Crushing treatment method for industrial lithium-containing waste

Abstract

The invention provides a crushing treatment method for industrial lithium-containing waste, which is characterized in that lithium-containing electrolyte, lithium-containing smelting tailings and lithium-containing glass in the industrial lithium-containing waste are respectively treated by adopting different pretreatment procedures by adopting a composite process assembly mode, so that the water content of a first material and the water content of a third material are both less than 5%; and the second material does not contain large magnetic iron pieces, so that the lithium-containing powder with proper granularity is finally obtained. The crushing treatment method adopts intensive layout, is suitable for treating various types of industrial lithium-containing waste materials, and is high in applicability, simple to operate, small in occupied area, high in early-stage investment cost and high in production line operation rate.

Description

Technical Field

[0001] The invention relates to the technical field of waste recycling, and in particular to a method for crushing and processing industrial lithium-containing waste. Background Art

[0002] Industrial lithium-containing waste generally refers to waste lithium batteries, pole piece waste, lithium mine tailings, and lithium-containing salts. Generally, when recycling such lithium-containing waste, it is necessary to crush it. With the continuous accumulation of technology, the crushing and recycling technology of conventional industrial lithium-containing waste has become increasingly mature, and it continues to break through new technical standards. In 2023, China will reach 70% of the world's lithium battery production capacity, but its domestic lithium reserves account for 6% of the world, but it will consume 50% of the world's lithium. Therefore, in the face of the shortage of domestic lithium resources and the peak of retired lithium batteries has not yet arrived, it is of great significance to develop other types of industrial lithium-containing waste to ensure the supply of strategic minerals.

[0003] In the electrolytic production process, lithium fluoride salts are added to the electrolyte to improve the properties of the electrolyte and achieve the purpose of improving current efficiency and reducing energy consumption. During the electrolytic production process, the electrolytic cell adsorbs additives such as lithium salts and forms a lithium-containing electrolyte. This lithium-containing electrolyte contains a large amount of fluorine, which poses a serious threat to the environment. In the glass production process, in order to improve the chemical stability, corrosion resistance and optical properties of the glass, lithium is added to solar photovoltaic glass, mobile phone screen glass, lens glass, etc., so that the glass has higher optical transparency, resistivity and strength. As a powerhouse of electronic products, China can meet the needs of environmental protection and corporate carbon emission reduction by recycling and high-value utilization of lithium-containing glass. In the lithium slag beneficiation and smelting process, a large amount of lithium-containing smelting slag is produced due to the process limitations of the production line. Since the grade of smelting waste slag is between 0.3% and 1.0%, the current process has a low utilization rate of lithium for this grade of waste slag, which is easy to cause resource waste.

[0004] In summary, faced with new industrial lithium-containing waste represented by lithium-containing electrolytes, lithium-containing glass, and lithium-containing smelting tailings, a method for crushing and processing industrial lithium-containing waste is urgently needed to solve the above technical problems. Summary of the invention

[0005] The purpose of the present invention is to provide a method for crushing industrial lithium-containing waste, which is used to solve the technical problem that the existing technology is difficult to meet the crushing needs of non-standard industrial lithium-containing waste represented by lithium-containing electrolytes, lithium-containing glass, and lithium-containing smelting tailings.

[0006] In order to solve the above technical problems, the present invention provides a method for crushing industrial lithium-containing waste, comprising: The lithium-containing electrolyte, the lithium-containing smelting tailings and the lithium-containing glass in the industrial lithium-containing waste are treated by different pretreatment processes to obtain a first material, a second material and a third material respectively; The first material, the second material and the third material are mixed and then sieved to obtain coarse powder material on the sieve and fine powder material under the sieve; The fine powder under the sieve is subjected to fine iron removal treatment to obtain magnetic waste and lithium-containing materials; Grinding and pulverizing the lithium-containing material to obtain lithium-containing powder; The moisture content of the first material and the third material is less than 5%, and the second material does not contain large pieces of magnetic iron.

[0007] Preferably, the lithium-containing electrolyte is treated by a first pretreatment process to obtain the first material, and the first pretreatment process specifically includes: The battery crushed material is subjected to high temperature drying treatment to obtain the first material, and the temperature of the high temperature drying treatment is 250° C. to 350° C.

