Method for separating and recycling lithium battery ceramic separator
By soaking and rubbing the waste lithium battery ceramic separator with a stripping agent, combined with drying, sieving and calcining, the problem of separating and recycling lithium battery ceramic separators has been solved. This has enabled the efficient separation and recycling of the base membrane and inorganic coating materials, which is environmentally friendly and low-cost.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHALCO SHANDONG CO LTD
- Filing Date
- 2023-01-30
- Publication Date
- 2026-07-14
Smart Images
Figure CN116190840B_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of lithium battery recycling technology, and in particular to a method for separating and recycling lithium battery ceramic separators. Background Technology
[0002] With increasingly severe energy and environmental problems, new energy technologies using lithium-ion batteries as a power source are gradually developing. Lithium-ion batteries are widely used in automobiles. Compared to other materials, lithium-ion batteries require a separator to isolate the electrolyte materials of the positive and negative electrodes. Therefore, with the development of lithium-ion batteries, the requirements for the separators are becoming increasingly stringent. The industry average yield of separators is significantly low; calculations show that the industry average yield of ceramic-coated films used in lithium-ion batteries is around 60%. With hundreds of millions of lithium batteries being scrapped each year, improper disposal will seriously pollute the environment and waste resources. Furthermore, with the continued decline in the price of power batteries in the future, raw material costs will account for more than 80% of the battery cost. Therefore, the recycling and reuse of renewable resources in lithium batteries is essential.
[0003] Currently, there is a great deal of research on ceramic-coated separators for lithium batteries, mainly aimed at improving separator performance. However, research on separation and recycling technologies for ceramic separator materials is relatively limited. Existing separation and recycling technologies either easily generate pollutants, have poor separation effects between ceramic materials and substrates, have low efficiency in leaching alumina and generate large amounts of wastewater, use solvents that are unsafe for personnel and the environment, or only focus on recycling the entire separator material while neglecting the separation of materials on the separator surface.
[0004] Therefore, how to provide a separation and recycling method that can simultaneously recover inorganic materials and base membranes for lithium battery separators is a technical problem that urgently needs to be solved. Summary of the Invention
[0005] This application provides a method for separating and recycling ceramic separators for lithium batteries, which solves the technical problem in the prior art that it is difficult to grade and recycle the base membrane while also recovering inorganic materials.
[0006] In a first aspect, this application provides a method for separating and recycling lithium battery ceramic separators, the method comprising:
[0007] Waste lithium battery ceramic separators are sorted and cut to obtain separator materials;
[0008] The membrane material was added to the stripping agent solution and soaked, then rubbed and washed to obtain the base film material and the stripping material respectively.
[0009] The base film material is dried to obtain a base film;
[0010] The stripped material is purified or regenerated to obtain an inorganic coating material for the ceramic diaphragm.
[0011] The mass concentration of the stripping agent solution is 1% to 50%.
[0012] Optionally, the mass concentration of the stripping agent solution is 5% to 20%.
[0013] Optionally, the solute in the stripping agent solution includes at least one of fatty acid alkali metal salts, sodium alkyl sulfonate, sodium linear alkylbenzene sulfonate, nonionic surfactants, and anhydrous ethanol.
[0014] Optionally, the soaking temperature is 10℃ to 100℃, and the soaking time is 0.5h to 72h.
[0015] Optionally, the rubbing and cleaning method is a physical rubbing and cleaning method, and the cleaning agent used for the rubbing and cleaning includes at least one of reverse osmosis water, deionized water and high-purity water.
[0016] Optionally, the rubbing and washing time is 10 min to 60 min, and the rubbing and washing temperature is 10℃ to 100℃.
[0017] Optionally, the drying includes drying by static drying at a temperature of 50°C to 100°C.
[0018] Optionally, the purification process includes sieving to remove impurities and strong magnetic removal of iron.
[0019] Optionally, the screening and impurity removal includes screening and impurity removal using a 320-1000 mesh screen, and the strong magnetic iron removal includes strong magnetic iron removal using a permanent magnet rod and / or an electromagnetic iron remover.
