reduces the consumption of inert gas, improves the yield of F, P and organic solvent, and reduces the generation and discharge of three wastes;
(4) the flow, the equipment and the process are simple to control, and the industrial application is easy.
Drawings
The invention has the following drawings:
FIG. 1 is a schematic block diagram of a connection of an electrolyte recovery system for a retired lithium battery according to the present application;
FIG. 2 is a schematic flow chart illustrating the steps of electrolyte recovery for a retired lithium battery according to the present application.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings.
As shown in fig. 1-2, the electrolyte recovery system for retired lithium batteries according to the present invention comprises the following subsystems: a crushing and volatilizing subsystem, a dust collecting and heat exchanging subsystem, a condensing subsystem and an absorbing and preparing subsystem.
1. A crushing and volatilizing subsystem: the crushing and volatilization subsystem comprises: a storage bin, a crusher and a volatilization furnace kiln; the ex-service lithium battery is added into a stock bin, air in the stock bin is replaced by dry inert gas, the ex-service lithium battery enters a crusher with inert gas protection, and the crushed material enters a volatilization furnace kiln with inert gas protection. Dry inert gas or thermal cycle gas from a heat exchanger is introduced into the crusher and the volatilization furnace kiln, the thermal cycle gas is preferentially used, and micro negative pressure is kept in the crusher and the volatilization furnace kiln. Inert gas protective covers are arranged outside the crusher and the volatilization furnace kiln, dry inert gas is introduced into the inert gas protective covers, and micro-positive pressure is kept. And the volatilized materials enter a subsequent lithium battery recovery process, and hot volatile gas enters a dust collection and heat exchange subsystem. The inert gas is one or a mixture of several gases of nitrogen, helium and argon, preferably nitrogen; the temperature of the volatilization furnace for volatilizing the materials crushed by the crusher is as follows: 80-250 ℃, preferably 180 ℃;
2. dust collection and heat exchange subsystems: introducing hot volatile gas generated by the volatilization kiln into a heat exchanger after dust is collected by a dust collector, exchanging heat with the volatile gas which is not condensed or the volatile gas which is not absorbed in an absorption tower in the heat exchanger, cooling and precooling the hot volatile gas, and heating and preheating the volatile gas which is not condensed or the volatile gas which is not absorbed in the absorption tower (when PF is contained in the volatile gas which is not condensed)5When the concentration of the volatile gas is low, the uncondensed volatile gas is directly recycled, and hot circulating gas is formed by a heat exchanger and is introduced into a crusher and a volatilization furnace kiln; PF in the uncondensed volatile gas5When the concentration is high, the gas is absorbed and recycled, heat circulation gas is formed by the heat exchanger and is introduced into the crusher and the volatilization furnace kiln, and the specific operation can be flexibly controlled according to different raw materials and working conditions). And inert gas protective covers are arranged outside the dust collector and the heat exchanger, dry inert gas is introduced into the inert gas protective covers, and the micro-positive pressure is kept. The dust collector is preferably a high-temperature cloth bag dust collector; the heat exchanger is preferably a plate heat exchanger; the inert gas is one or a mixture of several gases of nitrogen, helium and argon, preferably nitrogen;
3. a condensation subsystem: and (4) condensing the precooled volatile gas in a condenser, and collecting the condensed organic solvent for later use. And arranging an inert gas protective cover outside the condenser, introducing dry inert gas into the inert gas protective cover, and keeping the micro-positive pressure. The condenser is preferably a pipeline condenser; the condensation temperature is-20 to 20 ℃; preferably three-stage condensation, wherein the condensation temperature is respectively 5-20 ℃, 5-5 ℃ and-20-5 ℃; the inert gas is one of nitrogen, helium and argon or a mixture of the above gases, and nitrogen is preferred.
4. An absorption and blending subsystem: the absorption tower is internally and pre-filled with condensed organic solvent according to a certain proportion, a certain amount of lithium fluoride is added, uncondensed volatile gas is introduced into the absorption tower for absorption, and the uncondensed volatile gas comprises: PF (particle Filter)5And a small amount of organic gases that are not condensed. The PF5React with LiF to generate LiPF6；LiPF6Mixed in an organic solvent to form an electrolyte. And (3) the electrolyte in the absorption tower is analyzed to reach the standard and then is put into a blending tank, and additives and the like are supplemented according to the formula, so that an electrolyte product is produced. And inert gas protective covers are arranged outside the absorption tower and the blending tank, dry inert gas is introduced into the inert gas protective covers, and the micro-positive pressure is kept. The temperature for absorbing the volatile gas which is not condensed in the absorption tower is 0-50 ℃, preferably 25 ℃; furthermore, more than two sets of parallel absorption and allocation subsystems can be arranged, and the working state is switched through a valve so as to keep the continuity of the flow; the inert gas is one of nitrogen, helium and argon or a mixture of the above gases, and nitrogen is preferred.
