CN116531851B - Waste lithium battery electrolyte recovery system and process - Google Patents
Waste lithium battery electrolyte recovery system and process Download PDFInfo
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- CN116531851B CN116531851B CN202310822625.5A CN202310822625A CN116531851B CN 116531851 B CN116531851 B CN 116531851B CN 202310822625 A CN202310822625 A CN 202310822625A CN 116531851 B CN116531851 B CN 116531851B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 138
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 90
- 238000011084 recovery Methods 0.000 title claims abstract description 47
- 239000002699 waste material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title abstract description 16
- 230000008569 process Effects 0.000 title abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 58
- 239000011261 inert gas Substances 0.000 claims abstract description 23
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 89
- 238000010438 heat treatment Methods 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 33
- 238000010257 thawing Methods 0.000 claims description 17
- 239000012855 volatile organic compound Substances 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 230000005540 biological transmission Effects 0.000 claims description 8
- 238000005520 cutting process Methods 0.000 claims description 8
- 230000007246 mechanism Effects 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- 238000004891 communication Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 239000011343 solid material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 abstract description 9
- 230000008020 evaporation Effects 0.000 abstract description 9
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract 1
- 238000009833 condensation Methods 0.000 description 12
- 230000005494 condensation Effects 0.000 description 12
- 239000012071 phase Substances 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 8
- 230000001360 synchronised effect Effects 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 239000012634 fragment Substances 0.000 description 6
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- 238000007710 freezing Methods 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000005057 refrigeration Methods 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010892 electric spark Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
- B01D45/12—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces
- B01D45/16—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces by centrifugal forces generated by the winding course of the gas stream, the centrifugal forces being generated solely or partly by mechanical means, e.g. fixed swirl vanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D45/00—Separating dispersed particles from gases or vapours by gravity, inertia, or centrifugal forces
- B01D45/18—Cleaning-out devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0033—Other features
- B01D5/0036—Multiple-effect condensation; Fractional condensation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0057—Condensation of vapours; Recovering volatile solvents by condensation in combination with other processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D5/00—Condensation of vapours; Recovering volatile solvents by condensation
- B01D5/0078—Condensation of vapours; Recovering volatile solvents by condensation characterised by auxiliary systems or arrangements
- B01D5/0096—Cleaning
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/002—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by condensation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Manufacturing & Machinery (AREA)
- Electrochemistry (AREA)
- Secondary Cells (AREA)
Abstract
The application relates to a waste lithium battery electrolyte recovery system and a process, wherein the recovery system comprises a closed rotary volatilization box, a first cyclone separation device, a refrigerating unit, a second cyclone separation device and a vacuum pump, which are sequentially connected through pipelines, the vacuum pump is connected with the closed rotary volatilization box through the pipelines, so that a closed circulation system is formed, inert gas is introduced into the closed rotary volatilization box, flow control valves are arranged on the pipelines between the first cyclone separation device and the refrigerating unit and between the second cyclone separation device and the vacuum pump, a circulation return valve is arranged on the pipeline between the vacuum pump and the closed rotary volatilization box, and an exhaust valve for connecting the outside of a pipeline is arranged on the pipeline between the vacuum pump and the circulation return valve; by adopting the technical scheme of the application to recycle the electrolyte, the problems that the lithium battery needs to be discharged, the electrolyte loss is large, the evaporation temperature of the lithium battery is high, the waste gas is discharged and treated, the electrolyte is difficult to collect after solidification, and the electrolyte recycling rate is low are solved.
Description
Technical Field
The application belongs to the technical field of lithium battery electrolyte recovery, and particularly relates to a waste lithium battery electrolyte recovery system and a waste lithium battery electrolyte recovery process.
Background
The lithium battery electrolyte mainly comprises lithium salt, an organic solvent and an additive, wherein the lithium salt accounts for about 15% of the total mass of the electrolyte and is mainly lithium hexafluorophosphate which can be decomposed at 200 ℃; the organic solvent accounts for more than 80% of the total mass of the electrolyte, is used for dissolving lithium salt and improving electrochemical stability of the electrolyte, and is mostly carbonate organic matters such as dimethyl carbonate (DMC), ethylene Carbonate (EC), fluoroethylene carbonate (FEC), propylene Carbonate (PC), vinylene Carbonate (VC) and the like, and has a boiling point range of 90-250 ℃ and a solidifying point of 35-38 ℃ at most.
The current mainstream recovery process is that the lithium battery is firstly discharged, then crushed, heated to volatilize electrolyte, and then the volatilized gas is condensed to finally obtain electrolyte. The problems that exist in this process are mainly: (1) lithium batteries take a long time to discharge; (2) The lithium battery is inflammable and explosive in the breaking process, the dangerous degree is high, and a large amount of electrolyte is lost if the lithium battery is burnt; (3) The waste lithium battery electrolyte has complex components and wide boiling point range (dimethyl carbonate 90 ℃ and ethylene carbonate 248 ℃), and the required evaporation temperature is high through conventional heating evaporation, and the high temperature can cause melting of a lithium battery diaphragm and decomposition of lithium salt; (4) Exhaust emission in the electrolyte recovery process not only affects the electrolyte recovery rate, but also increases high exhaust treatment investment cost, otherwise, environmental pollution is caused; (5) The freezing point of electrolyte molecules is high, such as dimethyl carbonate freezing point 0.5 ℃ and ethylene carbonate freezing point 35-38 ℃, and carbonate gas molecules solidify when the temperature is reduced below the freezing point, so that equipment and pipelines are blocked, and materials cannot be collected from the equipment.
Disclosure of Invention
In order to solve at least one of the problems listed above, the application provides a waste lithium battery electrolyte recovery system and an electrolyte recovery process based on the recovery system.
