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CN109355506A - A kind of harmless treatment method and system of metal lithium waste residue - Google Patents

A kind of harmless treatment method and system of metal lithium waste residue Download PDF

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Publication number
CN109355506A
CN109355506A CN201811229986.4A CN201811229986A CN109355506A CN 109355506 A CN109355506 A CN 109355506A CN 201811229986 A CN201811229986 A CN 201811229986A CN 109355506 A CN109355506 A CN 109355506A
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waste residue
lithium
heating chamber
lithium metal
heating
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CN201811229986.4A
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CN109355506B (en
Inventor
钟兆资
曹乃珍
陈欣
刘强
邹崴
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Tianqi Lithium Industry (jiangsu) Co Ltd
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Tianqi Lithium Industry (jiangsu) Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/001—Dry processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses the method for innocent treatment and system of a kind of lithium metal waste residue.The described method includes: lithium metal waste residue is placed in closed heating chamber, and the indoor gas of heating chamber is thoroughly replaced into the protective gas not reacted with lithium；Lithium metal waste residue is heated to the first temperature and is disturbed, and heating chamber is vacuumized, realizes oil removal treatment；After completing the oil removal treatment, continue lithium metal waste residue being heated to second temperature and disturb, melt lithium metal therein and be collected as lithium metal liquid, and is layered lithium metal liquid and solid impurity；It flows out the lithium metal liquid out of heating chamber by being placed in after the indoor strainer of heating chamber, and retains solid impurity by the strainer.Method for innocent treatment of the invention is not chemically reacted when handling lithium metal waste residue, is not contacted with air, has prevented security risk, and directly can fast and effeciently recycle the lithium metal in lithium metal waste residue, simple process, high financial profit.

Description

A kind of method for innocent treatment and system of lithium metal waste residue
Technical field
The present invention relates to a kind of method for innocent treatment of lithium metal waste residue, in particular to a kind of fast and effeciently lithium metal The method for innocent treatment and system of waste residue, recycle lithium metal therein, belong to the recovery technology field of lithium.
Background technique
Lithium metal is Sweden chemist A Aerfuweitesang 1817 and finds in a kind of rare rock first 's.The symbol of element of lithium metal is Li, is argenteous metal, relative atomic mass 6.941, density 0.534g/cm3, it is most Light metal, 180.54 DEG C of fusing point, 1317 DEG C of boiling point.Lithium metal has strong reducing property, can be with a large amount of inorganic reagents and organic examination Agent reacts, with the equal energy chemical combination such as oxygen, nitrogen, sulphur.It is uniquely to be reacted at room temperature with nitrogen, generates lithium nitride (Li3N alkali) Metal.It is exposed to and is easy to react with oxygen in humid air, meet the burning of water vigorous reaction or explosion.In 500 DEG C or so easy and hydrogen It reacts, is that can uniquely generate to be stable enough to melt and the alkali metal of Undec hydride.Lithium metal vulnerable to oxidation and Density ratio kerosene is small, therefore generally deposits in atoleine.At present lithium metal be widely used in lithium battery, aviation, metallurgy, chemical industry, Medicine and building materials etc. are industrial, for producing lithium battery, lightweight lithium-aluminium alloy, organic synthesis vitamin and synthetic rubber etc..
The oily refining stage in lithium metal manufacturing process can generate a large amount of waste residues containing lithium, and quality is about lithium metal yield 3%, main component includes lithium metal, potassium, sodium and its oxide, nitride, carbide.Lithium metal waste residue be usually be immersed in it is white In oil, after pulling out in white oil, surface can uniformly cover one layer of oil film, this layer of oil film prevent water in lithium metal and air, The direct contact of oxygen and nitrogen etc. plays the role of protecting lithium metal waste residue.After lithium metal waste residue recycles barrelling, with putting The extension of time is set, the oil film on lithium metal waste residue surface is gradually thinning, and in the handling process, rubbing between lithium metal waste residue The destruction for promoting oil film is wiped, the generations such as the lithium metal that oil film is protected and water, oxygen and nitrogen in air is lost and reacts as follows:
Li+H2O=LiOH+H2↑
4Li+O2=2Li2O
Li2O+H2O=2LiOH
6Li+N2=2Li3N
Li3N+3H2O=3LiOH+NH3↑
Above-mentioned reaction discharges a large amount of reaction heat, and generates gas, if these lithium metal waste residues cannot be disposed in time, heat Amount cannot discharge in time, gather by prolonged heat, and the temperature of lithium metal waste residue gradually rises, and accumulate to a certain extent just Spontaneous combustion can occur even to explode, cause fire, cause any property loss and personal injury, 3 lithium metals only just occurred within 2012 Waste residue auto-ignition event.Therefore the safe handling of lithium metal waste residue is particularly important, and has very big social value and economic valence Value.
Current lithium metal waste slag treatment method is predominantly following several:
1. lithium metal waste residue, which is dissolved in water, obtains the compound of lithium.For example, patent CN1326640C provides a kind of conjunction At the method for hydrolysis of lithium slag from lithium alkyl, lithium alkylide is filtered in resulting lithium slag income lithium slag surge tank, lithium is then passed through Lithium slag is slowly pressed into hydrolysis kettle by slag metering pump, hydrolysis occurs with water a large amount of in hydrolysis kettle, reaction temperature control exists 60 DEG C hereinafter, and control the additional amount of lithium slag by the temperature of hydrolysis kettle；Reaction heat is taken away by autoclave body collet cooling water, instead The gases such as the hydrocarbon solvent for answering process to be evaporated then are recycled by the way that blowdown condenser is cooling.But lithium metal waste residue is dissolved in Water obtains the compound of lithium, and due to the active character of lithium metal, reaction acutely, generates a large amount of hydrogen when lithium metal waste residue is dissolved in water Gas inevitably will appear the dangerous situations such as burning even explosion, in terms of there is safety and environmental protection.
