CN109355506B - Harmless treatment method and system for lithium metal waste residues - Google Patents
Harmless treatment method and system for lithium metal waste residues Download PDFInfo
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- CN109355506B CN109355506B CN201811229986.4A CN201811229986A CN109355506B CN 109355506 B CN109355506 B CN 109355506B CN 201811229986 A CN201811229986 A CN 201811229986A CN 109355506 B CN109355506 B CN 109355506B
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Abstract
The invention discloses a harmless treatment method and system for lithium metal waste residues. The method comprises the following steps: placing lithium metal waste residues in a closed heating cavity, and thoroughly replacing gas in the heating cavity with protective gas which does not react with lithium; heating metal lithium waste residues to a first temperature, disturbing, and vacuumizing a heating chamber to realize oil removal treatment; after the oil removal treatment is finished, continuously heating the metal lithium waste residue to a second temperature and performing disturbance to enable the metal lithium in the waste residue to be melted and aggregated into metal lithium liquid, and layering the metal lithium liquid and solid impurities; the lithium metal liquid flows out of the heating cavity after passing through a filter screen arranged in the heating cavity, so that solid impurities are trapped by the filter screen. The harmless treatment method does not generate chemical reaction or contact with air when treating the metal lithium waste residue, eliminates potential safety hazard, can directly, rapidly and effectively recover the metal lithium in the metal lithium waste residue, and has simple process and high economic benefit.
Description
Technical Field
The invention relates to a harmless treatment method of metal lithium waste residues, in particular to a harmless treatment method and a system for rapidly and effectively recovering metal lithium from the metal lithium waste residues, and belongs to the technical field of lithium recovery.
Background
Lithium metal was first found in a rare rock in the sweden chemist alalfuvite, 1817. The element symbol of the metallic lithium is Li, which is silvery white metal with relative atomic mass 6.941 and density 0.534g/cm 3 Is the lightest metal, melting point 180.54 ℃, boiling point 1317 ℃. The metal lithium has strong reducibility, can react with a large amount of inorganic reagents and organic reagents, and can be combined with oxygen, nitrogen, sulfur and the like. Is the only reaction with nitrogen at room temperature to produce lithium nitride (Li 3 N) alkali metal. Is easy to react with oxygen when exposed to wet air, and burns or explodes when exposed to water. Is readily reacted with hydrogen at around 500 c, is the only alkali metal that can produce a hydride that is stable enough to melt without decomposition. Lithium metal is susceptible to oxidation and has a lower density than kerosene, and is therefore generally stored in liquid paraffin. At present, the metal lithium is widely used in industries such as lithium batteries, aviation, metallurgy, chemical industry, medicine, building materials and the like, and is used for producing lithium batteries, light lithium aluminum alloy, organic synthetic vitamins, synthetic rubber and the like.
The oil refining stage in the process of manufacturing metallic lithium produces a great amount of lithium-containing waste residues, the mass of which is about 3% of the yield of metallic lithium, and the main components of which include metallic lithium, potassium, sodium and oxides, nitrides and carbides thereof. The metal lithium waste residue is generally soaked in white oil, and after the metal lithium waste residue is fished out from the white oil, the surface of the metal lithium waste residue is uniformly covered with a layer of oil film, and the layer of oil film prevents the metal lithium waste residue from directly contacting with water, oxygen, nitrogen and the like in the air, so that the metal lithium waste residue is protected. After the metal lithium waste residue is recycled and barreled, along with the extension of the standing time, an oil film on the surface of the metal lithium waste residue becomes thinner gradually, and in the carrying process, friction between the metal lithium waste residues promotes the damage of the oil film, and the metal lithium losing the protection of the oil film reacts with water, oxygen, nitrogen and the like in the air as follows:
Li+H 2 O＝LiOH+H 2 ↑
4Li+O 2 ＝2Li 2 O
Li 2 O+H 2 O＝2LiOH
6Li+N 2 ＝2Li 3 N
Li 3 N+3H 2 O＝3LiOH+NH 3 ↑
the reaction releases a large amount of reaction heat and generates gas, if the metal lithium waste residues cannot be timely treated, the heat cannot be timely discharged, after long-time heat accumulation, the temperature of the metal lithium waste residues gradually rises, spontaneous combustion and even explosion can occur to a certain extent after accumulation, fire disaster is caused, property loss and personal injury are caused, and 3 spontaneous combustion events of the metal lithium waste residues occur only in 2012. Therefore, the safe treatment of the metal lithium waste residue is particularly important, and has great social and economic values.
The existing metal lithium waste residue treatment method mainly comprises the following steps:
1. and dissolving the metal lithium waste residue in water to obtain the lithium compound. For example, patent CN1326640C provides a hydrolysis method of lithium slag obtained by synthesizing alkyl lithium, in which the lithium slag obtained by filtering alkyl lithium is collected in a lithium slag buffer tank, then the lithium slag is slowly pressed into a hydrolysis kettle by a lithium slag metering pump, and is subjected to hydrolysis reaction with a large amount of water in the hydrolysis kettle, the reaction temperature is controlled below 60 ℃, and the addition amount of the lithium slag is controlled by the temperature of the hydrolysis kettle; the reaction heat is taken away by cooling water of the kettle jacket, and the hydrocarbon solvent and other gases evaporated in the reaction process are cooled and recovered by the emptying condenser. However, the lithium compound is obtained by dissolving the metal lithium waste residue in water, and because of the active property of the metal lithium, the metal lithium waste residue reacts vigorously when being dissolved in water, a large amount of hydrogen is generated, and the dangerous conditions such as combustion, explosion and the like are inevitably caused, so that the problem of safety and environmental protection exists.