[0020] Optionally, the regeneration process includes regeneration by calcination, wherein the calcination equipment includes at least one of a muffle furnace, tunnel kiln, pusher kiln, roller kiln, and microwave-heated kiln, and the final temperature of the calcination is 400℃ to 900℃.
[0021] The technical solutions provided in this application have the following advantages compared with the prior art:
[0022] This application provides a method for separating and recycling ceramic separators for lithium batteries. First, the ceramic separators from waste lithium batteries are sorted and cut to extract the separator material. Then, the separator material is peeled off in a stripping agent solution. The stripping agent reacts with the binder in the ceramic separator coating, causing the long-chain molecules in the coating to break down. This separates the inorganic material (Al2O3 or boehmite) from the PE / PP base membrane. The base membrane is then dried, and the inorganic coating material is purified or regenerated. This yields pure base membrane material and inorganic coating material, facilitating the tiered reuse of the base membrane material. The recovered inorganic coating material can be reused, thus completing the recycling of the ceramic separator and achieving both tiered base membrane recycling and the separation and recycling of inorganic materials. Attached Figure Description
[0023] The accompanying drawings, which are incorporated in and form part of this specification, illustrate embodiments consistent with this application and, together with the description, serve to explain the principles of this application.
[0024] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, for those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0025] Figure 1 A schematic flowchart illustrating the separation and recovery method provided in the embodiments of this application;
[0026] Figure 2 This is a schematic diagram of the actual production process of the separation and recycling method provided in the embodiments of this application;
[0027] Figure 3 SEM image of the recovered boehmite sample provided for an embodiment of this application;
[0028] Figure 4 SEM image of the recovered alumina sample provided in the embodiments of this application. Detailed Implementation
[0029] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.
[0030] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this application can be purchased from the market or prepared by existing methods.
[0031] The creative thinking behind this application is:
[0032] Currently, there is much research on ceramic-coated separators for lithium batteries, mainly aimed at improving their performance. However, research on separation and recycling technologies for ceramic separator materials is relatively limited. For example, CN106299532A discloses a method for recycling ceramic separators from lithium batteries. This method involves calcining the ceramic separator in a high-temperature furnace at 380–450°C. The residue obtained from calcination is then leached with acid to extract aluminum, followed by the addition of an alkaline solution to precipitate Al(OH)3. Finally, the Al(OH)3 is heat-treated at 140–150°C to obtain γ-Al2O3. In this method, the polyolefin separator is directly burned off, which can easily lead to the formation of pollutants such as dioxins. Furthermore, this method consumes a large amount of acid and alkali, resulting in a significant wastewater volume.
[0033] CN114006065A discloses a method for recycling ceramic separators from waste lithium-ion batteries. This method involves immersing the separated ceramic separator in water and stirring to remove impurities adhering to its surface. The separator is then subjected to heat treatment, ball milling, and ultrasonic treatment in sequence. Finally, the ceramic material and separator substrate are separated by density difference. The entire separation process uses physical methods, resulting in poor separation of the ceramic material from the substrate. CN108110360A discloses a method for recovering alumina from ceramic separators in waste lithium-ion batteries. This method involves calcining the ceramic separator in a muffle furnace to remove residual binders. The calcined ceramic separator is then dissolved in an alkaline solution to obtain a solution. Carbon dioxide gas is passed into the solution to generate a precipitate, which is then calcined to obtain alumina powder. This method has low efficiency in dissolving alumina in the alkaline solution and generates a large amount of wastewater.
[0034] CN111403838A discloses a method for recycling and reusing decommissioned power lithium battery separator paper. The method involves immersing the separator in an organic solvent to swell, and then repeatedly raising and lowering the temperature several times to obtain a separator base film and an inorganic coating layer. The organic solvents used in this method, such as N-methylpyrrolidone and hexamethylphosphoramide, are carcinogenic, have an odor, are flammable and corrosive, and are detrimental to personal safety and the environment.
[0035] CN105742743A discloses a method for recovering separator material from waste lithium-ion batteries, which mainly includes separating the battery separator by soaking in a salt solution, and the battery separator being cleaned in sequence by an organic solvent, ultrasonically cleaned with a dispersant, cleaned with anhydrous ethanol, and dried.