2. handling lithium metal waste residue by high-temp combustion, oxidation is formed when the metal component in lithium metal waste residue burns Object, and metallic state lithium is then heated to melt and is detached from main body, individually recycles after cooling.For example, patent CN104764024B provides one Kind sodium-potassium-lithium and lithium slag waste treatment device, including combustion chamber, flue gas processing device and flue gas discharger.Point in the combustion chamber Fire sodium-potassium-lithium and lithium slag material, lithium material conversion is oxide, and since the fusing point of lithium metal is low when burning, lithium metal is heated to Row's lithium leak hole is crossed after molten condition and is drained into and is contained lithium basin.The oxide obtained after burning is by the i.e. recyclable lithium money of hydrolysis process Source.A large amount of flue gas is generated in combustion process, which does harmless treatment by flue gas processing device, arranges eventually by flue gas Device drains into the external world out.Lithium metal waste residue is handled by high-temp combustion, also due to the active character of lithium metal, Red-hot metal ball body easy to form under high temperature ignites the gas (hydrogen and organic gas etc.) that reaction generates, so that metal There is hidden danger out of control of burning when lithium waste residue burns in air, it cannot achieve the purpose that safe handling lithium metal waste residue, together When this processing method also have that equipment is more, process is complicated and the higher disadvantage of energy consumption.
3. recycling lithium metal using smelting process.For example, patent CN 106756067A is related to a kind of method for recycling lithium metal And the technique for preparing lithium metal, comprising the following steps: by 50~60 parts of lithium chlorides and 40~50 parts of potassium chloride mixed meltings, obtain To the first mixed molten liquid.Heating melting after addition lithium slag, obtains the second mixed molten liquid in the first mixed molten liquid.It is mixed to second It is melted after 8~10 parts of additives are added after melt removal of impurities, when supernatant liquid becomes silvery white, is recycled from supernatant liquid Lithium metal.Smelting process recycles lithium metal, needs to add more chloride, higher cost, process is longer, and equipment requirement is higher.
Summary of the invention
The main purpose of the present invention is to provide the method for innocent treatment and system of a kind of lithium metal waste residue, to overcome Deficiency in the prior art.
For achieving the above object, present invention employs following technical solutions:
The embodiment of the invention provides a kind of method for innocent treatment of lithium metal waste residue comprising:
Lithium metal waste residue is placed in closed heating chamber, and by the indoor gas of heating chamber be thoroughly replaced into not with lithium The protective gas of reaction；
Lithium metal waste residue is heated to the first temperature and is disturbed, and heating chamber is vacuumized, realizes oil removal treatment；
After completing the oil removal treatment, continues lithium metal waste residue being heated to second temperature and disturb, make wherein Lithium metal melt and be collected as lithium metal liquid, and be layered lithium metal liquid and solid impurity；
It flows out the lithium metal liquid out of heating chamber by being placed in after the indoor strainer of heating chamber, and keeps solid-state miscellaneous Matter is retained by the strainer.
In some embodiments, first temperature is 150~250 DEG C.
In some embodiments, the second temperature is 200~400 DEG C.
Further, the aperture of the strainer is 5 μm~1000 μm.
The embodiment of the invention also provides a kind of innocuity disposal systems of lithium metal waste residue comprising:
Waste residue heats container, with heating chamber, partition is equipped in the heating chamber, the partition is at least used to hold Lithium metal waste residue is carried, peripheral part and heating chamber the inner wall surrounding sealing of the partition cooperate；
Upper cover has protective gas pipeline and out lithium pipeline, and the upper cover lower part is equipped with strainer, when the upper cover When in conjunction with waste residue heating container, the heating chamber is closed, and the strainer is placed in heating chamber；
Heating unit is at least used to heat container to the waste residue and lithium pipeline heats out；
Gas control unit is at least used to input protective gas into the heating chamber or to the heating chamber It vacuumizes；
Rabbling mechanism is at least used to disturb the indoor material of the heating chamber；
Partition driving mechanism is at least used to that the partition to be driven to move up and down in heating chamber；And
Tui Bing mechanism is at least used to remove the residual filter cake remained on partition.
Compared with the prior art, the beneficial effects of the present invention are:
1) when handling lithium metal waste residue chemistry does not occur for the method for innocent treatment of lithium metal waste residue provided by the invention Reaction, does not contact with air, has prevented security risk, and can be directly fast and effeciently in innoxious recycling lithium metal waste residue Lithium metal, simple process, high financial profit；
2) present invention only consumes a small amount of working gas when handling lithium metal waste residue, and working gas can recycle, will not Generate inflammable and poisonous gas, safety and environmental protection；
3) lithium metal waste residue filters pressing at high temperature of the invention, process is rapid, and obtained lithium metal quality is higher, and processing is time-consuming Less, process flow is shorter；Also, treated, and filter cake has a safety feature, and reacts slow with air and water.
Detailed description of the invention
Fig. 1 is a kind of working condition knot of the innocuity disposal system of lithium metal waste residue in a typical embodiments of the invention Structure schematic diagram.
Fig. 2 is a kind of seperated state knot of the innocuity disposal system of lithium metal waste residue in a typical embodiments of the invention Structure schematic diagram.
Description of symbols: 1- waste residue heats container, 10- heating chamber, 11- partition, 200- upper cover, 21- protective gas Pipeline, 22- go out lithium pipeline, 23- strainer, 300- heating unit, 400- rabbling mechanism, 500- process gas pipes, and 600- pushes away cake Mechanism, 700- upper cover driving mechanism, 800- residual filter cake.
Specific embodiment
In view of deficiency in the prior art, inventor is studied for a long period of time and is largely practiced, and is able to propose of the invention Technical solution as follows will be further explained the technical solution, its implementation process and principle etc..
As the one aspect of technical solution of the present invention, involved in be a kind of lithium metal waste residue harmless treatment side Method comprising:
Lithium metal waste residue is placed in closed heating chamber, and by the indoor gas of heating chamber be thoroughly replaced into not with lithium The protective gas of reaction；
Lithium metal waste residue is heated to the first temperature and is disturbed, and heating chamber is vacuumized, realizes oil removal treatment；
After completing the oil removal treatment, continues lithium metal waste residue being heated to second temperature and disturb, make wherein Lithium metal melt and be collected as lithium metal liquid, and be layered lithium metal liquid and solid impurity；
It flows out the lithium metal liquid out of heating chamber by being placed in after the indoor strainer of heating chamber, and keeps solid-state miscellaneous Matter is retained by the strainer.