2. The metal lithium waste residue is treated by high-temperature combustion, the metal components in the metal lithium waste residue form oxides when being combusted, and the metal lithium is heated to melt and separate from the main body and is independently recovered after being cooled. For example, patent CN104764024B provides a sodium potassium lithium and lithium slag waste treatment device comprising a combustion chamber, a flue gas treatment device and a flue gas exhaust device. And igniting sodium, potassium, lithium and lithium slag materials in the combustion chamber, converting the lithium materials into oxides, and discharging the oxides to a lithium containing basin after the metal lithium is heated to a molten state due to the low melting point of the metal lithium. The oxide obtained after combustion is hydrolyzed to recover lithium resources. A large amount of flue gas is generated in the combustion process, and is subjected to harmless treatment through a flue gas treatment device and finally discharged to the outside through a flue gas discharge device. The method is characterized in that the lithium metal waste residue is treated by high-temperature combustion, and the lithium metal waste residue is also easy to form a hot metal sphere at high temperature due to the active property of the lithium metal, and the gas (hydrogen, organic gas and the like) generated by the reaction is ignited, so that the hidden danger of out-of-control combustion exists when the lithium metal waste residue is combusted in the air, the purpose of safely treating the lithium metal waste residue cannot be achieved, and meanwhile, the method also has the defects of more equipment, complex flow and higher energy consumption.
3. And recovering the metal lithium by adopting a smelting method. For example, patent CN 106756067a relates to a method for recovering metallic lithium and a process for preparing metallic lithium, comprising the steps of: 50-60 parts of lithium chloride and 40-50 parts of potassium chloride are mixed and melted to obtain a first mixed melt. And adding lithium slag into the first mixed solution, and then heating and melting to obtain a second mixed solution. And adding 8-10 parts of additives into the second mixed solution after removing impurities, melting, and recovering metal lithium from the upper layer liquid when the upper layer liquid turns silvery white. The smelting method for recovering the metal lithium needs to add more chloride, and has the advantages of higher cost, longer flow and higher equipment requirement.
Disclosure of Invention
The invention mainly aims to provide a harmless treatment method and system for lithium metal waste residues, so that the defects in the prior art are overcome.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the embodiment of the invention provides a harmless treatment method of lithium metal waste residues, which comprises the following steps:
placing lithium metal waste residues in a closed heating cavity, and thoroughly replacing gas in the heating cavity with protective gas which does not react with lithium;
heating metal lithium waste residues to a first temperature, disturbing, and vacuumizing a heating chamber to realize oil removal treatment;
after the oil removal treatment is finished, continuously heating the metal lithium waste residue to a second temperature and performing disturbance to enable the metal lithium in the waste residue to be melted and aggregated into metal lithium liquid, and layering the metal lithium liquid and solid impurities;
the lithium metal liquid flows out of the heating cavity after passing through a filter screen arranged in the heating cavity, so that solid impurities are trapped by the filter screen.
In some embodiments, the first temperature is 150 to 250 ℃.
In some embodiments, the second temperature is 200-400 ℃.
Further, the pore diameter of the filter screen is 5-1000 μm.
The embodiment of the invention also provides a harmless treatment system for the lithium metal waste residue, which comprises the following steps:
the waste residue heating container is provided with a heating cavity, a partition plate is arranged in the heating cavity and is at least used for bearing metal lithium waste residues, and the periphery of the partition plate is in surrounding sealing fit with the inner wall of the heating cavity;
the upper cover is provided with a protective gas pipeline and a lithium outlet pipeline, a filter screen is arranged at the lower part of the upper cover, when the upper cover is combined with the waste residue heating container, the heating cavity is sealed, and the filter screen is arranged in the heating cavity;
the heating unit is at least used for heating the waste residue heating container and the lithium outlet pipeline;
a gas control unit at least for inputting a protective gas into the heating chamber or evacuating the heating chamber;
a stirring mechanism at least for stirring the material in the heating chamber;
a diaphragm drive mechanism for at least driving the diaphragm up and down within the heating chamber; and
and the cake pushing mechanism is at least used for removing the residue filter cake remained on the partition plate.
Compared with the prior art, the invention has the beneficial effects that:
1) The harmless treatment method of the metal lithium waste residue provided by the invention has the advantages that no chemical reaction occurs during the treatment of the metal lithium waste residue, the metal lithium waste residue is not contacted with air, the potential safety hazard is eliminated, the metal lithium in the metal lithium waste residue can be directly, rapidly and effectively recycled in a harmless way, the process is simple and convenient, and the economic benefit is high;
2) When the method is used for treating the lithium metal waste residue, only a small amount of working gas is consumed, the working gas can be recycled, flammable and toxic gas can not be generated, and the method is safe and environment-friendly;
3) The metal lithium waste residue is subjected to filter pressing at high temperature, the process is rapid, the quality of the obtained metal lithium is higher, the treatment time is less, and the process flow is shorter; and the treated filter cake has good safety performance and is slow to react with air and water.