The technical scheme of the waste lithium battery electrolyte recovery system in the application is as follows:
a spent lithium battery electrolyte recovery system comprising: the sealed rotary volatilization box is used for heating and crushing the opened lithium battery, introducing inert gas into the sealed rotary volatilization box, heating the lithium battery to volatilize the electrolyte, and mixing the volatilized electrolyte with the inert gas to form electrolyte volatilized gas; the first cyclone separation device is used for separating solids and liquid in electrolyte volatile gas from the airtight rotary volatilization box, and a heat tracing wire is arranged on the first cyclone separation device so as to melt condensed electrolyte liquid; the refrigerating unit is used for cooling the electrolyte volatile gas from the first cyclone separation device to obtain electrolyte liquid and gas with electrolyte liquid drops, and has a defrosting function to melt the condensed electrolyte liquid; a second cyclone separator for separating electrolyte droplets in the gas from the refrigerator group; the vacuum pump is used for forming vacuum in the system and circulating inert gas in the system;
The closed rotary volatilizing box, the first cyclone separation device, the refrigerating unit, the second cyclone separation device and the vacuum pump are sequentially communicated through pipelines, and the vacuum pump is communicated with the closed rotary volatilizing box through the pipelines, so that a closed circulating system is formed; flow control valves are arranged on the pipelines between the first cyclone separation device and the refrigerating unit and between the second cyclone separation device and the vacuum pump, a circulation return air valve is arranged on the pipeline between the vacuum pump and the airtight rotary volatilizing box, and an exhaust valve for connecting the outside of the pipeline is arranged on the pipeline between the vacuum pump and the circulation return air valve.
On the basis of the scheme, the airtight rotary volatilizing box comprises a barrel body and a heating tube assembly, wherein the barrel body is a horizontally placed barrel, a plurality of baffles with sharp corners are uniformly arranged on the inner wall of the barrel body at intervals around the circumference, the heating tube assembly is arranged at the position of the central axis of the barrel body, and an openable end cover is arranged on the barrel body; the cylinder is connected with a driving mechanism, and the driving mechanism is used for driving the cylinder to rotate.
On the basis of the scheme, the heating tube assembly comprises two heating tube brackets and a plurality of heating tubes, the two heating tube brackets are respectively arranged at two ends of the inside of the cylinder, the heating tube brackets are fixedly connected with the cylinder, the heating tubes are placed in a posture parallel to the central axis of the cylinder, the two ends of the heating tubes are correspondingly connected with the two heating tube brackets, and the heating tubes are uniformly distributed around the circumference at intervals by taking the central axis of the cylinder as the center. On the basis of the above-mentioned scheme,
on the basis of the scheme, the driving mechanism comprises a motor, a transmission assembly and a hollow shaft, an output shaft of the motor is connected with the transmission assembly, the transmission assembly is connected with the hollow shaft, the axis of the hollow shaft and the central axis of the cylinder body are in the same straight line, one end of the hollow shaft is fixedly connected with the cylinder body, the other end of the hollow shaft is connected with a pipeline communicated with an air inlet of the first cyclone separation device through a rotary joint, and the hollow shaft is communicated with the cylinder body and the rotary joint.
On the basis of the scheme, a metal filter screen is arranged at the port of the hollow shaft, which is communicated with the cylinder body.
On the basis of the scheme, a temperature sensor for detecting the temperature inside the cylinder body is arranged on the cylinder body, the temperature sensor is in communication connection with a temperature controller, and the temperature controller is in communication connection with the heating pipe assembly; the temperature sensors are arranged in a plurality, and the temperature sensors are uniformly distributed on the circumference around the wall surface of the cylinder body.
On the basis of the scheme, the first cyclone separation device comprises a first cyclone separator, a silk screen and a heat tracing wire, the first cyclone separator is of a vertical cylinder structure, an air outlet is formed in the upper end, a liquid outlet is formed in the lower end, the silk screen is arranged on the air outlet of the first cyclone separator, and the heat tracing wire is spirally wound outside the wall of the lower portion of the first cyclone separator.
On the basis of the scheme, a first pressure indicator is arranged on the airtight rotary volatilizing box, a first temperature indicator is arranged on the air outlet of the first cyclone separator, and a second temperature indicator is arranged on the air outlet of the refrigerating unit.
On the basis of the scheme, a second pressure indicator is arranged on a pipeline between the first cyclone separator and the refrigerating unit, a third pressure indicator and a third temperature indicator are arranged on a pipeline between the second cyclone separator and the vacuum pump, and a fourth pressure indicator is arranged at an air outlet of the vacuum pump.
The electrolyte recovery process based on the waste lithium battery electrolyte recovery system comprises the following steps:
s1, cutting off a shell at the position of a tab of a waste lithium battery;
s2, placing the sheared waste lithium batteries into a closed rotary volatilization box;
s3, starting the refrigerating unit, setting the refrigerating temperature to be minus 20 ℃, wherein the temperature after cooling is 5-10 ℃ higher than the refrigerating temperature, and enabling the temperature after cooling of the refrigerating unit to be between minus 10 ℃ and minus 15 ℃;
s4, when the refrigerating temperature of the refrigerating unit is minus 20 ℃, starting a vacuum pump, closing a circulating air return valve, opening an exhaust valve, discharging residual air in the system, reducing the vacuum degree of the whole system, and ensuring safety;
s5, introducing inert gas into the airtight rotary volatilizing box, opening a circulation air return valve, and closing an exhaust valve;
s6, starting the airtight rotary volatilizing box to rotate and heat, gradually increasing the temperature inside the airtight rotary volatilizing box and finally keeping the temperature at 130 ℃, controlling the content of VOCs in gas from the exhaust valve to be not more than 600ppm during the temperature increasing, controlling the gas phase temperature of the gas outlet of the airtight rotary volatilizing box to be not more than 50 ℃, controlling the gas phase temperature of the gas outlet of the refrigerating unit to be not more than-10 ℃, and adjusting the temperature increasing speed of the airtight rotary volatilizing box or reducing the flow of circulating gas by adjusting the flow control valve when any one of the gas phase temperatures exceeds the temperature;
S7, keeping the flow of the circulating gas unchanged when the internal temperature of the closed rotary volatilizing box is 130 ℃, and running the whole system for 5min;
s8, adjusting a flow control valve to gradually reduce the flow of circulating gas, reducing the air pressure in the airtight rotary volatilizing box to-0.1 MPa, detecting the content of VOCs in the gas at an exhaust valve, closing the circulating air return valve when the content of the VOCs is below 50ppm, and then sequentially closing the airtight rotary volatilizing box to heat, rotating the airtight rotary volatilizing box, and a vacuum pump and a refrigerating unit;
s9, closing a flow control valve, and cutting off the connection of all the devices;
s10, starting a defrosting function of a refrigerating unit, setting the defrosting temperature to be higher than 50 ℃, and starting a heat tracing wire of a first cyclone separation device to enable the heating temperature to be higher than 40 ℃;
s11, collecting electrolyte liquid collected in the first cyclone separation device, the second cyclone separation device and the refrigerating unit;
s12, opening the airtight rotary volatilizing box, and collecting the lithium battery solid material after the lithium battery solid material is cooled.