For fast and effeciently handling lithium metal waste residue and recycling lithium metal therein, concrete application range includes the present invention But it is not limited only to: the mixture of the processing of lithium metal waste residue and other mixtures containing lithium metal, alkali metal and alkali metal containing Processing.
In some embodiments, first temperature is 150~250 DEG C.
In some embodiments, the second temperature is 200~400 DEG C.When heating, the temperature of lithium metal waste residue molten liquid Degree can also isolate lithium metal molten liquid at slightly below 200 DEG C by strainer, but filter process is extremely slow, filtration time It is too long；The temperature of lithium metal waste residue molten liquid can also isolate lithium metal molten liquid, but high temperature at 400 DEG C or more by strainer In the case of impurity may burn, volatilize and melt, and energy consumption is excessively high, and filtering rate will not improve.
Further, the aperture of the strainer is 5 μm~1000 μm.When the aperture of the strainer is then easier to block up lower than 5 μm Plug, influences filter efficiency；Higher than 1000 μm, then impurity is easier to impurity in the lithium metal for causing recycling by strainer in the aperture of strainer Content is higher.
In some embodiments, which comprises when lithium metal waste residue temperature is increased to 150~250 DEG C, to heating It is 100~1000Pa that chamber, which is evacuated to pressure, and maintains the pressure and carry out the oil removal treatment.The melting of lithium metal waste residue After liquid heating can not also oil removing, but white oil can be flowed out with lithium metal molten liquid when filters pressing, influence filter efficiency and lithium metal Quality.
In some embodiments, which comprises lithium metal waste residue is heated to second temperature and is stirred, is stirred Time is 1min~60min, is layered the lithium metal liquid obtained and solid impurity.When being stirred after the heating of lithium metal waste residue molten liquid Between can be lower than 1min, but to be stirred the ratio scattered smaller for the solid impurity for wrapping up liquid metal lithium, influences filtering rate；It stirs 60min can be higher than by mixing the time, but energy consumption is excessively high, and time-consuming excessive, filtering rate will not improve.
The present invention heats lithium metal waste residue, lower melting-point lithium metal melting in slag, impurity in the environment of completely cutting off air Still it is in solid-state, but lithium metal drop is wrapped up or separated by nitride and impurity, melts bulk in lithium, the present invention can break by stirring Interval between the molten group of lithium, promotes lithium liquid enrichment, realizes the layering (lithium liquid is in upper, impurity under) of lithium liquid and impurity, then again Apply pressure by mechanical or gas, allow molten lithium liquid by filter screen outflow, impurity is then intercepted, can be in separating Li slag Lithium metal and impurity.Lithium metal waste residue molten liquid heating after can not also stir, but solid impurity still as heat up it is previous as wrap up Liquid metal lithium, filter efficiency is low when pressure filtration.
Further, after making the lithium metal liquid and solid impurity layering, then 1min~60min is stood.Lithium metal is useless Time of repose can be lower than 1min after the heating stirring of slag molten liquid, but the layering of lithium metal molten liquid is unobvious, influences filtering rate； Time of repose can be higher than 60min, but time-consuming excessive, and filtering rate will not improve.
Among some specific implementation cases, the method be may particularly include:
Lithium metal waste residue merging waste residue is heated in the heating chamber of container, and is distributed in metal waste residue on partition, institute Stating partition can move up and down in the heating chamber；
By upper cover in conjunction with waste residue heating container, keep the heating chamber closed, the upper cover has protective gas pipe Road and out lithium pipeline, and the upper cover lower part is equipped with strainer；
The indoor gas of the heating chamber is thoroughly replaced into protective gas by the protective gas pipeline；
To the waste residue heating container heat, start when lithium metal waste residue temperature therein rises to the first temperature into Row stirring, and heating chamber is vacuumized, carry out the oil removal treatment；
After completing the oil removal treatment, continues lithium metal waste residue being heated to second temperature and accelerate to stir, make to obtain The lithium metal liquid and solid impurity obtained is layered, and is stopped stirring later and is simultaneously stood；
Drive partition to move from bottom to top, and cooperate with the strainer, to the lithium metal liquid and solid impurity into Row filters pressing processing after so that lithium metal liquid is passed through strainer, then is gone out lithium pipeline and is exported to collection lithium tank, and cuts solid impurity by strainer It stays.
Further, which comprises pressure is applied to lithium metal waste residue molten liquid from lower to upper, forces lithium metal molten Melt liquid and passes through strainer.Wherein, applying pressure to lithium metal waste residue molten liquid from top to bottom can also force lithium metal molten liquid logical Filter screen, but since the impurity of lithium metal waste residue molten liquid after stirring and stratification concentrates on lower layer, the net of strainer when filtering Hole is easy blocking, and filter efficiency is lower.
In some embodiments, the method also includes: after the completion of the described filters pressing processing, pass through the protective gas Pipeline is blown into protective gas, the lithium liquid of strainer upper space is discharged into completely in collection lithium tank.
In some embodiments, the method also includes: after the completion of the described filters pressing processing, in waste residue heating container Temperature when being lower than 150 DEG C, pressure recovery to normal pressure, upper cover and waste residue are heated into container and separated, and will be remained on partition Residual filter cake removes, and then makes partition return to initial position.
Further, the method also includes: by process gas pipes into the heating chamber input service gas, To drive the partition to move from bottom to top in the heating chamber.
Further, the maximum pressure of the filters pressing processing is 0.5~5MPa.Wherein, promotion is provided by mechanical or gas The pressure of lithium metal waste residue molten liquid.
In some embodiments, the method also includes: after completing the oil removal treatment, by waste residue heat container, Process gas pipes, the working gas being connected to process gas pipes heat container and lithium pipeline is both heated to second temperature out 200~400 DEG C, the disturbance, standing, filters pressing processing are successively carried out later.
Further, the protective gas or working gas include more than one inert gases.Further, work Make gas or protective gas can be mixing for a kind of pure gas not react with lithium or a variety of gases not reacted with lithium Close gas.