Drawings
Fig. 1 is a schematic diagram showing the operation state structure of a harmless treatment system for lithium metal waste residue in an exemplary embodiment of the present invention.
Fig. 2 is a schematic diagram showing a split state structure of a harmless treatment system for lithium metal waste residues in an exemplary embodiment of the present invention.
Reference numerals illustrate: 1-waste residue heating container, 10-heating chamber, 11-baffle, 200-upper cover, 21-protection gas pipeline, 22-lithium outlet pipeline, 23-filter screen, 300-heating unit, 400-stirring mechanism, 500-working gas pipeline, 600-cake pushing mechanism, 700-upper cover driving mechanism and 800-residue cake.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and put forward a technical solution of the present invention, and the technical solution, the implementation process and principle thereof will be further explained as follows.
As one aspect of the technical scheme of the invention, the harmless treatment method of the metal lithium waste residue comprises the following steps:
placing lithium metal waste residues in a closed heating cavity, and thoroughly replacing gas in the heating cavity with protective gas which does not react with lithium;
heating metal lithium waste residues to a first temperature, disturbing, and vacuumizing a heating chamber to realize oil removal treatment;
after the oil removal treatment is finished, continuously heating the metal lithium waste residue to a second temperature and performing disturbance to enable the metal lithium in the waste residue to be melted and aggregated into metal lithium liquid, and layering the metal lithium liquid and solid impurities;
the lithium metal liquid flows out of the heating cavity after passing through a filter screen arranged in the heating cavity, so that solid impurities are trapped by the filter screen.
The invention is used for rapidly and effectively treating the waste residue of the metal lithium and recovering the metal lithium in the waste residue, and the specific application range comprises but is not limited to: treatment of lithium metal waste residues and other metal lithium containing mixtures, treatment of alkali metals and alkali metal containing mixtures.
In some embodiments, the first temperature is 150 to 250 ℃.
In some embodiments, the second temperature is 200-400 ℃. When the temperature is raised, the metal lithium waste residue molten liquid can be separated out through a filter screen at the temperature slightly lower than 200 ℃, but the filtering process is very slow, and the filtering time is too long; the temperature of the molten metal lithium waste residue liquid is above 400 ℃, and the molten metal lithium liquid can be separated through the filter screen, but impurities can be burnt, volatilized and melted at high temperature, the energy consumption is too high, and the filtering rate is not improved.
Further, the pore diameter of the filter screen is 5-1000 μm. When the pore diameter of the filter screen is less than 5 mu m, the filter screen is easy to block, and the filtering efficiency is affected; the pore diameter of the filter screen is higher than 1000 mu m, so that impurities can easily pass through the filter screen, and the content of impurities in the recovered metal lithium is higher.
In some embodiments, the method comprises: when the temperature of the lithium metal waste slag is raised to 150-250 ℃, vacuumizing the heating chamber to 100-1000 Pa, and maintaining the pressure to perform the oil removal treatment. After the temperature of the molten metal lithium waste residue liquid is raised, oil can not be removed, but white oil flows out along with the molten metal lithium liquid during filter pressing, so that the filtering efficiency and the quality of the metal lithium are affected.
In some embodiments, the method comprises: heating the metal lithium waste residue to a second temperature, and stirring for 1-60 min to separate the obtained metal lithium liquid from the solid impurities. The stirring time after the temperature of the molten metal lithium waste residue liquid is raised can be less than 1min, but the proportion of the solid impurities wrapping the liquid metal lithium which are stirred and dispersed is smaller, so that the filtering rate is affected; the stirring time can be higher than 60min, but the energy consumption is too high, the time consumption is too much, and the filtration rate is not improved.
According to the invention, the metal lithium waste residue is heated in an air-isolated environment, the metal lithium with a lower melting point in the residue is melted, the impurities are still solid, but the metal lithium liquid drops are wrapped or separated by the nitride and the impurities and are in a lithium smelting block shape. After the temperature of the molten metal lithium waste residue liquid is raised, the molten metal lithium waste residue liquid can be stirred, but solid impurities still wrap liquid metal lithium as before the temperature is raised, and the filtration efficiency is low during the pressure filtration.
Further, after layering the lithium metal liquid and the solid impurities, standing for 1-60 min. The standing time after the temperature of the molten metal lithium waste residue liquid is raised and stirred can be less than 1min, but the layering of the molten metal lithium liquid is not obvious, and the filtration rate is affected; the standing time can be higher than 60min, but the time is too long, and the filtration rate is not increased.