[0036] Therefore, how to provide a separation and recycling method that can simultaneously recover inorganic materials and base membranes for lithium battery separators is a technical problem that urgently needs to be solved.
[0037] like Figure 1 and Figure 2 As shown in the embodiment of this application, a method for separating and recycling lithium battery ceramic separators is provided, the method comprising:
[0038] S1. The waste lithium battery ceramic separator is sorted and cut to obtain separator material;
[0039] S2. The membrane material is added to the stripping agent solution for soaking, followed by rubbing and washing to obtain the base film material and the stripping material respectively;
[0040] S3. Dry the base film material to obtain a base film;
[0041] S4. The stripped material is purified or regenerated to obtain an inorganic coating material for the ceramic diaphragm;
[0042] The mass concentration of the stripping agent solution is 1% to 50%.
[0043] In this embodiment of the application, the positive effect of limiting the mass concentration of the stripping agent solution to 1% to 50% is that within this mass concentration range, the stripping effect on the diaphragm material can be guaranteed, thereby ensuring that pure base film material and stripping material can be stripped from the ceramic diaphragm.
[0044] Ceramic separators generally include defective products from lithium battery processing, waste products from retired lithium batteries, and ceramic separators recycled through other means. The inorganic coating material of ceramic separators is generally boehmite or Al2O3.
[0045] In some alternative embodiments, the mass concentration of the stripping agent solution is 5% to 20%.
[0046] In this embodiment, limiting the mass concentration of the stripping agent solution to 5% to 20% has the positive effect of further ensuring the stripping effect on the membrane material within this mass concentration range, thereby ensuring that sufficiently pure base membrane material and stripping material can be stripped from the ceramic membrane.
[0047] In some alternative embodiments, the solute in the stripping agent solution includes at least one of fatty acid alkali metal salts, sodium alkyl sulfonate, sodium linear alkylbenzene sulfonate, nonionic surfactants, and anhydrous ethanol.
[0048] In this embodiment, the positive effect of defining the specific effective components of the stripping agent solution is to ensure the stripping effect of the stripping agent solution on the base membrane material and the inorganic coating material of the diaphragm material, thereby ensuring the subsequent separation and recycling of the base membrane material and the inorganic coating material.
[0049] In some optional embodiments, the soaking temperature is 10°C to 100°C, and the soaking time is 0.5h to 72h.
[0050] In this embodiment, the soaking temperature and time are limited to ensure that the stripping agent solution can fully strip the base film and inorganic coating on the ceramic diaphragm, thereby facilitating subsequent recycling.
[0051] The soaking temperature can be 60℃~80℃, and the soaking time can be 4h~24h.
[0052] In some optional embodiments, the rubbing and cleaning method is a physical rubbing and cleaning method, and the cleaning agent used for the rubbing and cleaning includes at least one of reverse osmosis water, deionized water and high-purity water.
[0053] In this embodiment of the application, the specific method of rubbing and cleaning and the type of cleaning agent used are specified to ensure that the impurities of the base film material and the peeled inorganic coating material are cleaned, thereby ensuring that pure base film and inorganic coating material can be recovered in the future.
[0054] In some optional embodiments, the rubbing and washing time is 10 min to 60 min, and the rubbing and washing temperature is 10℃ to 100℃.
[0055] In this embodiment, the time and temperature of the rubbing and washing are limited to ensure the effectiveness of the rubbing and washing, thereby ensuring that the impurities on the peeled base film material and inorganic coating material are cleaned, which facilitates the subsequent utilization of the recovered base film and inorganic coating material.
[0056] The rubbing and washing time can be 30 to 60 minutes, and the rubbing and washing temperature can be 40℃ to 60℃.
[0057] In some alternative embodiments, the drying includes static drying at a temperature of 50°C to 100°C.
[0058] In this embodiment, a specific drying temperature is defined to ensure that moisture and other liquid impurities on the base film material are completely removed, thereby obtaining a pure base film that facilitates subsequent cascade reuse.
[0059] The drying temperature can be 60℃~80℃.
[0060] In some alternative implementations, the purification process includes sieving to remove impurities and strong magnetic removal of iron.