The technical scheme of the application has the advantages that:
(1) According to the waste lithium battery electrolyte recovery system, the waste lithium batteries are heated and crushed through the airtight rotary volatilization box, inert gas is introduced into the airtight rotary volatilization box, vacuum negative pressure is arranged, air is isolated in the heating process, combustion is avoided, the problem of large electrolyte loss is solved, discharging is not needed in the early stage, only the shell at the tab of the lithium battery is needed to be cut off, the processing time of the lithium battery is shortened, and then volatilization of electrolyte molecules is promoted by vacuum negative pressure, so that the volatilization rate of the electrolyte molecules is high at a lower volatilization temperature, and the problems of melting of a lithium battery diaphragm and decomposition of lithium salt caused by high conventional heating evaporation temperature are solved; finally, the electrolyte is heated uniformly and the volatilization area is larger by rotating the airtight rotary volatilization box and crushing the lithium battery, so that the electrolyte is volatilized more thoroughly and has higher efficiency.
(2) The waste lithium battery electrolyte recovery system solves the problems of exhaust gas emission and treatment by adopting a gas circulation mode, only small amounts of low-VOCs-content gas are discharged in the early-stage establishment vacuum stage and the later-stage unpacking and discharging process of the gas circulation, and no exhaust gas is discharged in the whole process.
(3) The waste lithium battery electrolyte recovery system solves the problem that electrolyte cannot be collected from equipment, the refrigerating unit has a defrosting function, solids generated during condensation can be timely melted through defrosting, and a heat tracing wire is arranged on the first cyclone separation device, so that the separated and condensed electrolyte can be melted.
(4) According to the waste lithium battery electrolyte recovery system, the electrolyte is recovered through a series of measures such as simple disassembly, airtight crushing, vacuum evaporation, low partial pressure volatilization, inert gas circulating carrying, cyclone separation, low-temperature condensation recovery and the like, and the electrolyte recovery rate is high.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a waste lithium battery electrolyte recovery system of the present application;
FIG. 2 is a front view of a sealed rotary volatilization box in the electrolyte recovery system of the waste lithium battery of the application;
FIG. 3 is a left side view of a sealed rotary volatilization box in the waste lithium battery electrolyte recycling system of the application;
fig. 4 is a schematic structural diagram of a first cyclone separation device in the electrolyte recovery system of the waste lithium battery.
Reference numerals illustrate:
10. sealing the rotary volatilizing box; 11. a cylinder; 111. a baffle; 112. an end cap; 1211. a support rod; 1212. mounting a plate; 122. a heating tube; 131. a motor; 1321. a synchronous pulley; 1322. a synchronous belt; 133. a hollow shaft; 134. a rotary joint; 14. a metal filter screen; 15. a temperature sensor; 16. a support frame body; 161. rotating the mounting base; 162. rubber rollers; 1631. a roller support bar; 1632. a fork-shaped connecting rod; 1633. a threaded pull rod; 1634. a first adjustment nut; 1641. a threaded column; 1642. a second adjustment nut; 17. a conductive slip ring; 18. a rupture disk device; 20. a first cyclonic separating apparatus; 21. a first cyclone separator; 22. a silk screen; 23. a heat trace line; 30. a refrigerating unit; 40. a second cyclonic separating apparatus; 50. a vacuum pump; 60. a flow control valve; 70. a circulation return valve; 80. an exhaust valve; 90. an inert gas make-up valve.
Detailed Description
In order that the above objects, features and advantages of the application will be readily understood, a more particular description of the application will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application. The present application may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the application, whereby the application is not limited to the specific embodiments disclosed below.
In the description of the present application, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", "axial", "radial", "circumferential", etc. indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings are merely for convenience in describing the present application and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present application.
Furthermore, the terms "first," "second," and the like, are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
In the present application, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present application can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present application, unless expressly stated or limited otherwise, a first feature "up" or "down" a second feature may be the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" and "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is less level than the second feature.
Referring to fig. 1, the application provides a waste lithium battery electrolyte recovery system, which comprises a sealed rotary volatilization box 10, a first cyclone separation device 20, a refrigerating unit 30, a second cyclone separation device 40 and a vacuum pump 50, wherein the sealed rotary volatilization box 10, the first cyclone separation device 20, the refrigerating unit 30, the second cyclone separation device 40 and the vacuum pump 50 are sequentially communicated through pipelines, and the vacuum pump 50 is communicated with the sealed rotary volatilization box 10 through the pipelines, so that a sealed circulation system is formed; flow control valves 60 are respectively arranged on the pipelines between the first cyclone separation device 20 and the refrigerating unit 30 and between the second cyclone separation device 40 and the vacuum pump 50, a circulation return air valve 70 is arranged on the pipeline between the vacuum pump 50 and the airtight rotary volatilization box 10, an exhaust valve 80 for connecting the outside of the pipeline is arranged on the pipeline between the vacuum pump 50 and the circulation return air valve 70, and an inert gas supplementing valve 90 is arranged on the pipeline between the airtight rotary volatilization box 10 and the circulation return air valve 70.