In some embodiments, the method may specifically include:
placing metal lithium waste residues into a heating cavity of a waste residue heating container, and distributing the metal waste residues on a partition board, wherein the partition board can move up and down in the heating cavity;
combining an upper cover with a waste residue heating container to enable the heating chamber to be sealed, wherein the upper cover is provided with a protective gas pipeline and a lithium outlet pipeline, and a filter screen is arranged at the lower part of the upper cover;
thoroughly replacing the gas in the heating cavity with protective gas through the protective gas pipeline;
heating the waste residue heating container, stirring when the temperature of lithium metal waste residue in the waste residue heating container is raised to a first temperature, vacuumizing a heating cavity, and performing the oil removal treatment;
after the oil removal treatment is finished, continuously heating the metal lithium waste residue to a second temperature, accelerating stirring to laminate the obtained metal lithium liquid and solid impurities, and stopping stirring and standing;
the separator is driven to move from bottom to top and is matched with the filter screen, filter pressing treatment is carried out on the metal lithium liquid and the solid impurities, so that the metal lithium liquid passes through the filter screen and is output to the lithium collecting tank through the lithium outlet pipeline, and the solid impurities are trapped by the filter screen.
Further, the method comprises: and applying pressure to the molten metal lithium waste residue liquid from bottom to top, and forcing the molten metal lithium waste residue liquid to pass through the filter screen. The pressure applied to the molten metal lithium waste residue liquid from top to bottom can force the molten metal lithium waste residue liquid to pass through the filter screen, but impurities of the molten metal lithium waste residue liquid are concentrated in the lower layer after stirring and standing layering, and meshes of the filter screen are easy to be blocked during filtering, so that the filtering efficiency is lower.
In some embodiments, the method further comprises: after the filter pressing treatment is finished, protective gas is blown in through the protective gas pipeline, and lithium liquid in the upper space of the filter screen is completely discharged into the lithium collecting tank.
In some embodiments, the method further comprises: after the filter pressing treatment is completed, when the temperature in the waste residue heating container is lower than 150 ℃ and the pressure is restored to normal pressure, the upper cover is separated from the waste residue heating container, the residue filter cake remained on the partition plate is removed, and then the partition plate is returned to the initial position.
Further, the method further comprises: and a working gas is input into the heating chamber through a working gas pipeline, so that the partition plate is driven to move from bottom to top in the heating chamber.
Further, the maximum pressure of the filter pressing treatment is 0.5-5 MPa. Wherein, the pressure for pushing the molten metal lithium waste slag is provided by a machine or a gas.
In some embodiments, the method further comprises: after the oil removal treatment is completed, the waste residue heating container, the working gas pipeline, the working gas heating container communicated with the working gas pipeline and the lithium outlet pipeline are heated to the second temperature of 200-400 ℃, and then the disturbance, standing and filter pressing treatment is sequentially carried out.
Further, the protective gas or working gas includes more than one inert gas. Still further, the working gas or the protective gas may be a pure gas that does not react with lithium or a mixed gas of a plurality of gases that do not react with lithium.
In one of the more specific embodiments of the present invention, the innocent treatment method for the lithium metal waste residue may specifically include the following steps:
1. taking lithium metal waste residues, and placing the lithium metal waste residues into a waste residue heating container;
2. a filter screen with a certain aperture is arranged on an upper cover with a protective gas pipeline and a lithium outlet pipeline, the upper cover is put down through a hydraulic lifting rod (namely an upper cover driving mechanism), a waste residue heating container is sealed, and a device after sealing is shown in figure 1;
3. the gas control unit is started, the atmosphere in the waste residue heating container is replaced by a protective gas pipeline of the upper cover, and the replacement gas is inert gas such as argon, so that the air in the waste residue heating container is thoroughly replaced;
4. closing the gas control unit, and opening the heating unit (namely a temperature control system) to heat the waste residue heating container, the working gas pipeline and the lithium outlet pipeline;
5. when the temperature of lithium metal waste residues in the waste residue heating container is raised to 150-250 ℃, stirring is started, the waste residue heating container is vacuumized through the gas control unit, the pressure is maintained within the range of 100-1000 Pa for a certain time to remove oil, and an external oil cooling system is started for recovery treatment;
6. after thorough degreasing, closing the gas control unit, continuously heating to 200-400 ℃, accelerating stirring, and promoting the layering of molten lithium slag by stirring;
7. stopping stirring and standing for a period of time, gradually pressurizing the partition board by machinery or gas, performing filter pressing, enabling molten lithium liquid to pass through the filter screen, and enabling the molten lithium liquid to enter the lithium collecting tank through the lithium outlet pipeline, wherein the maximum pressure is controlled to be 0.5-5 MPa in the process;
8. argon is blown in through a protective gas pipeline, molten lithium liquid in the upper space of the filter screen is completely discharged into the lithium collecting tank, and then high-purity argon is stopped from being blown in from the protective gas pipeline;
9. stopping heating and pressurizing, lifting the upper cover through a hydraulic lifting rod (namely an upper cover driving mechanism) when the temperature of the waste residue heating container is lower than 150 ℃ and the pressure is reduced to normal pressure, separating the upper cover from the waste residue heating container, lifting a residue filter cake through a bottom pressurizing partition plate, pushing out the residue filter cake through a cake pushing mechanism (namely a hydraulic cake pushing rod), releasing pressure, putting down the partition plate, and repeating the next treatment flow;
10. the analysis result shows that the metal lithium in the lithium collecting tank meets the industrial-grade requirement, the content of the metal lithium in the residue filter cake is obviously reduced, the recovery rate of the metal lithium can reach more than 80%, and the reactivity of the residue filter cake and water is obviously reduced.