[0061] In this embodiment of the application, the specific method of purification is defined. By screening to remove impurities and strong magnetic removal of iron, the impurities in the inorganic coating material can be removed cleanly, thereby obtaining a pure inorganic coating material, which facilitates the subsequent use of the inorganic coating material.
[0062] In some optional embodiments, the screening and impurity removal includes screening and impurity removal using a 320-mesh to 1000-mesh screen, and the strong magnetic iron removal includes strong magnetic iron removal using a permanent magnet rod and / or an electromagnetic iron remover.
[0063] In this embodiment of the application, the screen mesh size for screening and removing impurities and the equipment for strong magnetic iron removal can ensure that impurities in the inorganic coating material are completely removed, thereby obtaining a pure inorganic coating material, which facilitates the subsequent use of the inorganic coating material.
[0064] In some alternative embodiments, the regeneration process includes regeneration by calcination, wherein the calcination equipment includes at least one of a muffle furnace, tunnel kiln, pusher kiln, roller kiln, and microwave-heated kiln, and the final temperature of the calcination is 400°C to 900°C.
[0065] In this embodiment, the calcination equipment and calcination temperature for the regeneration process are specified to ensure that the stripped inorganic coating material is thoroughly cleaned, thereby obtaining a pure inorganic coating material, which facilitates the subsequent use of the inorganic coating material.
[0066] The final temperature for roasting can be 400℃ to 600℃.
[0067] The present application is further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the application. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to national standards. If there is no corresponding national standard, then general international standards, conventional conditions, or conditions recommended by the manufacturer are followed.
[0068] Example 1
[0069] like Figure 2 As shown, defective ceramic diaphragms with boehmite coatings and cut scraps were selected and placed in a beaker containing a 10% sodium fatty acid solution. After soaking in a constant temperature water bath at 90°C for 8 hours, the diaphragms were removed and hand-washed for 10 minutes. Then, they were repeatedly washed with 40°C reverse osmosis water and dried in an oven at 60°C. The dried base membrane material was collected for tiered reuse. The peeled-off ceramic inorganic coating material was passed through a 500-mesh sieve, repeatedly washed with 40°C reverse osmosis water, repeatedly removed with iron by a permanent magnet rod, dried in an oven at 150°C, and pulverized to obtain the recovered boehmite sample, with a recovery rate of 85%.
[0070] Example 2
[0071] Comparing Example 2 with Example 1, the difference between Example 2 and Example 1 is as follows:
[0072] Defective ceramic diaphragms with alumina coating and trimmed scraps were selected and placed in a beaker containing a 10% sodium fatty acid solution. After soaking in a constant temperature water bath at 90°C for 8 hours, the diaphragms were removed and hand-washed for 15 minutes. Then, they were repeatedly washed with 45°C reverse osmosis water and dried in an oven at 60°C. The dried base membrane material was collected for tiered reuse. The peeled-off ceramic inorganic coating material was passed through a 500-mesh sieve, repeatedly washed with 40°C reverse osmosis water, repeatedly removed by a permanent magnet rod, dried in an oven at 150°C, calcined in a muffle furnace at 550°C, and pulverized to obtain a recovered alumina sample with a recovery rate of 87%.
[0073] Example 3
[0074] Comparing Example 3 with Example 1, the difference between Example 3 and Example 1 is as follows:
[0075] Boehmite-coated ceramic separators from retired lithium batteries were selected and placed in a beaker containing a 15% sodium linear alkylbenzene sulfonate solution. After soaking in a constant temperature water bath at 95°C for 24 hours, the separators were removed and ultrasonically cleaned for 30 minutes. Then, they were repeatedly washed with reverse osmosis water at 45°C and dried in an oven at 55°C. The dried base membrane material was collected for tiered reuse. The peeled-off inorganic ceramic coating material was passed through a 500-mesh sieve, repeatedly washed with deionized water at 40°C, repeatedly removed with iron by a permanent magnet rod, dried in an oven at 150°C, and pulverized to obtain the recovered boehmite sample, with a recovery rate of 83%.