The sealed rotary volatilizing box 10 is used for accommodating retired lithium batteries, heating and crushing the lithium batteries under the protection of inert gas, and mixing electrolyte volatilized with the inert gas to form electrolyte volatilized gas; the airtight rotary volatilizing box 10 is completely closed to be in contact with the outside air, the whole is in an inert gas condition, the ignition problem of the battery can be avoided, and the ignition phenomenon of the battery piece can not occur after the electrolyte volatilizes; the lithium battery treated by the sealed rotary volatilization box 10 is a single battery, an opening is cut on the shell at the lug so as to enable the interior of the lithium battery to be communicated with the exterior, the lithium battery is low in voltage on the premise that electrolyte can enter the sealed rotary volatilization box 10 from the interior of the lithium battery, the damage to human bodies is not enough in the cutting process, and the voltage in the box can be led out through the metal shell of the device so as to treat the undischarged battery; the airtight rotary volatilization box 10 rotates in the heating process, and turns over and breaks the lithium battery, so that the lithium battery is heated uniformly, the volatilization area of the electrolyte is larger, and the electrolyte is volatilized more thoroughly and has higher efficiency.
The first cyclone separation device 20 is configured to separate solids and liquids in the electrolyte volatile gas from the sealed rotary volatilizing box 10, wherein the solids are mainly small battery fragments and black powder, the liquids are mainly heavy components in the electrolyte with high condensation temperature, the small battery fragments and the black powder are separated so as to avoid blockage caused by the fact that the small battery fragments and the black powder enter subsequent pipelines and devices along with airflow, and the condensed heavy components are separated so as to avoid blockage of the pipelines and valves after the condensed heavy components are further cooled in the pipelines; the first cyclone separation device 20 is mainly structured as a cyclone separator, the cyclone separator has a larger surface area, the electrolyte volatile gas is in a cyclone state on the inner surface of the cyclone separator, the retention time is long, the electrolyte volatile gas and the environment exchange heat to cool down, and the electrolyte volatile gas is precooled before entering the refrigerating unit 30, so that the cooling load of the refrigerating unit 30 can be reduced, and a good energy-saving effect is achieved; the cyclone separator is wound with the heat tracing wire, and before the electrolyte liquid is collected by the cyclone separator, the heat tracing wire is started to prevent the heavy components from solidifying and simultaneously to heat and melt the heavy components after solidification, so that the heavy components are prevented from solidifying to block the liquid outlet, and the collection is facilitated. According to different treatments, different pipe diameters and pipeline flow rates are set, cyclone separators are arranged in the way, the temperature of gas before entering the refrigerating unit 30 can be completely controlled to be below 50 ℃, and the cooling load of the refrigerating unit 30 is reduced by 50%.
The refrigerating unit 30 is configured to cool the electrolyte volatile gas coming out of the first cyclone separation device 20, thereby obtaining an electrolyte liquid and an inert gas with electrolyte droplets; the freezing point of a part of components in the electrolyte is higher, and the part of components are solidified during condensation to cause that the components cannot be discharged, so that the refrigerating unit 30 is provided with a defrosting function, and the solidified liquid is melted during condensation through defrosting of the heat exchange tube and defrosting of the heat exchanger shell, so that the collection is facilitated.
The second cyclone separation device 40 is used for separating electrolyte droplets in the gas from the refrigerating unit 30, further improving the recovery rate of the electrolyte, and simultaneously exchanging heat between the gas and the environment to raise the temperature, so that the temperature of the gas is above 0 ℃ before the gas enters the vacuum pump 50, and effectively avoiding operation problems of the vacuum pump 50 caused by too low gas temperature.
The vacuum pump 50 is used for forming vacuum inside the electrolyte recovery system and circulating inert gas in the system; the vacuum pump 50 is started, the circulation air return valve 70 is closed, the exhaust valve 80 is opened, and the electrolyte recovery system can be emptied; the vacuum pump 50 is started, the circulation air return valve 70 is opened, the exhaust valve 80 is closed, and the inert gas can circulate in the system; the outlet of the vacuum pump 50 is slightly positive in pressure, and the inlet can reach the minimum pressure of-0.1 MPa.
The flow control valve 60 is used for controlling the flow of circulating gas in the system, opening a large valve, increasing the pumping capacity of the vacuum pump 50, reducing the pressure in the airtight rotary volatilizing box 10 to the minimum of-0.1 MPa; the flow of the circulating gas needs to be regulated by referring to the temperature of each section in the system, the content of VOCs in the gas at the outlet of the vacuum pump 50 and the like, and the excessive flow of the circulating gas can lead the gas to stay in the refrigerating unit 30 for too short time, so that the condensation effect is poor and the temperature of each section is ultrahigh; the flow control valve 60 should be placed after the cyclone, since liquid and solid matter in the gas in the pipe is very prone to collect at the throttle or flow change position.
The exhaust valve 80 is connected with a VOCs concentration detection device to detect the content of VOCs in the gas at the outlet of the vacuum pump 50.
The technical principle of the waste lithium battery electrolyte recovery system of the application is as follows: placing the opened waste lithium batteries into a closed rotary volatilizing box 10, gasifying electrolyte under the action of heating and circulating air flow, and entering a first cyclone separation device 20 along with inert gas; the electrolyte gas exchanges heat with the environment in the first cyclone separation device 20 to cool down, the liquefied or solidified heavy components are separated out, and then the electrolyte gas enters the low-temperature refrigerating unit 30; in the refrigerating unit 30, the temperature of the electrolyte gas is reduced to below 0 ℃, most of electrolyte molecules are condensed and recovered, and the uncondensed gas enters the second cyclone separation device 40; in the second cyclone separation device 40, liquid molecules and liquid beads in the gas phase are further separated and recovered, and the rest gas enters the vacuum pump 50; in the vacuum pump 50, the circulating gas is pressurized and returned to the sealed rotary evaporation tank 10 through a pipe, thereby completing the gas circulation.
The structure of each device of the electrolyte recovery system for waste lithium batteries of the present application will be described below.