In conclusion, the harmless treatment method of the metal lithium waste residue provided by the invention does not generate chemical reaction or contact with air when the metal lithium waste residue is treated, thus avoiding potential safety hazards, being capable of directly, rapidly and effectively recovering the metal lithium in the metal lithium waste residue in a harmless way, and having simple and convenient process and high economic benefit; when the waste lithium metal slag is treated, only a small amount of working gas is consumed, the working gas can be recycled, and flammable and toxic gas is not generated, so that the method is safe and environment-friendly.
As another aspect of the technical scheme of the present invention, the present invention relates to a harmless treatment system for lithium metal waste residues, comprising:
the waste residue heating container is provided with a heating cavity, a partition plate is arranged in the heating cavity and is at least used for bearing metal lithium waste residues, and the periphery of the partition plate is in surrounding sealing fit with the inner wall of the heating cavity;
the upper cover is provided with a protective gas pipeline and a lithium outlet pipeline, a filter screen is arranged at the lower part of the upper cover, when the upper cover is combined with the waste residue heating container, the heating cavity is sealed, and the filter screen is arranged in the heating cavity;
the heating unit is at least used for heating the waste residue heating container and the lithium outlet pipeline;
a gas control unit at least for inputting a protective gas into the heating chamber or evacuating the heating chamber;
a stirring mechanism at least for stirring the material in the heating chamber;
a diaphragm drive mechanism for at least driving the diaphragm up and down within the heating chamber; and
and the cake pushing mechanism is at least used for removing the residue filter cake remained on the partition plate.
In some embodiments, the cake pushing mechanism comprises a cake pushing rod which is horizontally arranged, the partition plate can at least reciprocate between a first station, a second station and a third station, and the first station, the second station and the third station are sequentially arranged from bottom to top; at the second station, the separator can be matched with the filter screen to form a filter pressing mechanism, and the filter pressing mechanism is at least used for filtering out metal lithium liquid from the mixture of the metal lithium liquid and solid impurities and outputting the metal lithium liquid to a lithium outlet pipeline, and enabling the solid impurities to remain on the separator to form a residue filter cake; at the third station, the residue cake is flush with the cake pusher bar.
In some embodiments, the diaphragm drive mechanism includes a working gas conduit in communication with the heating chamber, a working gas heating vessel in communication with the working gas conduit, and the heating unit is further configured for at least the working gas heating vessel and working gas conduit heating.
The working gas heating container refers to a container in which the working gas is preheated before entering the lithium metal waste residue heating container, and after the working gas is heated to the second temperature, the working gas enters the waste residue heating container through heat preservation of a working gas pipeline heated to the second temperature, so that the temperature of molten waste residue caused by directly introducing the working gas with lower temperature into the waste residue heating container is prevented from being reduced or even solidified.
Further, the lithium outlet pipeline is communicated with the lithium collecting tank.
Further, the heating chamber is also in communication with an external oil cooling system.
In some embodiments, the system further comprises: and the upper cover driving mechanism is at least used for driving the upper cover to be separated from or combined with the waste residue heating container.
Specifically, referring to fig. 1 and 2, a harmless treatment system for lithium metal waste residue in an exemplary embodiment of the invention includes: the waste residue heating vessel 100, the upper cover 200, the heating unit 300, the gas control unit, the stirring mechanism 400 (stirrer is used in this embodiment), the partition plate driving mechanism, the cake pushing mechanism 600 (hydraulic cake pushing rod is used in this embodiment), and the upper cover driving mechanism 700 (hydraulic lifting rod is used in this embodiment).
The waste residue heating container 100 is provided with a heating chamber 10, a partition plate 11 is arranged in the heating chamber 10, the partition plate 11 is at least used for bearing metal lithium waste residues, and the outer periphery of the partition plate 11 is in surrounding sealing fit with the inner wall of the heating chamber 10. The heating chamber 10 is also in communication with an external oil cooling system.
The upper cover 200 is provided with a protective gas pipeline 21 and a lithium outlet pipeline 22, the lithium outlet pipeline 22 is communicated with the lithium collecting tank, a filter screen 23 is arranged at the lower part of the upper cover 200, when the upper cover 200 is combined with the waste residue heating container 100, the heating chamber 10 is sealed, and the filter screen 23 is arranged in the heating chamber 10. The upper cover driving mechanism 700 (i.e., hydraulic lifting lever) is at least for driving the upper cover 200 to be separated from or combined with the waste heating container 100.
The heating unit 300 (a heating layer is used in this embodiment) is at least used for heating the waste residue heating container 100 and the lithium discharge pipe 22. The gas control unit is at least used for inputting protective gas into the heating chamber 10 or vacuumizing the heating chamber 10. The stirring mechanism 400 (i.e., stirrer) is used at least to disturb the material in the heating chamber 10.
The diaphragm driving mechanism includes a working gas pipe 500 communicating with the heating chamber 10, and a working gas heating vessel communicating with the working gas pipe 500, at least for driving the diaphragm 11 to move up and down in the heating chamber 10.