Wherein, as more specifically one of case study on implementation of the invention, the harmless treatment side of the lithium metal waste residue Method may particularly include following steps:
1. taking lithium metal waste residue, it is put into waste residue heating container；
2. passing through hydraulic pressure lift having protective gas pipeline and installing the strainer of certain pore size on the upper lid of lithium pipeline out Bar (i.e. upper cover driving mechanism) puts down upper cover, and sealing waste residue heats container, and device is as shown in Figure 1 after sealing；
3. opening gas control unit, atmosphere in container, displacement are heated by the protective gas pipeline displacement waste residue of upper cover Gas is the inert gases such as argon gas, guarantees that waste residue heating tainer air is thoroughly replaced；
4. closing gas control unit, open heating unit (i.e. temperature control system), container, work gas are heated to waste residue Body heats container, process gas pipes and lithium pipeline is heated out；
5. opening stirring, and pass through when waste residue heating container interior metal lithium waste residue temperature is increased to 150~250 DEG C Gas control unit heats container vacuum-pumping to waste residue, and pressure certain time within the scope of 100~1000Pa is maintained to carry out oil removing, And it opens external oil cooled system system and is recycled；
6. after thorough oil removing, closing gas control unit, 200~400 DEG C being continuously heating to, and accelerate to stir, by stirring It mixes and molten lithium slag is promoted to be layered；
7. stopping stirring and standing a period of time, gradually pressurizeed by mechanical or gas to partition, carry out filters pressing, is melted Melt lithium liquid and enter collection lithium tank by going out lithium pipeline across strainer, controlling maximum pressure in the process is 0.5~5MPa；
8. being blown into argon gas by protective gas pipeline, the molten lithium liquid of strainer upper space is discharged into completely in collection lithium tank, Then stop being blown into high-purity argon gas from protective gas pipeline；
9. stopping heating pressurization, when waste residue heating vessel temp is down to normal pressure lower than 150 DEG C, pressure, mentioned by hydraulic Rising stem (i.e. upper cover driving mechanism) promotes upper cover, and separation upper cover and waste residue heat container, increases residue filter by bottom compression partition Cake, then residual filter cake is released with Tui Bing mechanism (i.e. hydraulic thrust cake bar), then partition is put down in pressure release, repeats to handle next time Process；
10. analysis is the results show that lithium metal is required up to technical grade in collection lithium tank, lithium metal content obviously drops in residual filter cake Low, up to 80% or more, residual filter cake is substantially reduced the lithium metal rate of recovery with water reactivity.
To sum up, the method for innocent treatment of lithium metal waste residue provided by the invention is not changed when handling lithium metal waste residue Reaction is learned, is not contacted with air, has prevented security risk, and can be directly fast and effeciently in innoxious recycling lithium metal waste residue Lithium metal, simple process, high financial profit；A small amount of working gas, and working gas are only consumed when handling lithium metal waste residue It can recycle, inflammable and poisonous gas, safety and environmental protection will not be generated.
As the other side of technical solution of the present invention, involved in be a kind of lithium metal waste residue harmless treatment System comprising:
Waste residue heats container, with heating chamber, partition is equipped in the heating chamber, the partition is at least used to hold Lithium metal waste residue is carried, peripheral part and heating chamber the inner wall surrounding sealing of the partition cooperate；
Upper cover has protective gas pipeline and out lithium pipeline, and the upper cover lower part is equipped with strainer, when the upper cover When in conjunction with waste residue heating container, the heating chamber is closed, and the strainer is placed in heating chamber；
Heating unit is at least used to heat container to the waste residue and lithium pipeline heats out；
Gas control unit is at least used to input protective gas into the heating chamber or to the heating chamber It vacuumizes；
Rabbling mechanism is at least used to disturb the indoor material of the heating chamber；
Partition driving mechanism is at least used to that the partition to be driven to move up and down in heating chamber；And
Tui Bing mechanism is at least used to remove the residual filter cake remained on partition.
In some embodiments, the Tui Bing mechanism include it is horizontally disposed push away cake bar, the partition at least can be It is moved back and forth between one station, second station and 3rd station, first station, second station and 3rd station are from bottom to top It sets gradually；At the second station, the partition can cooperatively form pressure filtration mechanism with strainer, and the pressure filtration mechanism is at least For filtering out lithium metal liquid from the mixture of lithium metal liquid and solid impurity and transport to out lithium pipeline, and make more than solid impurity It stays in forming residual filter cake on partition；At the 3rd station, the residual filter cake is concordant with cake bar is pushed away.
In some embodiments, the partition driving mechanism includes the process gas pipes and work being connected to heating chamber Make the working gas heating container of gas pipeline connection, and the heating unit is at least also used to the working gas heating container It is heated with process gas pipes.
Wherein, the working gas heating container refers to that working gas carries out before entering lithium metal waste residue heating container A pre-heated container, after working gas first heats second temperature wherein, using the work for being heated to second temperature Gas pipeline heat preservation enters waste residue and heats container, avoids leading after the working gas of lower temperature is directly passed through waste residue heating container The melting waste residues temperature of cause, which reduces, even to be solidified.
Further, the lithium pipeline out is connected to collection lithium tank.
Further, the heating chamber is also connected to external oil cooled system system.
In some embodiments, the system also includes: upper cover driving mechanism is at least used to that upper cover to be driven to add with waste residue Heat container separation combines.
Specifically, please refer to shown in Fig. 1 and Fig. 2, a kind of lithium metal waste residue is innoxious in an exemplary embodiments of the invention Processing system includes: waste residue heating container 100, upper cover 200, heating unit 300, gas control unit, (this of rabbling mechanism 400 Blender is used in embodiment), partition driving mechanism, Tui Bing mechanism 600 (in the present embodiment use hydraulic thrust cake bar), upper cover drive Motivation structure 700 (uses hydraulic pressure lift bar) in the present embodiment.
Wherein, the waste residue heating container 100 has heating chamber 10, is equipped with partition 11, institute in the heating chamber 10 Partition 11 is stated at least for bearing metal lithium waste residue, and peripheral part and the sealing of 10 inner wall surrounding of heating chamber of the partition 11 are matched It closes.The heating chamber 10 is also connected to external oil cooled system system.