Referring to fig. 2 and 3, the airtight rotary volatilizing box 10 includes a barrel 11 and a heating tube assembly, the barrel 11 is a horizontally placed barrel, a plurality of baffles 111 with sharp corners are uniformly arranged on the inner wall of the barrel 11 at intervals around the circumference, the baffles 111 are long-bar stainless steel plates, the length direction of the baffles 111 is along the axial direction of the barrel 11 and extends to two ends of the barrel, the width direction of the baffles 111 is perpendicular to the arc tangent line of the barrel at the installation position, a 3mm gap is reserved between the baffles 111 and the inner wall of the barrel 11, triangular metal sheets are arranged on the baffles 111 and perpendicular to the long and wide surfaces of the baffles, the tops of the metal sheets are cut into sharp corners, the heating tube assembly is arranged at the position of the central axis of the barrel 11, openable end covers 112 are arranged at the two ends of the barrel 11 at the central axis, the end covers 112 are arc cover plates with raised middle parts, the end covers 112 can be reliably fixed and sealed with the barrel 11, and the middle parts of the end covers 112 are connected with a pipeline through rotary joints. The sealed rotary volatilizing box 10 is used for loading and unloading lithium batteries by opening the end cover 112, the baffle 111 with sharp corners can crush the lithium batteries, the cambered surface cover plate is beneficial to the uniform flow of gas, the formation of flowing dead angles is avoided, and volatilized electrolyte is discharged as much as possible.
Optionally, the heating tube assembly includes two heating tube brackets and a plurality of heating tubes 122, the two heating tube brackets are respectively disposed at two ends of the interior of the cylinder 11, the heating tube brackets include a plurality of support rods 1211 and mounting plates 1212, one end of each support rod 1211 is fixedly connected to the inner wall of the cylinder 11, and the other end is fixedly connected to the mounting plate 1212; the heating pipes 122 are placed in a posture parallel to the central axis of the cylinder 11, two ends of the heating pipes 122 are correspondingly connected with the two mounting plates 1212, and a plurality of the heating pipes 122 are uniformly distributed around the circumference at intervals with the central axis of the cylinder 11 as the center; specifically, 6 heating tubes 122 are selected. The lithium battery is baked through the plurality of heating pipes 122, so that the baking heat is more uniform.
Referring to fig. 2, the airtight rotary volatilizing box 10 is connected with a driving mechanism, the driving mechanism is used for driving the cylinder 11 to rotate, the driving mechanism includes a motor 131, a transmission assembly and a hollow shaft 133, the transmission assembly includes two synchronous pulleys 1321 and a synchronous belt 1322 wound around the two synchronous pulleys 1321, the synchronous pulleys 1321 are connected with an output shaft of the motor 131, the other synchronous pulley 1321 is connected with the hollow shaft 133, an axis of the hollow shaft 133 is in the same straight line with a central shaft of the cylinder 11, one end of the hollow shaft 133 is fixedly connected with an end cover 112 of the airtight rotary volatilizing box 10, the other end is connected with a pipeline communicated with an air inlet of the first cyclone separating device 20 through a rotary joint 134, and the hollow shaft 133 is communicated with the cylinder 11 and the rotary joint 134.
Optionally, a metal filter screen 14 is disposed at the port of the hollow shaft 133, where the port is in communication with the barrel 11, where the metal filter screen 14 is used to prevent fragments of lithium batteries from entering the pipe, prevent the fragments from being doped in the collected electrolyte, and prevent the fragments from possibly entering the vacuum pump 50 to damage the vacuum pump 50.
Optionally, a temperature sensor 15 for detecting the temperature inside the cylinder 11 is disposed on the cylinder 11, and the temperature sensor 15 is communicatively connected to a temperature controller, and the temperature controller is communicatively connected to the heating tube 122; the temperature sensors 15 may be provided in plurality, the temperature sensors 15 are uniformly distributed around the wall surface of the cylinder 11 on the circumference, and the temperature sensors 15 detect temperatures at a plurality of positions to comprehensively determine the heating condition inside the cylinder 11; specifically, 3 temperature sensors 15 are provided. Therefore, the heating intensity of the lithium battery can be regulated by controlling the heating tube 122 through the temperature controller so as to control the volatilization rate of the electrolyte, and when the measurement average value of each temperature sensor 15 reaches 130 ℃, the heating tube 122 can be stopped in time to stop heating.
Optionally, an electrically conductive slip ring 17 is disposed on the hollow shaft 133, a rotating portion of the electrically conductive slip ring 17 is fixedly mounted on the hollow shaft 133, the temperature sensor 15 is electrically connected to the rotating portion of the electrically conductive slip ring 17, the temperature controller is electrically connected to the fixed portion of the electrically conductive slip ring 17, and the temperature controller is disposed on an electric control cabinet outside the airtight rotary volatilizing box 10.
Optionally, a rupture disc device 18 is arranged on the airtight rotary volatilizing case 10, if the evacuation is incomplete, explosion may occur in the process of heating the lithium battery, so that the pressure in the case body is rapidly increased, and the pressure is released in time by breaking the rupture disc of the rupture disc device 18.
Optionally, referring to fig. 2 and 3, a supporting frame body 16 is disposed below the airtight rotary volatilizing case 10, the supporting frame body 16 supports a rotary mounting seat 161, and the hollow shaft 133 is penetrated on the rotary mounting seat 161; the supporting frame body 16 supports two rubber rollers 162, the two rubber rollers 162 are symmetrically arranged on two sides of the cylinder 11 of the airtight rotary volatilizing box 10, and the rubber rollers 162 contact the outer wall surface of the lower part of the cylinder 11; the rubber roller 162 is positioned at the end of the cylinder 11 far away from the rotary mounting seat 161 as much as possible; the two rubber rollers 162 support and restrain the cylinder 11, ensure concentricity of the cylinder 11 during rotation, and improve stability of the cylinder 11 during rotation.
Further, the position of the rubber roller 162 can be adjusted, the rubber roller 162 is connected to the supporting frame body 16 through a roller adjusting component, the roller adjusting component comprises a roller supporting rod 1631, a fork-shaped connecting rod 1632 and a threaded pull rod 1633, the threaded pull rod 1633 penetrates through the fork-shaped connecting rod 1632 and is arranged in a collinear manner with the fork-shaped connecting rod 1632, the roller supporting rod 1631 and the fork-shaped connecting rod 1632 are rotationally connected to the supporting frame body 16 at intervals, one end of the threaded pull rod 1633 far away from the fork-shaped connecting rod 1632 is rotationally connected to the roller supporting rod 1631, the rubber roller 162 is rotationally arranged at the free end of the roller supporting rod 1631, two first adjusting nuts 1634 are in threaded connection with the threaded pull rod 1633, and the two first adjusting nuts 1634 are respectively positioned at two sides of the top end of the fork-shaped connecting rod 1632; the position of the rubber roller 162 is adjusted by adjusting the length of the threaded pull rod 1633 extending out of the forked connecting rod 1632, and the threaded pull rod 1633 is fixed by rotating the two first adjustment nuts 1634 to clamp the top end of the forked connecting rod 1632.