The cake pushing mechanism 600 comprises a cake pushing rod horizontally arranged, the partition plate 11 can at least reciprocate among a first station, a second station and a third station, and the first station, the second station and the third station are sequentially arranged from bottom to top; at the second station, the separator 11 can cooperate with the filter screen 23 to form a filter pressing mechanism at least for filtering out the metal lithium liquid from the mixture of the metal lithium liquid and the solid impurities and delivering the metal lithium liquid to the lithium outlet pipe 22, and leaving the solid impurities on the separator 11 to form a residue filter cake 800; at the third station, as shown in fig. 2, the residue cake 800 is flush with the cookie pusher bar. Namely, heating, filtering and the like of the lithium metal slag can be completed in the same chamber, so that the required operation space can be effectively reduced, the operation efficiency is improved, and the recovery rate and the quality of the lithium metal can be improved.
The harmless treatment system for the metal lithium waste residue provided by the invention has the advantages that the structural design is simple and reasonable, the metal lithium waste residue can be subjected to filter pressing at high temperature, the process is rapid, the quality of the obtained metal lithium is higher, the treatment time is less, and the process flow is shorter; and the treated filter cake has good safety performance and is slow to react with air and water.
The technical solution of the present invention will be described in further detail below with reference to a number of preferred embodiments and accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The test methods in the following examples, in which specific conditions are not noted, generally follow conventional conditions.
Example 1
The harmless treatment method of the lithium metal waste residues in the embodiment specifically comprises the following steps:
1. 1000g of lithium metal waste residue is taken in the protective atmosphere of high-purity argon and put into a waste residue heating container;
2. a filter screen with the aperture of 50 mu m is arranged on an upper cover with a protective gas pipeline and a lithium outlet pipeline, the upper cover is put down by a hydraulic lifting rod, and a waste residue heating container is sealed;
3. starting a gas control unit, discharging the internal atmosphere of the waste residue heating container to the vacuum degree of 0.09MPa through a protective gas pipeline of the upper cover, and filling high-purity argon to normal pressure, and stopping after 3 times of circulation;
4. closing the gas control unit, starting the temperature control system, and heating the waste residue heating container, the working gas pipeline and the lithium outlet pipeline;
5. when the temperature of lithium metal waste residues in the waste residue heating container is increased to 200 ℃, stirring is started, the waste residue heating container is vacuumized through the gas control unit, the vacuum degree is maintained to be 1000Pa, an external oil cooling system is started for recycling treatment, and oil smoke can be seen to be discharged from the protective gas pipeline;
6. no oil smoke is discharged from the protective gas pipeline, namely after the oil is thoroughly removed, the gas control unit is closed, the waste residue heating container, the working gas pipeline and the lithium outlet pipeline are continuously heated, and the temperature is kept after 300 ℃ is reached, and the stirring is accelerated for 10min;
7. stopping stirring, standing the metal lithium waste residue molten liquid for 10min, introducing heated high-purity argon through a working gas pipeline at the lower part of the waste residue heating container, pushing the partition plate to rise, uniformly increasing the pressure to 1.0MPa after the metal lithium waste residue molten liquid contacts the filter screen, performing filter pressing, and enabling the molten lithium liquid to pass through the filter screen and enter the lithium collecting tank through a lithium outlet pipeline;
8. after observing that no metal lithium melt flows out of the lithium outlet pipeline from the observation hole of the lithium collecting tank, blowing high-purity argon through the protective gas pipeline, completely discharging the lithium melt in the upper space of the filter screen into the lithium collecting tank, and stopping blowing the high-purity argon from the protective gas pipeline;
9. stopping heating and pressurizing, lifting the upper cover through a hydraulic lifting rod when the temperature of the waste residue heating container is lower than 150 ℃ and the pressure is reduced to normal pressure, separating the upper cover from the waste residue heating container, lifting a residue filter cake through a bottom pressurizing partition plate, pushing out the residue filter cake through a hydraulic cake pushing rod, and then decompressing and putting down the partition plate;
10. taking out the cooled metal lithium blocks and filter cakes in a high-purity argon protective atmosphere, and carrying out sample preparation detection, wherein the mass of the metal lithium blocks is 853g, and the lithium recovery rate is 85.3%. The Li content in the metal lithium block is 99.7 percent, the Na content is 0.14 percent, and the requirement of industrial grade metal lithium is met. The content of metallic lithium in the residue filter cake is 5.2%, and the reactivity of the residue with water is obviously reduced.