The technical principle of the technical scheme of the application is as follows: dry inert gas is introduced into the crusher, the volatilization furnace kiln and the blending tank; inert gas protective covers are arranged outside the crusher, the volatilization furnace kiln, the heat exchanger, the dust collector, the condenser, the absorption tower and the blending tank, and double insurance is realized, so that H in the air is isolated2O、O2And CO2And the like, so that organic solvents, F, P and the like in the electrolyte of the retired lithium battery are not decomposed or subjected to side reaction, impurities except inert gas are not introduced, the inert gas is nitrogen, helium or argon, the properties are extremely stable, and the organic solvents, F, P and the like do not participate in the reaction in the whole system. In the crushing and volatilizing process, the organic solvent is volatilized into hot volatile gas, and the electrolyte LiPF6Decomposed to LiF andPF5LiF remains in the crushed material, PF5Then enters into the hot volatile gas and exists stably. Collecting dust, condensing to obtain liquid organic solvent, introducing uncondensed volatile gas into absorption tower, and collecting PF in uncondensed volatile gas5Absorbed by lithium fluoride pre-loaded in an absorption tower and reacted to generate LiPF6And the organic solvent obtained by condensation is used as a medium for absorption reaction in the absorption tower, and after the absorption is finished, a certain amount of additives and the like are supplemented according to formulas required by different customers, so that qualified electrolyte products are finally produced.
In the crushing and volatilizing subsystem, the equation (high temperature) of the electrolyte decomposition reaction is shown as formula (1),
LiPF6＝PF5+LiF (1)
in the absorption and preparation subsystem, the electrolyte synthesis reaction equation (low temperature) is shown as formula (2),
PF5+LiF＝LiPF6 (2)
the heat in the system is mainly carried by gas, and the heat exchanger is arranged, so that the energy consumption can be greatly reduced.
In the hot recycle gas, mainly small amounts of uncondensed organic gases and PF5And a large amount of inert gas (the inert gas flowing in the whole retired lithium battery electrolyte recovery system) without other components, so that the system is very suitable for being reused in a crushing and volatilizing subsystem, and the consumption of the inert gas can be greatly reduced. The circulation that relapses like this only needs to discharge a very small amount of tail gas, goes to carry out exhaust-gas treatment to prevent that the operation day is long after, the gas expansion of system, greatly reduced exhaust-gas treatment's volume and cost, and greatly reduced organic solvent waste gas, spray liquid waste water, spray dangerously useless such as waste residue and useless activated carbon useless, more saved high investment and the high energy consumption's of second combustion chamber and RTO stove equipment.
The key points and points to be protected of the technology of the invention are as follows:
(1) a process flow;
(2) inert gas shield for isolating air, preventing decomposition of organic solvent, and preventing F, P from producing POF in large amount3、HF、H3PO4And the qualified electrolyte product is produced;
(3) recycling the thermal cycle gas;
(4) the heat exchanger makes full use of heat.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be made within the scope of the present invention.
Those not described in detail in this specification are within the knowledge of those skilled in the art.

Claims (10)

1. The utility model provides a retired lithium cell electrolyte recovery system which characterized in that: the method comprises the following steps: a crushing and volatilizing subsystem, a dust collecting and heat exchanging subsystem, a condensing subsystem and a plurality of sets of absorbing and preparing subsystems;
the crushing and volatilization subsystem comprises: a storage bin, a crusher and a volatilization furnace kiln;
the dust collection and heat exchange subsystem comprises: a heat exchanger and a dust collector;
the condensing subsystem includes: a condenser;
each set of absorption and deployment subsystems includes: an absorption tower and a blending tank;
the storage bin is connected with a crusher, and the crusher is connected with the volatilization furnace kiln;
the volatilization furnace kiln is connected with a dust collector, and the dust collector is connected with a heat exchanger;
the heat exchanger is connected with the condenser; the condenser is connected with a plurality of sets of absorption and allocation subsystems through valves;
in each set of absorption and allocation subsystem, the absorption tower is connected with the allocation tank;
dry inert gas is introduced into the crusher, the volatilization furnace kiln and the blending tank;
micro negative pressure is kept in the crusher, the volatilization furnace kiln and the blending tank;
the feed bin is used for: adding a retired lithium battery;
the crusher is used for: crushing the retired lithium battery in the storage bin;
the volatilization furnace kiln is used for: volatilizing the materials crushed by the crusher to generate volatilized materials and hot volatilized gas;
the dust collector is used for: receiving hot volatile gas generated by the volatilization furnace kiln, and collecting dust for the hot volatile gas;
the heat exchanger is used for: receiving the hot volatile gas after dust collection, and carrying out temperature reduction and precooling on the hot volatile gas to form precooled volatile gas;
the condenser is used for: receiving the precooled volatile gas, condensing out the organic solvent, and outputting uncondensed volatile gas;
the non-condensed volatile gas comprises: PF (particle Filter)5And organic gases that are not condensed;
the absorption tower is used for: receiving the organic solvent condensed by the condenser, adding LiF into the absorption tower, and absorbing the uncondensed volatile gas;
the PF5React with LiF to generate LiPF6；
LiPF6Mixing the electrolyte in an organic solvent to form an electrolyte;
the blending tank is used for: receiving the electrolyte which is analyzed to reach the standard in the absorption tower, and adding an additive to produce an electrolyte product;
and the qualified electrolyte contains LiPF6The content of (A) is as follows: 0.9-1.5 mol/L.