The upper cover 200 lithium pipeline 22 with protective gas pipeline 21 and out, the lithium pipeline 22 out are connected to collection lithium tank, And 200 lower part of upper cover is equipped with strainer 23, and when the upper cover 200 is combined with waste residue heating container 100, the heating chamber Room 10 is closed, and the strainer 23 is placed in heating chamber 10.The upper cover driving mechanism 700 (i.e. hydraulic pressure lift bar) is extremely It is few to separate or combine for driving upper cover 200 to heat container 100 with waste residue.
The heating unit 300 (heating layer is used in the present embodiment) is at least for heating 100 He of container to the waste residue Lithium pipeline 22 is heated out.The gas control unit be at least used for into the heating chamber 10 input protective gas or The heating chamber 10 is vacuumized.The rabbling mechanism 400 (i.e. blender) is at least for disturbing in the heating chamber 10 Material.
The partition driving mechanism includes the process gas pipes 500 and process gas pipes being connected to heating chamber 10 The working gas of 500 connections heats container, is at least used to that the partition 11 to be driven to move up and down in heating chamber 10.
The Tui Bing mechanism 600 pushes away cake bar including horizontally disposed, and the partition 11 at least can be in the first station, second It is moved back and forth between station and 3rd station, first station, second station and 3rd station are set gradually from bottom to top；? At the second station, the partition 11 can cooperatively form pressure filtration mechanism with strainer 23, the pressure filtration mechanism be at least used for from Lithium metal liquid is filtered out in the mixture of lithium metal liquid and solid impurity and transports to out lithium pipeline 22, and remains in solid impurity Residual filter cake 800 is formed on partition 11；As shown in Fig. 2, the residual filter cake 800 is put down with cake bar is pushed away at the 3rd station Together.That is, can complete in the same chamber for heating, filtering of lithium metal slag etc., required working space can be effectively reduced, Operating efficiency is improved, may additionally facilitate the promotion of the lithium metal rate of recovery and quality.
The innocuity disposal system structure of lithium metal waste residue provided by the invention designs advantages of simple, can make lithium metal waste residue Filters pressing at high temperature, process is rapid, and obtained lithium metal quality is higher, and processing is time-consuming less, and process flow is shorter；Also, it handles Filter cake afterwards has a safety feature, and reacts slow with air and water.
Below with reference to several preferred embodiments and attached drawing, further details of the technical solution of the present invention, it is clear that Described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the implementation in the present invention Example, those of ordinary skill in the art's every other embodiment obtained without making creative work, all belongs to In the scope of protection of the invention.The test method of actual conditions is not specified in the following example, usually according to normal condition.
Embodiment 1
In the present embodiment lithium metal waste residue method for innocent treatment specifically includes the following steps:
1. taking 1000g lithium metal waste residue in high-purity argon gas protective atmosphere, it is put into waste residue heating container；
2. being mentioned in the strainer for having protective gas pipeline and the upper cover upper installing hole diameter of lithium pipeline is 50 μm out by hydraulic Rising stem puts down upper cover, and sealing waste residue heats container；
3. open gas control unit, waste residue is discharged by the protective gas pipeline of upper cover and heats container internal atmosphere to true Reciprocal of duty cycle is 0.09MPa and is filled with high-purity argon gas to normal pressure, is stopped after recycling 3 times；
4. close gas control unit, opening temperature control system, to waste residue heating container, working gas heating container, Process gas pipes and lithium pipeline is heated out；
5. opening stirring, and pass through gas control when waste residue heating container interior metal lithium waste residue temperature is increased to 200 DEG C Unit processed heats container vacuum-pumping to waste residue, and maintenance vacuum degree is 1000Pa, opens external oil cooled system system and is recycled, can To see that oil smoke is discharged from protective gas pipeline；
6. being discharged without oil smoke from protective gas pipeline, i.e., after thorough oil removing, gas control unit is closed, is continued to waste residue It heats container, working gas heating container, process gas pipes and lithium pipeline is heated out, kept the temperature after reaching 300 DEG C, and add Speed stirring 10min；
7. stopping stirring, lithium metal waste residue molten liquid 10min is stood, the working gas pipe of lower vessel portion is heated by waste residue Road is passed through the high-purity argon gas after heating, and partition is pushed to rise, and after lithium metal waste residue molten liquid touches strainer, at the uniform velocity improves pressure Filters pressing is carried out to 1.0MPa, molten lithium liquid passes through strainer and enters collection lithium tank by going out lithium pipeline；
8. being observed out in lithium pipeline after there is no the outflow of lithium metal molten liquid from the peephole of collection lithium tank, pass through protective gas Pipeline is blown into high-purity argon gas, the lithium liquid of strainer upper space is discharged into collection lithium tank completely, is then stopped from protective gas pipeline It is blown into high-purity argon gas；
9. stopping heating pressurization, when waste residue heating vessel temp is down to normal pressure lower than 150 DEG C, pressure, mentioned by hydraulic Rising stem promotes upper cover, and separation upper cover and waste residue heat container, increases residual filter cake by bottom compression partition, then with hydraulic thrust cake bar Residual filter cake is released, then partition is put down in pressure release；
10. lithium metal block and filter cake after cooling are taken out in high-purity argon gas protective atmosphere, sample preparation detection, lithium metal block matter Amount is 853g, and the lithium rate of recovery is 85.3%.It is 0.14% that Li content, which is 99.7%, Na content, in lithium metal block, reaches technical grade Lithium metal requirement.Lithium metal content is 5.2% in residual filter cake, and residue is substantially reduced with water reactivity.