Further, a ground leg assembly is disposed at each corner of the supporting frame 16, the ground leg assembly includes a threaded post 1641 fixed on the ground, the threaded post 1641 passes through the supporting frame 16, a second adjusting nut 1642 is screwed on the threaded post 1641, the second adjusting nut 1642 is disposed at the lower end of the supporting frame 16 to support the supporting frame 16, and the height of the supporting frame 16 is leveled by rotating each second adjusting nut 1642.
Referring to fig. 4, the first cyclone device 20 includes a first cyclone separator 21, a wire mesh 22, and a heat tracing wire 23, where the first cyclone separator 21 has a vertical canister structure, an air outlet is disposed at an upper end, a liquid outlet is disposed at a lower end, a horizontal radial tangential air inlet, and air flows tangentially along an inner wall of a cone in the first cyclone separator 21 to form centrifugal force to separate particles and liquid droplets in a gas phase, so that separation efficiency is high; the silk screen 22 is arranged on the air outlet of the first cyclone separator 21 to further improve the separation effect of liquid drops in the gas phase; the heat tracing wire 23 is spirally wound outside the wall of the lower part of the first cyclone separator 21 and used for heating, so that the temperature can be ensured to be higher than 40 ℃, the heavy components in the electrolyte are prevented from condensing, and the problem that the heavy components in the electrolyte are solidified at the liquid outlet of the airtight rotary volatilizing box 10 and the pipeline equipment is blocked is solved.
The second cyclone separation device 40 mainly has a second cyclone separator, and may also have a wire mesh and a heat tracing wire as the first cyclone separation device 20; if the liquid in the mist from the refrigerating unit 30 is collected at the valve and elbow in the subsequent pipeline, the valve will be blocked, so that the second cyclone separator should be arranged as close to the outlet of the refrigerating unit 30 as possible, and the temperature near the outlet is lower, so that the liquid phase in the gas phase is more, and the single-pass condensation recovery rate of the electrolyte can be further improved.
In addition, referring to fig. 1, a first pressure indicator is provided on the airtight rotary evaporation tank 10, a first temperature indicator is provided on the air outlet of the first cyclone separator 21, a second temperature indicator is provided on the air outlet of the refrigerating unit 30, a second pressure indicator is provided on the pipe between the first cyclone separator 21 and the refrigerating unit 30, a third pressure indicator and a third temperature indicator are provided on the pipe between the second cyclone separator and the vacuum pump 50, and a fourth pressure indicator is provided on the air outlet of the vacuum pump 50. These pressure and temperature indicators are set to observe the pressure and temperature conditions of each section of the system in real time to control the recovery process.
When the prior art is used for treating the waste lithium battery, the waste lithium battery is usually discharged and then mechanically crushed, if the discharge is incomplete, electric spark is generated in the crushing process, and the loss of electrolyte is large due to combustion, so that the prior art is not suitable for the prior treatment of the lithium battery by the electrolyte recovery process, and the improvement is needed. In the waste lithium battery electrolyte recovery system, the waste lithium battery is heated and crushed through the sealed rotary volatilization box 10, inert gas is introduced into the sealed rotary volatilization box 10, vacuum negative pressure is arranged, the heating process is firstly isolated from air, combustion is avoided, the problem of large electrolyte loss is solved, the discharge can be avoided in the early stage, only the shell at the lug of the lithium battery is needed to be sheared off, the processing time of the lithium battery is shortened, and then the volatilization of electrolyte molecules is promoted by the vacuum negative pressure, so that the volatilization rate of the electrolyte molecules is high at a lower volatilization temperature, and the problems of melting of a lithium battery diaphragm and decomposition of lithium salt caused by the high conventional heating evaporation temperature are solved; and finally, the lithium battery can be broken under the combined actions of electrolyte gasification, mutual friction and collision among battery blocks, cutting of sharp corners of a baffle, softening and embrittling of materials in a heating process and the like, and the electrolyte is heated uniformly and has larger volatilization area due to the rotation of the sealed rotary volatilization box 10 and the breaking of the lithium battery, so that the electrolyte is volatilized more thoroughly and has higher efficiency.
The waste lithium battery electrolyte recovery system solves the problems of exhaust gas emission and treatment by adopting a gas circulation mode, only small amounts of low-VOCs-content gas are discharged in the early-stage establishment vacuum stage and the later-stage unpacking and discharging process of the gas circulation, and no exhaust gas is discharged in the whole process.
The waste lithium battery electrolyte recovery system solves the problem that electrolyte cannot be collected from equipment, the refrigerating unit 30 has a defrosting function, the defrosting temperature is higher than 50 ℃ through defrosting of the heat exchange tube and defrosting of the heat exchanger shell, solids generated during condensation can be melted in time, and the heat tracing line 23 is arranged on the first cyclone separation device 20, so that the separated and condensed electrolyte can be melted.
According to the waste lithium battery electrolyte recovery system, the electrolyte is recovered through a series of measures such as simple disassembly, airtight crushing, vacuum evaporation, low partial pressure volatilization, inert gas circulating carrying, cyclone separation, low-temperature condensation recovery and the like, and the electrolyte recovery rate can reach more than 85%.