2. The ex-service lithium battery electrolyte recovery system of claim 1 further comprising: the crusher, the volatilization furnace kiln and the absorption tower are all connected with the heat exchanger;
the volatile gas which is not absorbed in the absorption tower flows back to the heat exchanger again to exchange heat with the hot volatile gas in the heat exchanger, and the heat exchanger outputs hot circulating gas;
the uncondensed volatile gas is sent into an absorption tower to be absorbed or reflows to a heat exchanger again, and exchanges heat with hot volatile gas in the heat exchanger, and the heat exchanger outputs hot circulating gas;
introducing hot circulating gas into the crusher and the volatilization furnace kiln;
and micro negative pressure is kept in the crusher and the volatilization furnace kiln.
3. The ex-service lithium battery electrolyte recovery system of claim 1 or 2, wherein: the air in the storage bin is replaced dry inert gas;
inert gas protective covers are arranged outside the crusher, the volatilization furnace kiln, the heat exchanger, the dust collector, the condenser, the absorption tower and the blending tank;
and introducing dry inert gas into the inert gas protective cover, and keeping the micro-positive pressure.
4. The ex-service lithium battery electrolyte recovery system of claim 3 wherein: the dust collector is as follows: a high temperature bag collector;
the heat exchanger is as follows: a plate heat exchanger;
the condenser is as follows: a pipe condenser;
the condensing temperature of the condenser is as follows: -20 to 20 ℃;
the inert gas is: one of nitrogen, helium and argon or a mixture of the above gases.
5. The ex-service lithium battery electrolyte recovery system of claim 4 wherein: the inert gas is: nitrogen gas.
6. The ex-service lithium battery electrolyte recovery system of claim 4 wherein: the condenser is sequentially divided into a front-section condenser, a middle-section condenser and a rear-section condenser;
the condensing temperature of the front-section condenser is as follows: 5-20 ℃;
the condensing temperature of the middle section condenser is as follows: -5 ℃ to 5 ℃;
the condensation temperature of the rear-section condenser is as follows: -20 ℃ to-5 ℃;
and the precooled volatile gas sequentially enters a front-section condenser, a middle-section condenser and a rear-section condenser.
7. The ex-service lithium battery electrolyte recovery system of claim 1 further comprising: the retired lithium battery electrolyte recovery system further comprises an induced draft fan;
the crusher, the volatilization furnace kiln and the blending tank are all connected with an induced draft fan;
the draught fan is used for: keeping the micro negative pressure in the crusher, the volatilization furnace kiln and the blending tank.
8. The ex-service lithium battery electrolyte recovery system of claim 1 further comprising: the temperature that volatilizees of material after the stove that volatilizees to the breaker is: 80-250 ℃; the temperature for absorbing the non-condensed volatile gas in the absorption tower is as follows: 0 to 50 ℃.
9. The ex-service lithium battery electrolyte recovery system of claim 8 wherein: the temperature that volatilizees of material after the stove that volatilizees to the breaker is: 180 ℃;
the temperature for absorbing the non-condensed volatile gas in the absorption tower is as follows: at 25 ℃.
10. An electrolyte recovery method using the electrolyte recovery system for retired lithium batteries according to any one of claims 1 to 9, wherein: the method comprises the following steps:
s1, adding the retired lithium battery into a bin;
s2, conveying the retired lithium battery in the bin into a crusher for crushing;
s3, conveying the material crushed by the crusher into a volatilization kiln;
s4, volatilizing the materials crushed by the crusher by a volatilizing kiln to generate volatilized materials and hot volatilized gas;
s5, receiving hot volatile gas generated by the volatilization furnace kiln by a dust collector, and collecting dust from the hot volatile gas;
s6, receiving the hot volatile gas after dust collection by a heat exchanger, and cooling and precooling the hot volatile gas to form precooled volatile gas;
s7, the condenser receives the precooled volatile gas, condenses out the organic solvent and outputs the non-condensed volatile gas;
s8, the absorption tower receives the organic solvent condensed by the condenser and the uncondensed volatile gas, lithium fluoride is added into the absorption tower, and the uncondensed volatile gas is absorbed;
and S9, the blending tank receives the electrolyte which is analyzed to reach the standard in the absorption tower, and the additive is added to produce an electrolyte product.
CN202111558067.3A 2021-12-20 2021-12-20 Recycling system and recycling method for electrolyte of retired lithium battery Pending CN114388920A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116525989A (en) * 2023-02-03 2023-08-01 广东杰成新能源材料科技有限公司 Harmless treatment method and device for retired lithium battery electrolyte

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116525989A (en) * 2023-02-03 2023-08-01 广东杰成新能源材料科技有限公司 Harmless treatment method and device for retired lithium battery electrolyte
CN116525989B (en) * 2023-02-03 2024-01-19 广东杰成新能源材料科技有限公司 Harmless treatment method and device for retired lithium battery electrolyte

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