Example 2
The harmless treatment method of the lithium metal waste residues in the embodiment specifically comprises the following steps:
1. 1000g of lithium metal waste residue is taken in the protective atmosphere of high-purity argon and put into a waste residue heating container;
2. a filter screen with the aperture of 1000 mu m is arranged on an upper cover with a protective gas pipeline and a lithium outlet pipeline, the upper cover is put down by a hydraulic lifting rod, and a waste residue heating container is sealed;
3. starting a gas control unit, discharging the internal atmosphere of the waste residue heating container to the vacuum degree of 0.09MPa through a protective gas pipeline of the upper cover, and filling high-purity argon to normal pressure, and stopping after 3 times of circulation;
4. closing the gas control unit, starting the temperature control system, and heating the waste residue heating container, the working gas pipeline and the lithium outlet pipeline;
5. when the temperature of lithium metal waste residues in the waste residue heating container is raised to 150 ℃, stirring is started, the waste residue heating container is vacuumized through the gas control unit, the vacuum degree is maintained to be 100Pa, an external oil cooling system is started for recovery treatment, and oil smoke can be seen to be discharged from the protective gas pipeline;
6. no oil smoke is discharged from the protective gas pipeline, namely after the oil is thoroughly removed, the gas control unit is closed, the waste residue heating container, the working gas pipeline and the lithium outlet pipeline are continuously heated, the temperature is kept after reaching 200 ℃, and the stirring is accelerated for 60min;
7. stopping stirring, standing the metal lithium waste residue molten liquid for 60min, introducing heated high-purity argon through a working gas pipeline at the lower part of the waste residue heating container, pushing the partition plate to rise, uniformly increasing the pressure to 0.5MPa after the metal lithium waste residue molten liquid contacts the filter screen, performing filter pressing, and enabling the molten lithium liquid to pass through the filter screen and enter the lithium collecting tank through a lithium outlet pipeline;
8. after observing that no metal lithium melt flows out of the lithium outlet pipeline from the observation hole of the lithium collecting tank, blowing high-purity argon through the protective gas pipeline, completely discharging the lithium melt in the upper space of the filter screen into the lithium collecting tank, and stopping blowing the high-purity argon from the protective gas pipeline;
9. stopping heating and pressurizing, lifting the upper cover through a hydraulic lifting rod when the temperature of the waste residue heating container is lower than 150 ℃ and the pressure is reduced to normal pressure, separating the upper cover from the waste residue heating container, lifting a residue filter cake through a bottom pressurizing partition plate, pushing out the residue filter cake through a hydraulic cake pushing rod, and then decompressing and putting down the partition plate;
10. taking out the cooled metal lithium blocks and filter cakes in a high-purity argon protective atmosphere, and carrying out sample preparation detection, wherein the mass of the metal lithium blocks is 866g, and the lithium recovery rate is 86.6%. The Li content in the metal lithium block is 99.6%, the Na content is 0.15%, and the requirement of industrial grade metal lithium is met. The content of metallic lithium in the residue filter cake is 5.1%, and the reactivity of the residue with water is obviously reduced.
Example 3
The harmless treatment method of the lithium metal waste residues in the embodiment specifically comprises the following steps:
1. 1000g of lithium metal waste residue is taken in the protective atmosphere of high-purity argon and put into a waste residue heating container;
2. a filter screen with the aperture of 5 mu m is arranged on an upper cover with a protective gas pipeline and a lithium outlet pipeline, the upper cover is put down by a hydraulic lifting rod, and a waste residue heating container is sealed;
3. starting a gas control unit, discharging the internal atmosphere of the waste residue heating container to the vacuum degree of 0.09MPa through a protective gas pipeline of the upper cover, and filling high-purity argon to normal pressure, and stopping after 3 times of circulation;
4. closing the gas control unit, starting the temperature control system, and heating the waste residue heating container, the working gas pipeline and the lithium outlet pipeline;
5. when the temperature of lithium metal waste residues in the waste residue heating container is raised to 250 ℃, stirring is started, the waste residue heating container is vacuumized through the gas control unit, the vacuum degree is maintained to be 500Pa, an external oil cooling system is started for recycling treatment, and oil smoke can be seen to be discharged from the protective gas pipeline;
6. no oil smoke is discharged from the protective gas pipeline, namely after the oil is thoroughly removed, the gas control unit is closed, the waste residue heating container, the working gas pipeline and the lithium outlet pipeline are continuously heated, the temperature is kept after reaching 400 ℃, and stirring is accelerated for 1min;
7. stopping stirring, standing the molten metal lithium waste residue liquid for 1min, introducing heated high-purity argon through a working gas pipeline at the lower part of the waste residue heating container, pushing the partition plate to rise, uniformly increasing the pressure to 5.0MPa after the molten metal lithium waste residue liquid contacts the filter screen, performing filter pressing, and enabling the molten metal lithium liquid to pass through the filter screen and enter the lithium collecting tank through a lithium outlet pipeline;
8. after observing that no metal lithium melt flows out of the lithium outlet pipeline from the observation hole of the lithium collecting tank, blowing high-purity argon through the protective gas pipeline, completely discharging the lithium melt in the upper space of the filter screen into the lithium collecting tank, and stopping blowing the high-purity argon from the protective gas pipeline;
9. stopping heating and pressurizing, lifting the upper cover through a hydraulic lifting rod when the temperature of the waste residue heating container is lower than 150 ℃ and the pressure is reduced to normal pressure, separating the upper cover from the waste residue heating container, lifting a residue filter cake through a bottom pressurizing partition plate, pushing out the residue filter cake through a hydraulic cake pushing rod, and then decompressing and putting down the partition plate;
10. taking out the cooled metal lithium blocks and filter cakes in a high-purity argon protective atmosphere, and carrying out sample preparation detection, wherein the mass of the metal lithium blocks is 834g, and the lithium recovery rate is 83.4%. The Li content in the metal lithium block is 99.7 percent, the Na content is 0.15 percent, and the requirement of industrial grade metal lithium is met. The content of metallic lithium in the residue filter cake is 5.9%, and the reactivity of the residue with water is obviously reduced.