The electrolyte recovery process based on the waste lithium battery electrolyte recovery system provided by the application comprises the following steps:
s1, cutting off a shell at the position of a tab of a waste lithium battery;
S2, placing the sheared waste lithium batteries into a closed rotary volatilization box 10;
s3, starting the refrigerating unit 30, setting the refrigerating temperature to be minus 20 ℃, wherein the temperature after cooling is 5-10 ℃ higher than the refrigerating temperature, and enabling the temperature after cooling of the refrigerating unit 30 to be between minus 10 ℃ and minus 15 ℃;
s4, when the refrigerating temperature of the refrigerating unit 30 is minus 20 ℃, starting the vacuum pump 50, closing the circulation air return valve 70, opening the exhaust valve 80, discharging the residual air in the system, reducing the vacuum degree of the whole system and ensuring the safety;
s5, introducing inert gas into the airtight rotary volatilizing box 10, opening the circulation air return valve 70, and closing the air outlet valve 80;
s6, starting the airtight rotary volatilizing box 10 to rotate and heat, gradually increasing the temperature inside the airtight rotary volatilizing box 10 and finally keeping the temperature at 130 ℃, controlling the content of VOCs in the gas from the exhaust valve 80 to be not more than 600ppm during the temperature increasing, controlling the gas phase temperature of the gas outlet of the airtight rotary volatilizing box 10 to be not more than 50 ℃, controlling the gas phase temperature of the gas outlet of the refrigerating unit 30 to be not more than-10 ℃, and adjusting by reducing the temperature increasing speed of the airtight rotary volatilizing box 10 or reducing the flow of circulating gas by adjusting the flow control valve 60 when any one of the gas phase temperatures exceeds;
S7, keeping the flow of the circulating gas unchanged when the temperature inside the airtight rotary volatilizing box 10 is 130 ℃, and running the whole system for 5min;
s8, adjusting the flow control valve 60 to gradually reduce the flow of the circulating gas, reducing the air pressure in the sealed rotary volatilizing box 10 to minus 0.1MPa, detecting the content of VOCs in the gas at the exhaust valve 80, closing the circulating air return valve 70 when the content of the VOCs is below 50ppm, and then sequentially closing the sealed rotary volatilizing box 10 to heat, rotating the sealed rotary volatilizing box 10, and the vacuum pump 50 and the refrigerating unit 30;
s9, closing the flow control valve 60, and cutting off the connection of all the devices;
s10, starting a defrosting function of the refrigerating unit 30, setting the defrosting temperature to be higher than 50 ℃, and starting a heat tracing line 23 of the first cyclone separation device 20 to enable the heating temperature to be higher than 40 ℃;
s11, collecting electrolyte liquid collected in the first cyclone separation device 20, the second cyclone separation device 40 and the refrigerating unit 30;
s12, opening the airtight rotary volatilizing box 10, and collecting the lithium battery solid material after the lithium battery solid material is cooled.
Experiments prove that at the temperature above 130 ℃, the diaphragm in the waste lithium battery can melt and blend with other components on the pole piece, which is not beneficial to subsequent separation treatment, so that the volatilization temperature is controlled below 130 ℃. The circulating air flow is a necessary means for realizing the evaporation of electrolyte molecules and timely taking away the sealed rotary volatilizing box 10, and through experiments, under the condition of vacuum-0.1 MPa, the temperature is continuously vacuumized for a period of time at 150 ℃, electrolyte liquid still exists in the volatilizing box after cooling, and under the condition of gas circulation, the evaporation temperature of 130 ℃ is set, the vacuum-0.1 MPa, the place where the gas flows is basically free of liquid, and a large amount of atomized liquid drops of the electrolyte exist after the dead zone of the gas flow is cooled.
The temperature of the refrigerating unit 30 after cooling is between-10 ℃ and-15 ℃; tests prove that in the same group of tests, under the condition of not changing the flow of circulating gas, the refrigeration temperature is-20 ℃, -40 ℃, -60 ℃, -80 ℃, the change of VOCs in the exhaust gas of the outlet of the refrigeration unit 30 is small, and the refrigeration temperature is higher than-10 ℃, and the content of VOCs in the exhaust gas is sharply increased. According to the composition components of the electrolyte, the most main component and the lightest component in the common electrolyte are dimethyl carbonate, the condensation temperature of the dimethyl carbonate is 90 ℃ under normal pressure, and the boiling point of the dimethyl carbonate is-6 ℃ under the pressure of-0.1 MPa, so that the condensation temperature is not required to be too low when the electrolyte of the waste lithium battery is condensed and recovered. By optimizing and improving the condensation temperature, the manufacturing cost of equipment can be reduced for a refrigerating system, and meanwhile, the running COP value of the equipment is improved, so that the energy-saving effect is achieved.
The process has great improvement in the aspects of safety, environmental protection, electrolyte evaporation rate, electrolyte liquid recovery efficiency, operability, device running time, device treatment efficiency and the like; the process avoids the safety and environmental protection problems in the battery recycling process, and enables the waste batteries to volatilize electrolyte from battery materials at a lower evaporation temperature, thereby avoiding the damage of other materials; in addition, the process also solves the problem of exhaust emission in the process of recovering the electrolyte.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the application, which are described in detail and are not to be construed as limiting the scope of the claims. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. Accordingly, the scope of protection of the present application is to be determined by the appended claims.
Claims (8)
1. The utility model provides a old and useless lithium cell electrolyte recovery system which characterized in that includes:
the sealed rotary volatilization box is used for heating and crushing the opened lithium battery, introducing inert gas into the sealed rotary volatilization box, heating the lithium battery to volatilize the electrolyte, and mixing the volatilized electrolyte with the inert gas to form electrolyte volatilized gas; the airtight rotary volatilizing box comprises a barrel body and a heating tube assembly, wherein the barrel body is a horizontally placed barrel, the barrel is connected with a driving mechanism for driving the barrel to rotate, a plurality of baffles with sharp corners are uniformly arranged on the inner wall of the barrel body at intervals around the circumference, the heating tube assembly comprises two heating tube brackets and a plurality of heating tubes, the two heating tube brackets are respectively fixedly connected to two ends of the interior of the barrel body, the heating tubes are placed in a posture parallel to the central axis of the barrel body, the two ends of the heating tube brackets are respectively correspondingly connected with the two heating tube brackets, and the heating tubes are circumferentially distributed around the central axis of the barrel body at intervals;
The first cyclone separation device is used for separating solids and liquid in electrolyte volatile gas from the airtight rotary volatilization box, and a heat tracing wire is arranged on the first cyclone separation device so as to melt condensed electrolyte liquid;
the refrigerating unit is used for cooling the electrolyte volatile gas from the first cyclone separation device to obtain electrolyte liquid and gas with electrolyte liquid drops, and has a defrosting function to melt the condensed electrolyte liquid;
a second cyclone separator for separating electrolyte droplets in the gas from the refrigerator group;
a vacuum pump for forming a vacuum inside the system and circulating an inert gas inside the system;
the closed rotary volatilizing box, the first cyclone separation device, the refrigerating unit, the second cyclone separation device and the vacuum pump are sequentially communicated through pipelines, and the vacuum pump is communicated with the closed rotary volatilizing box through the pipelines, so that a closed circulating system is formed; flow control valves are arranged on the pipelines between the first cyclone separation device and the refrigerating unit and between the second cyclone separation device and the vacuum pump, a circulation return air valve is arranged on the pipeline between the vacuum pump and the airtight rotary volatilizing box, and an exhaust valve for connecting the outside of the pipeline is arranged on the pipeline between the vacuum pump and the circulation return air valve.