Embodiment 2
In the present embodiment lithium metal waste residue method for innocent treatment specifically includes the following steps:
1. taking 1000g lithium metal waste residue in high-purity argon gas protective atmosphere, it is put into waste residue heating container；
2. in the strainer for having protective gas pipeline and the upper cover upper installing hole diameter of lithium pipeline is 1000 μm out, by hydraulic Lift lever puts down upper cover, and sealing waste residue heats container；
3. open gas control unit, waste residue is discharged by the protective gas pipeline of upper cover and heats container internal atmosphere to true Reciprocal of duty cycle is 0.09MPa and is filled with high-purity argon gas to normal pressure, is stopped after recycling 3 times；
4. close gas control unit, opening temperature control system, to waste residue heating container, working gas heating container, Process gas pipes and lithium pipeline is heated out；
5. opening stirring, and pass through gas control when waste residue heating container interior metal lithium waste residue temperature is increased to 150 DEG C Unit processed heats container vacuum-pumping to waste residue, and maintenance vacuum degree is 100Pa, opens external oil cooled system system and is recycled, can To see that oil smoke is discharged from protective gas pipeline；
6. being discharged without oil smoke from protective gas pipeline, i.e., after thorough oil removing, gas control unit is closed, is continued to waste residue It heats container, working gas heating container, process gas pipes and lithium pipeline is heated out, kept the temperature after reaching 200 DEG C, and add Speed stirring 60min；
7. stopping stirring, lithium metal waste residue molten liquid 60min is stood, the working gas pipe of lower vessel portion is heated by waste residue Road is passed through the high-purity argon gas after heating, and partition is pushed to rise, and after lithium metal waste residue molten liquid touches strainer, at the uniform velocity improves pressure Filters pressing is carried out to 0.5MPa, molten lithium liquid passes through strainer and enters collection lithium tank by going out lithium pipeline；
8. being observed out in lithium pipeline after there is no the outflow of lithium metal molten liquid from the peephole of collection lithium tank, pass through protective gas Pipeline is blown into high-purity argon gas, the lithium liquid of strainer upper space is discharged into collection lithium tank completely, is then stopped from protective gas pipeline It is blown into high-purity argon gas；
9. stopping heating pressurization, when waste residue heating vessel temp is down to normal pressure lower than 150 DEG C, pressure, mentioned by hydraulic Rising stem promotes upper cover, and separation upper cover and waste residue heat container, increases residual filter cake by bottom compression partition, then with hydraulic thrust cake bar Residual filter cake is released, then partition is put down in pressure release；
10. lithium metal block and filter cake after cooling are taken out in high-purity argon gas protective atmosphere, sample preparation detection, lithium metal block matter Amount is 866g, and the lithium rate of recovery is 86.6%.It is 0.15% that Li content, which is 99.6%, Na content, in lithium metal block, reaches technical grade Lithium metal requirement.Lithium metal content is 5.1% in residual filter cake, and residue is substantially reduced with water reactivity.
Embodiment 3
In the present embodiment lithium metal waste residue method for innocent treatment specifically includes the following steps:
1. taking 1000g lithium metal waste residue in high-purity argon gas protective atmosphere, it is put into waste residue heating container；
2. being mentioned in the strainer for having protective gas pipeline and the upper cover upper installing hole diameter of lithium pipeline is 5 μm out by hydraulic Rising stem puts down upper cover, and sealing waste residue heats container；
3. open gas control unit, waste residue is discharged by the protective gas pipeline of upper cover and heats container internal atmosphere to true Reciprocal of duty cycle is 0.09MPa and is filled with high-purity argon gas to normal pressure, is stopped after recycling 3 times；
4. close gas control unit, opening temperature control system, to waste residue heating container, working gas heating container, Process gas pipes and lithium pipeline is heated out；
5. opening stirring, and pass through gas control when waste residue heating container interior metal lithium waste residue temperature is increased to 250 DEG C Unit processed heats container vacuum-pumping to waste residue, and maintenance vacuum degree is 500Pa, opens external oil cooled system system and is recycled, can To see that oil smoke is discharged from protective gas pipeline；
6. being discharged without oil smoke from protective gas pipeline, i.e., after thorough oil removing, gas control unit is closed, is continued to waste residue It heats container, working gas heating container, process gas pipes and lithium pipeline is heated out, kept the temperature after reaching 400 DEG C, and add Speed stirring 1min；
7. stopping stirring, lithium metal waste residue molten liquid 1min is stood, the working gas pipe of lower vessel portion is heated by waste residue Road is passed through the high-purity argon gas after heating, and partition is pushed to rise, and after lithium metal waste residue molten liquid touches strainer, at the uniform velocity improves pressure Filters pressing is carried out to 5.0MPa, molten lithium liquid passes through strainer and enters collection lithium tank by going out lithium pipeline；
8. being observed out in lithium pipeline after there is no the outflow of lithium metal molten liquid from the peephole of collection lithium tank, pass through protective gas Pipeline is blown into high-purity argon gas, the lithium liquid of strainer upper space is discharged into collection lithium tank completely, is then stopped from protective gas pipeline It is blown into high-purity argon gas；
9. stopping heating pressurization, when waste residue heating vessel temp is down to normal pressure lower than 150 DEG C, pressure, mentioned by hydraulic Rising stem promotes upper cover, and separation upper cover and waste residue heat container, increases residual filter cake by bottom compression partition, then with hydraulic thrust cake bar Residual filter cake is released, then partition is put down in pressure release；
10. lithium metal block and filter cake after cooling are taken out in high-purity argon gas protective atmosphere, sample preparation detection, lithium metal block matter Amount is 834g, and the lithium rate of recovery is 83.4%.It is 0.15% that Li content, which is 99.7%, Na content, in lithium metal block, reaches technical grade Lithium metal requirement.Lithium metal content is 5.9% in residual filter cake, and residue is substantially reduced with water reactivity.
In conclusion method for innocent treatment provided by the invention is in processing lithium metal waste residue by above-mentioned technical proposal When do not chemically react, do not contacted with air, prevented security risk, and it is useless directly can fast and effeciently to recycle lithium metal Lithium metal in slag, simple process, high financial profit.
In addition, inventor also refers to the mode of embodiment 1-3, with the other raw materials and condition listed in this specification Etc. being tested, and the equally successful lithium metal directly fast and effeciently recycled in lithium metal waste residue, simple process are economical High efficiency.
It should be noted that, in this document, under normal circumstances, the element limited by sentence " including ... " is not arranged Except there is also other identical elements in including the steps that the element, process, method or experimental facilities.
It should be appreciated that the above preferred embodiment is merely to illustrate the contents of the present invention, in addition to this, there are also other by the present invention Embodiment, as long as those skilled in the art because of technical inspiration involved in the present invention, and use equivalent replacement or equivalent deformation The technical solution that mode is formed is fallen within the scope of protection of the present invention.