In summary, by the technical scheme, the harmless treatment method provided by the invention does not generate chemical reaction or contact with air when treating the metal lithium waste residue, eliminates potential safety hazard, can directly, rapidly and effectively recover the metal lithium in the metal lithium waste residue, and has simple process and high economic benefit.
In addition, the inventor also refers to examples 1-3 to perform experiments on other raw materials, conditions and the like listed in the specification, and directly, quickly and effectively recover the metal lithium in the metal lithium waste residue with simple process and high economic benefit.
It should be noted that, in this document, an element defined by the phrase "including … …" generally does not exclude that there are additional identical elements in a step, a process, a method or an experimental apparatus including the element.
It should be understood that the foregoing preferred embodiments are merely illustrative of the present invention, and other embodiments of the present invention are contemplated herein, which fall within the scope of the invention, as will be appreciated by those skilled in the art upon attaining an equivalent to or more than one of the following claims.
Claims (10)
1. A harmless treatment method of lithium metal waste residue is characterized by comprising the following steps:
placing metal lithium waste residues into a heating cavity of a waste residue heating container, and distributing the metal waste residues on a partition board, wherein the partition board can move up and down in the heating cavity;
combining an upper cover with a waste residue heating container to enable the heating chamber to be sealed, wherein the upper cover is provided with a protective gas pipeline and a lithium outlet pipeline, and a filter screen is arranged at the lower part of the upper cover;
thoroughly replacing the gas in the heating cavity by protective gas which does not react with lithium through the protective gas pipeline;
heating the waste residue heating container, stirring when the temperature of lithium metal waste residue in the waste residue heating container is raised to a first temperature, vacuumizing a heating cavity, and carrying out oil removal treatment;
after the oil removal treatment is finished, continuously heating the metal lithium waste residue to a second temperature, accelerating stirring, melting and gathering the metal lithium in the metal lithium waste residue to form metal lithium liquid, layering the obtained metal lithium liquid and solid impurities, and stopping stirring and standing;
the separator is driven to move from bottom to top and is matched with the filter screen, filter pressing treatment is carried out on the metal lithium liquid and the solid impurities, so that the metal lithium liquid passes through the filter screen and is output to the lithium collecting tank through the lithium outlet pipeline, and the solid impurities are trapped by the filter screen.
2. The harmless treatment method of the lithium metal waste residue according to claim 1, which is characterized in that: the first temperature is 150-250 ℃; and/or, the second temperature is 200-400 ℃; and/or the pore diameter of the filter screen is 5-1000 μm.
3. The harmless treatment method of the lithium metal waste residue according to claim 1, characterized by comprising the steps of: and vacuumizing the heating chamber to 100-1000 Pa, and maintaining the pressure to perform the oil removal treatment.
4. The harmless treatment method of the lithium metal waste residue according to claim 1, characterized by comprising the steps of: heating the metal lithium waste residue to a second temperature, and stirring for 1-60 min to separate the obtained metal lithium liquid from the solid impurities.
5. The harmless treatment method of the lithium metal waste residue according to claim 1, characterized by comprising the steps of: and layering the lithium metal liquid and the solid impurities, and standing for 1-60 min.
6. The harmless treatment method of the lithium metal waste residue according to claim 1, further comprising: after the filter pressing treatment is finished, protective gas is blown in through the protective gas pipeline, and lithium liquid in the upper space of the filter screen is completely discharged into the lithium collecting tank.
7. The harmless treatment method of the lithium metal waste residue according to claim 1, further comprising: after the filter pressing treatment is completed, when the temperature in the waste residue heating container is lower than 150 ℃ and the pressure is restored to normal pressure, the upper cover is separated from the waste residue heating container, the residue filter cake remained on the partition plate is removed, and then the partition plate is returned to the initial position.
8. The harmless treatment method of the lithium metal waste residue according to claim 1, characterized by comprising the steps of: and a working gas is input into the heating chamber through a working gas pipeline, so that the partition plate is driven to move from bottom to top in the heating chamber.
9. The harmless treatment method of the lithium metal waste residue according to claim 1, which is characterized in that: the maximum pressure of the filter pressing treatment is 0.5-5 MPa.
10. The harmless treatment method of the lithium metal waste residue according to claim 8, further comprising: after the oil removal treatment is completed, heating a waste residue heating container, a working gas pipeline, a working gas heating container communicated with the working gas pipeline and a lithium outlet pipeline to a second temperature, and then sequentially performing disturbance, standing and filter pressing treatment;
and/or the protective gas or the working gas comprises more than one inert gas.
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| CN113839114A (en) * | 2020-06-24 | 2021-12-24 | 天津中能锂业有限公司 | Lithium metal negative electrode recovery |
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| CN106159367B (en) * | 2016-08-11 | 2018-08-03 | 天齐锂业股份有限公司 | The recovery method of lithium metal battery negative plate |
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