2. The waste lithium battery electrolyte recycling system according to claim 1, wherein the driving mechanism comprises a motor, a transmission assembly and a hollow shaft, an output shaft of the motor is connected with the transmission assembly, the transmission assembly is connected with the hollow shaft, the axis of the hollow shaft and the central axis of the cylinder are in the same straight line, one end of the hollow shaft is fixedly connected with the cylinder, the other end of the hollow shaft is connected with a pipeline communicated with an air inlet of the first cyclone separation device through a rotary joint, and the hollow shaft is communicated with the cylinder and the rotary joint.
3. The waste lithium battery electrolyte recycling system according to claim 2, wherein a metal filter screen is arranged at a port of the hollow shaft, which is communicated with the cylinder.
4. The waste lithium battery electrolyte recycling system according to claim 1, wherein a temperature sensor for detecting the temperature inside the cylinder is arranged on the cylinder, the temperature sensor is in communication connection with a temperature controller, and the temperature controller is in communication connection with the heating pipe assembly; the temperature sensors are arranged in a plurality, and the temperature sensors are uniformly distributed on the circumference around the wall surface of the cylinder body.
5. The waste lithium battery electrolyte recycling system according to claim 1, wherein the first cyclone separation device comprises a first cyclone separator, a silk screen and a heat tracing wire, the first cyclone separator is of a vertical cylinder structure, an air outlet is formed in the upper end, a liquid outlet is formed in the lower end, the silk screen is arranged on the air outlet of the first cyclone separator, and the heat tracing wire is spirally wound outside the wall of the lower portion of the first cyclone separator.
6. The waste lithium battery electrolyte recycling system according to claim 1, wherein a first pressure indicator is arranged on the airtight rotary volatilizing box, a first temperature indicator is arranged on an air outlet of the first cyclone separation device, and a second temperature indicator is arranged on an air outlet of the refrigerating unit.
7. The waste lithium battery electrolyte recycling system according to claim 6, wherein a second pressure indicator is arranged on a pipeline between the first cyclone separation device and the refrigerating unit, a third pressure indicator and a third temperature indicator are arranged on a pipeline between the second cyclone separation device and the vacuum pump, and a fourth pressure indicator is arranged at an air outlet of the vacuum pump.
8. An electrolyte recovery process based on the waste lithium battery electrolyte recovery system as claimed in any one of claims 1 to 7, characterized by comprising the steps of:
s1, cutting off a shell at the position of a tab of a waste lithium battery;
s2, placing the sheared waste lithium batteries into a closed rotary volatilization box;
s3, starting the refrigerating unit, setting the refrigerating temperature to be minus 20 ℃, wherein the temperature after cooling is 5-10 ℃ higher than the refrigerating temperature, and enabling the temperature after cooling of the refrigerating unit to be between minus 10 ℃ and minus 15 ℃;
s4, when the refrigerating temperature of the refrigerating unit is minus 20 ℃, starting a vacuum pump, closing a circulating air return valve, opening an exhaust valve, discharging residual air in the system, reducing the vacuum degree of the whole system, and ensuring safety;
s5, introducing inert gas into the airtight rotary volatilizing box, opening a circulation air return valve, and closing an exhaust valve;
s6, starting the airtight rotary volatilizing box to rotate and heat, gradually increasing the temperature inside the airtight rotary volatilizing box and finally keeping the temperature at 130 ℃, controlling the content of VOCs in gas from the exhaust valve to be not more than 600ppm during the temperature increasing, controlling the gas phase temperature of the gas outlet of the airtight rotary volatilizing box to be not more than 50 ℃, controlling the gas phase temperature of the gas outlet of the refrigerating unit to be not more than-10 ℃, and adjusting the temperature increasing speed of the airtight rotary volatilizing box or reducing the flow of circulating gas by adjusting the flow control valve when any one of the gas phase temperatures exceeds the temperature;
S7, when the internal temperature of the closed rotary volatilizing box is 130 ℃, keeping the flow of the circulating gas unchanged, and running the whole system for 5min;
s8, adjusting a flow control valve to gradually reduce the flow of circulating gas, reducing the air pressure in the closed rotary volatilizing box to-0.1 MPa, detecting the content of VOCs in the gas at an exhaust valve, closing the circulating air return valve when the content of the VOCs is below 50ppm, and then sequentially closing the heating of the closed rotary volatilizing box, the rotation of the closed rotary volatilizing box, the vacuum pump and the refrigerating unit;
s9, closing a flow control valve, and cutting off the connection of all the devices;
s10, starting a defrosting function of a refrigerating unit, setting the defrosting temperature to be higher than 50 ℃, and starting a heat tracing wire of a first cyclone separation device to enable the heating temperature to be higher than 40 ℃;
s11, collecting electrolyte liquid collected in the first cyclone separation device, the second cyclone separation device and the refrigerating unit;
s12, opening the airtight rotary volatilizing box, and collecting the lithium battery solid material after the lithium battery solid material is cooled.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114084924A (en) * | 2021-12-22 | 2022-02-25 | 河南巨峰环保科技有限公司 | Lithium battery electrolyte closed heating volatilization device |
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| CN219123317U (en) * | 2022-12-28 | 2023-06-02 | 清研(湖南)新材料有限公司 | Recycling system for positive and negative plates, diaphragms and electrolyte of waste lithium batteries |
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