Claims (10)

1.一种金属锂废渣的无害化处理方法，其特征在于包括：1. a harmless treatment method of metallic lithium waste residue is characterized in that comprising: 将金属锂废渣置于密闭的加热腔室内，并将加热腔室内的气体彻底置换为不与锂反应的保护性气体；The metal lithium waste residue is placed in a closed heating chamber, and the gas in the heating chamber is completely replaced with a protective gas that does not react with lithium; 将金属锂废渣加热至第一温度并进行扰动，且对加热腔室抽真空，实现除油处理；The metal lithium waste residue is heated to the first temperature and disturbed, and the heating chamber is evacuated to realize degreasing treatment; 完成所述的除油处理后，继续将金属锂废渣加热至第二温度并进行扰动，使其中的金属锂熔融并聚集为金属锂液，且使金属锂液与固态杂质分层；After completing the degreasing treatment, continue to heat the metal lithium waste residue to a second temperature and perform disturbance, so that the metal lithium therein is melted and aggregated into a metal lithium liquid, and the metal lithium liquid and solid impurities are layered; 使所述的金属锂液通过置于加热腔室内的滤网后从加热腔室内流出，而使固态杂质被所述的滤网截留。The metal lithium liquid flows out from the heating chamber after passing through the filter screen placed in the heating chamber, so that the solid impurities are retained by the filter screen. 2.根据权利要求1所述的金属锂废渣的无害化处理方法，其特征在于：所述的第一温度为150～250℃；和/或，所述的第二温度为200～400℃；和/或，所述滤网的孔径为5μm～1000μm。2 . The harmless treatment method of metal lithium waste residue according to claim 1 , wherein the first temperature is 150-250° C.; and/or the second temperature is 200-400° C. 3 . and/or, the pore size of the filter screen is 5 μm˜1000 μm. 3.根据权利要求1所述的金属锂废渣的无害化处理方法，其特征在于包括：3. the harmless treatment method of metal lithium waste residue according to claim 1 is characterized in that comprising: 对加热腔室抽真空至压力为100～1000Pa，并维持该压力而进行所述的除油处理；Evacuate the heating chamber to a pressure of 100-1000 Pa, and maintain the pressure to carry out the degreasing treatment; 和/或，将金属锂废渣加热至第二温度并进行搅拌，搅拌时间为1min～60min，使获得的金属锂液与固态杂质分层；And/or, the metal lithium waste residue is heated to the second temperature and stirred, and the stirring time is 1min～60min, so that the obtained metal lithium liquid and solid impurities are layered; 和/或，使所述的金属锂液与固态杂质分层后，再静置1min～60min。And/or, after layering the metal lithium liquid and the solid impurities, it is allowed to stand for 1 min to 60 min. 4.根据权利要求1-3中任一项所述的金属锂废渣的无害化处理方法，其特征在于具体包括：4. the harmless treatment method of metal lithium waste residue according to any one of claim 1-3, it is characterized in that specifically comprising: 将金属锂废渣置入废渣加热容器的加热腔室内，并使金属废渣分布于隔板上，所述隔板可以在所述加热腔室内上下移动；Putting the metal lithium waste residue into the heating chamber of the waste residue heating container, and distributing the metal waste residue on the separator, the separator can move up and down in the heating chamber; 将上盖与废渣加热容器结合，使所述加热腔室被密闭，所述上盖带有保护气体管道和出锂管道，且所述上盖下部安装有滤网；The upper cover is combined with the waste residue heating container, so that the heating chamber is sealed, the upper cover is provided with a protective gas pipeline and a lithium outlet pipeline, and a filter screen is installed at the lower part of the upper cover; 通过所述的保护气体管道将所述加热腔室内的气体彻底置换为保护性气体；Completely replace the gas in the heating chamber with a protective gas through the protective gas pipeline; 对所述废渣加热容器进行加热，当其中的锂金属废渣温度升至第一温度时开始进行搅拌，并对加热腔室抽真空，进行所述的除油处理；Heating the waste residue heating container, start stirring when the temperature of the lithium metal waste residue rises to the first temperature, and evacuating the heating chamber to carry out the degreasing treatment; 在完成所述的除油处理后，继续将金属锂废渣加热至第二温度并加速搅拌，使获得的金属锂液与固态杂质分层，之后停止搅拌并静置；After completing the degreasing treatment, continue to heat the metal lithium waste residue to the second temperature and accelerate the stirring, so that the obtained metal lithium liquid and solid impurities are layered, then stop stirring and let stand; 驱使隔板从下向上移动，并与所述的滤网配合，对所述的金属锂液及固态杂质进行压滤处理，使金属锂液通过滤网后，再经出锂管道输出至集锂罐，而使固态杂质被滤网截留。The separator is driven to move from bottom to top, and cooperates with the filter screen to perform pressure filtration on the metal lithium liquid and solid impurities, so that the metal lithium liquid passes through the filter screen, and then is output to the lithium collector through the lithium outlet pipeline. tank, so that solid impurities are trapped by the filter screen. 5.根据权利要求4所述的金属锂废渣的无害化处理方法，其特征在于还包括：5. the harmless treatment method of metal lithium waste residue according to claim 4 is characterized in that also comprising: 在所述的压滤处理完成后，通过所述保护气体管道吹入保护性气体，将滤网上部空间的锂液完全排入集锂罐内；After the pressure filtration treatment is completed, the protective gas is blown into the protective gas pipeline, and the lithium liquid in the upper space of the filter screen is completely discharged into the lithium collecting tank; 和/或，在所述的压滤处理完成后，待废渣加热容器内的温度低于150℃、压力恢复至常压时，将上盖与废渣加热容器分离，并将余留于隔板上的残渣滤饼移除，而后使隔板回返至初始位置；And/or, after the pressure filtration treatment is completed, when the temperature in the waste residue heating container is lower than 150°C and the pressure returns to normal pressure, the upper cover is separated from the waste residue heating container, and the residue is left on the separator. The residual filter cake is removed, and then the separator is returned to its original position; 和/或，通过工作气体管道向所述加热腔室内输入工作气体，从而驱使所述隔板在所述加热腔室内从下向上移动；And/or, input working gas into the heating chamber through the working gas pipeline, so as to drive the partition plate to move from bottom to top in the heating chamber; 和/或，所述压滤处理的最大压力为0.5～5MPa。