[0076] Example 4
[0077] Comparing Example 4 with Example 1, the difference between Example 4 and Example 1 is as follows:
[0078] Alumina-coated ceramic separators from retired lithium batteries were selected and placed in a beaker containing a 20% sodium linear alkylbenzene sulfonate solution. After soaking in a constant temperature water bath at 95°C for 24 hours, the separators were removed and ultrasonically cleaned for 60 minutes. Then, they were repeatedly washed with reverse osmosis water at 45°C and dried in an oven at 55°C. The dried base membrane material was collected for tiered reuse. The peeled-off ceramic inorganic coating material was passed through a 500-mesh sieve, repeatedly washed with deionized water at 40°C, repeatedly de-ironized with a permanent magnet rod, dried in an oven at 150°C, calcined in a muffle furnace at 600°C, and pulverized to obtain a recovered alumina sample with a recovery rate of 86%.
[0079] Example 5
[0080] Comparing Example 5 with Example 1, the difference between Example 5 and Example 1 is as follows:
[0081] The recycled waste ceramic membranes were selected and placed in a beaker containing a 10% nonionic surfactant solution. After soaking in a constant temperature water bath at 85°C for 24 hours, the membranes were removed and pounded for 10 minutes. Then, they were repeatedly washed with 50°C reverse osmosis water and dried in an oven at 60°C. The dried base membrane material was collected for tiered reuse. The peeled-off ceramic inorganic coating material was passed through a 325-mesh sieve, repeatedly washed with 40°C high-purity water, repeatedly removed from iron by a permanent magnet rod, dried in an oven at 150°C, calcined in a muffle furnace at 600°C, and pulverized to obtain a recovered alumina sample with a recovery rate of 87%.
[0082] Example 6
[0083] Comparing Example 6 with Example 1, the difference between Example 6 and Example 1 is as follows:
[0084] The recycled waste ceramic membranes were selected and placed in a beaker containing a 15% nonionic surfactant solution. After soaking in a constant temperature water bath at 85°C for 12 hours, the membranes were removed, washed in a washing machine for 15 minutes, and then repeatedly washed with 50°C reverse osmosis water. After drying in an oven at 60°C, the dried base membrane material was collected for tiered reuse. The peeled-off ceramic inorganic coating material was passed through a 325-mesh sieve, repeatedly washed with 40°C high-purity water, repeatedly removed by a permanent magnet rod, dried in an oven at 150°C, calcined in a muffle furnace at 580°C, and pulverized to obtain a recovered alumina sample with a recovery rate of 87%.
[0085] Comparative Example 1
[0086] Comparative Example 1 and Example 1 will be compared. The difference between Comparative Example 1 and Example 1 is as follows:
[0087] Defective ceramic diaphragms with boehmite coatings and cut scraps were selected and placed in a beaker of clean water. After soaking in a constant temperature water bath at 95°C for 24 hours, the diaphragms were removed and rubbed by hand for 10 minutes. Then, they were repeatedly washed with reverse osmosis water at 40°C, passed through a 500-mesh sieve, and repeatedly de-ironed by a permanent magnet rod. Finally, they were dried in an oven at 150°C and pulverized to obtain recovered boehmite samples. The recovery rate was only 8%.
[0088] Comparative Example 2
[0089] Comparative Example 2 and Example 1 will be compared. The difference between Comparative Example 2 and Example 1 is as follows:
[0090] Defective ceramic diaphragms with alumina coating and cut scraps were selected and placed in a beaker of clean water. After soaking in a constant temperature water bath at 95℃ for 24 hours, the diaphragms were removed and rubbed by hand for 10 minutes. Then, they were repeatedly washed with reverse osmosis water at 40℃, passed through a 500-mesh sieve, and repeatedly de-ironed by a permanent magnet rod. Finally, they were dried in an oven at 150℃ and pulverized to obtain recovered boehmite samples. The recovery rate was only 11%.
[0091] Relevant experimental and effect data: Scanning electron microscopy was performed on the boehmite sample recovered in Example 1 and the alumina sample recovered in Example 2, respectively. The results are as follows: Figure 3 and Figure 4 As shown.
[0092] Depend on Figure 3 It can be seen that the boehmite sample stripped in this application has a uniform particle distribution and a particle size concentrated in the micrometer level, indicating that the ceramic inorganic coating material and base film material stripped in this application are relatively pure.