And/or, the maximum pressure of the filter press treatment is 0.5-5 MPa. 6.根据权利要求5所述的金属锂废渣的无害化处理方法，其特征在于还包括：在完成所述的除油处理后，将废渣加热容器、工作气体管道、与工作气体管道连通的工作气体加热容器和出锂管道均加热至第二温度，之后依次进行所述的扰动、静置、压滤处理；6. The harmless treatment method of metal lithium waste residue according to claim 5, characterized in that it further comprises: after completing the degreasing treatment, the waste residue heating container, the working gas pipeline, and the working gas pipeline are communicated with each other. Both the working gas heating container and the lithium outlet pipeline are heated to the second temperature, and then the disturbance, standing, and pressure filtration treatment are performed in sequence; 和/或，所述的保护性气体或工作气体包括一种以上惰性气体。And/or, the protective gas or working gas includes more than one inert gas. 7.一种金属锂废渣的无害化处理系统，其特征在于包括：7. a harmless treatment system of metal lithium waste residue, is characterized in that comprising: 废渣加热容器，其具有加热腔室，所述加热腔室内设有隔板，所述隔板至少用于承载金属锂废渣，所述隔板的外周部与加热腔室内壁环绕密封配合；A waste slag heating container, which has a heating chamber, and a separator is arranged in the heating chamber, the separator is at least used to carry metal lithium waste slag, and the outer periphery of the separator is in sealing fit with the inner wall of the heating chamber; 上盖，其带有保护气体管道和出锂管道，且所述上盖下部安装有滤网，当所述上盖与废渣加热容器结合时，所述加热腔室被密闭，而所述滤网被置于加热腔室内；The upper cover has a protective gas pipeline and a lithium outlet pipeline, and a filter screen is installed at the lower part of the upper cover. When the upper cover is combined with the waste residue heating container, the heating chamber is sealed, and the filter screen be placed in a heating chamber; 加热单元，其至少用于对所述废渣加热容器和出锂管道进行加热；a heating unit, which is at least used for heating the waste residue heating container and the lithium outlet pipeline; 气体控制单元，其至少用于向所述加热腔室内输入保护性气体或对所述加热腔室抽真空；a gas control unit, which is at least used for inputting protective gas into the heating chamber or evacuating the heating chamber; 搅拌机构，其至少用于扰动所述加热腔室内的物料；a stirring mechanism, which is at least used to disturb the material in the heating chamber; 隔板驱动机构，其至少用于驱使所述隔板在加热腔室内上下移动；以及a partition drive mechanism for at least driving the partition to move up and down within the heating chamber; and 推饼机构，其至少用于移除余留于隔板上的残渣滤饼。The cake pushing mechanism is at least used to remove the residual filter cake remaining on the separator. 8.根据权利要求7所述的金属锂废渣的无害化处理系统，其特征在于：所述推饼机构包括水平设置的推饼杆，所述隔板至少能够在第一工位、第二工位和第三工位之间往返移动，所述第一工位、第二工位和第三工位从下向上依次设置；在所述第二工位处，所述隔板能够与滤网配合形成压滤机构，所述压滤机构至少用于从金属锂液与固态杂质的混合物中滤出金属锂液并输往出锂管道，以及使固态杂质余留于隔板上形成残渣滤饼；在所述第三工位处，所述残渣滤饼与推饼杆平齐。8 . The harmless treatment system for metal lithium waste residue according to claim 7 , wherein the cake pushing mechanism comprises a cake pushing rod arranged horizontally, and the separator can at least The reciprocating movement between the station and the third station, the first station, the second station and the third station are arranged in order from bottom to top; at the second station, the partition can be connected with the filter. The mesh cooperates to form a filter press mechanism, and the filter press mechanism is at least used to filter out the metal lithium liquid from the mixture of the metal lithium liquid and the solid impurities and output it to the lithium pipeline, and to make the solid impurities remain on the separator to form a residue filter. cake; at the third station, the residue filter cake is flush with the cake push rod. 9.根据权利要求7所述的金属锂废渣的无害化处理系统，其特征在于：所述隔板驱动机构包括与加热腔室连通的工作气体管道、与工作气体管道连通的工作气体加热容器，且所述加热单元至少还用于所述工作气体加热容器和工作气体管道加热；和/或，所述出锂管道与集锂罐连通；和/或，所述加热腔室还与外部油冷系统连通。9 . The harmless treatment system for metal lithium waste residue according to claim 7 , wherein the partition drive mechanism comprises a working gas pipeline communicated with the heating chamber, and a working gas heating container communicated with the working gas pipeline. 10 . , and the heating unit is at least also used for heating the working gas heating container and the working gas pipeline; and/or, the lithium outlet pipeline is communicated with the lithium collecting tank; and/or the heating chamber is also connected to an external oil The cooling system is connected. 10.根据权利要求7所述的金属锂废渣的无害化处理系统，其特征在于还包括：上盖驱动机构，其至少用于驱使上盖与废渣加热容器分离或结合。10 . The harmless treatment system for metal lithium waste residue according to claim 7 , further comprising: an upper cover driving mechanism, which is at least used to drive the upper cover to separate or combine with the waste residue heating container. 11 .
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CN110607449A (en) * 2019-10-09 2019-12-24 四川轻化工大学 A fine-grained hydrolysis system for alkali metal slag and its application method
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CN114807630A (en) * 2022-05-06 2022-07-29 昆明理工大学 Method and device for continuously treating waste lithium metal residues and recycling lithium metal
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CN110436489A (en) * 2019-08-23 2019-11-12 苏州清陶新能源科技有限公司 A kind of method for innocent treatment of lithium metal
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Denomination of invention: A method and system for harmless treatment of lithium slag waste

Granted publication date: 20230505

Pledgee: Bank of China Limited Zhangjiagang branch

Pledgor: TIANQI LITHIUM (JIANGSU) CO.,LTD.

Registration number: Y2025980058552