[0093] Depend on Figure 4 It can be seen that the alumina sample particles stripped from this application are uniformly distributed and the particle size is concentrated at the micron level, indicating that the ceramic inorganic coating material and base film material stripped from this application are relatively pure.
[0094] One or more technical solutions in the embodiments of this application have at least the following technical effects or advantages:
[0095] (1) The method for separating and recycling lithium battery ceramic separators provided in this application embodiment can efficiently separate and recycle lithium battery ceramic separator materials. The recycled base membrane can be reused in stages, such as through secondary granulation and processing for public facility construction. The recycled inorganic materials can be used again as ceramic coatings for separators, electrode coatings, or in fields such as high-efficiency non-toxic flame retardants, polishing materials, and ceramic materials, thereby realizing the recycling of resources.
[0096] (2) The separation and recycling method of lithium battery ceramic separator provided in this application embodiment is simple, environmentally friendly, low cost and has good market prospects.
[0097] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the referred range.
[0098] In this application, unless otherwise stated, directional terms such as "upper" and "lower" specifically refer to the drawing directions in the accompanying drawings. Furthermore, in the description of this application, terms such as "comprising" and "including" mean "including but not limited to." In this document, relational terms such as "first" and "second" are used merely to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. In this document, "and / or" describes the relationship between related objects, indicating that three relationships can exist; for example, A and / or B can represent: A alone, A and B simultaneously, or B alone. A and B can be singular or plural. In this document, "at least one" means one or more, and "more than one" means two or more. "At least one," "at least one of the following," or similar expressions refer to any combination of these items, including any combination of single or plural items. For example, "at least one of a, b, or c" or "at least one of a, b, and c" can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be a single or multiple.
[0099] The above description is merely a specific embodiment of this application, enabling those skilled in the art to understand or implement this application. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of this application. Therefore, this application is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features claimed herein.
Claims
1. A method for separating and recycling lithium battery ceramic separators, characterized in that, The separation and recovery method includes: Waste lithium battery ceramic separators are sorted and cut to obtain separator materials; The membrane material was added to the stripping agent solution and soaked, then rubbed and washed to obtain the base film material and the stripping material respectively. The base film material is dried to obtain a base film; The stripped material is purified or regenerated to obtain an inorganic coating material for the ceramic diaphragm. The mass concentration of the stripping agent solution is 1% to 50%. The solute in the stripping agent solution includes at least one of the following: alkali metal salts of fatty acids, sodium alkyl sulfonate, sodium linear alkylbenzene sulfonate, nonionic surfactants, and anhydrous ethanol.
2. The separation and recovery method according to claim 1, characterized in that, The mass concentration of the stripping agent solution is 5% to 20%.
3. The separation and recovery method according to claim 1, characterized in that, The soaking temperature is 10℃~100℃, and the soaking time is 0.5h~72h.
4. The separation and recovery method according to claim 1, characterized in that, The rubbing and cleaning method is a physical rubbing and cleaning method, and the cleaning agent used in the rubbing and cleaning includes at least one of reverse osmosis water, deionized water and high-purity water.
5. The separation and recovery method according to claim 1, characterized in that, The rubbing and washing time is 10 min to 60 min, and the rubbing and washing temperature is 10℃ to 100℃.
6. The separation and recovery method according to claim 1, characterized in that, The drying process includes static drying, and the drying temperature is 50℃~100℃.
7. The separation and recovery method according to claim 1, characterized in that, The purification process includes sieving to remove impurities and strong magnetic removal of iron.
8. The separation and recovery method according to claim 7, characterized in that, The screening and impurity removal includes screening and impurity removal using a 320-1000 mesh screen, and the strong magnetic iron removal includes strong magnetic iron removal using a permanent magnet rod and / or an electromagnetic iron remover.
9. The separation and recovery method according to claim 7, characterized in that, The regeneration process includes regeneration by roasting, and the roasting equipment includes at least one of muffle furnace, tunnel kiln, pusher kiln, roller kiln and microwave heating kiln, and the final temperature of the roasting is 400℃~900℃.