[0008] Preferably, the second pretreatment process is used to process the lithium-containing smelting tailings to obtain the second material, and the second pretreatment process specifically includes: Coarsely crushing the lithium-containing smelting tailings to obtain first smelting tailings; Performing a rough iron removal treatment on the first smelting tailings to obtain a second smelting tailings; The second smelting tailings are finely crushed to obtain the second material.

[0009] Preferably, the lithium-containing glass is processed by a third pretreatment process to obtain a third material, and the third pretreatment process specifically includes: The lithium-containing glass is subjected to low-temperature drying treatment to obtain glass waste, wherein the temperature of the low-temperature drying treatment is 80°C to 120°C; The waste glass is finely crushed to obtain the third material.

[0010] Preferably, the step of treating the lithium-containing electrolyte, lithium-containing smelting tailings and lithium-containing glass in the industrial lithium-containing waste using different pretreatment processes also includes: performing the second pretreatment process in the middle shift according to the production plan, and performing the first pretreatment process or the third pretreatment process in the morning and evening shifts.

[0011] Preferably, after the first material, the second material and the third material are mixed and sieving, the process further comprises: The coarse powder on the sieve is subjected to secondary coarse iron removal treatment to obtain coarse iron waste and lithium-containing return material; The lithium-containing return material, the second smelting tailings and the glass waste are mixed and then finely crushed.

[0012] Preferably, an electromagnetic self-unloading iron remover on a belt conveyor is used to perform the primary rough iron removal process and the secondary rough iron removal process respectively.

[0013] Preferably, a strong magnetic iron remover on a belt conveyor is used to carry out fine iron removal on the fine powder under the sieve.

[0014] Preferably, the particle size of the fine powder obtained after screening is less than 6 mesh.

[0015] Preferably, the lithium-containing material is ground and pulverized using a Raymond mill, and the particle size of the lithium-containing powder is less than 180 meshes.

[0016] The beneficial effects of the present invention are as follows: Different from the prior art, the present invention provides a method for crushing and treating industrial lithium-containing waste, which uses a composite process combination to treat the lithium-containing electrolyte, lithium-containing smelting tailings and lithium-containing glass in the industrial lithium-containing waste respectively using different pretreatment procedures, so that the moisture content of the first material and the third material is less than 5%, and the second material does not contain large pieces of magnetic iron, and finally obtains lithium-containing powder of suitable particle size. The crushing and treating method of the present invention adopts an intensive layout, which is suitable for treating various types of industrial lithium-containing waste, has strong applicability, simple operation, small footprint, high initial investment cost, but high production line start-up rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] Figure 1 A flow chart of a method for crushing and treating industrial lithium-containing waste provided by an embodiment of the present invention; Figure 2 This is a process flow chart of the crushing method for industrial lithium-containing waste provided in Example 1 of the present invention. DETAILED DESCRIPTION

[0018] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0019] The purpose of the present invention is to overcome the above-mentioned technical deficiencies and provide a method for crushing and processing industrial lithium-containing waste, which is used to solve the technical problem that the existing technology is difficult to meet the crushing needs of non-standard industrial lithium-containing waste represented by lithium-containing electrolytes, lithium-containing glass, and lithium-containing smelting tailings.

[0020] See also Figure 1 , Figure 1 A flow chart of a method for crushing and treating industrial lithium-containing waste provided by an embodiment of the present invention; wherein the method for crushing and treating industrial lithium-containing waste specifically includes: S10, treating the lithium-containing electrolyte, lithium-containing smelting tailings and lithium-containing glass in the industrial lithium-containing waste by different pretreatment processes to obtain a first material, a second material and a third material respectively.

[0021] Specifically, step S10 also includes: Provide industrial lithium-containing waste, including lithium-containing electrolyte, lithium-containing smelting tailings and lithium-containing glass.

[0022] Specifically, lithium-containing electrolytes often cause equipment breakdown due to their large pieces over 20 cm, irregular surface, high hardness, and high water content. Lithium-containing glass has a smooth surface, hard texture, and small size. At the same time, the surface is moist and the water is not easy to volatilize, which makes it impossible to process it at existing crushing sites. Smelting tailings are prone to blockage of crushing equipment and wear of parts due to their large pieces over 30 cm, many internal debris, complex composition, and high hardness. Therefore, it is necessary to use different pretreatment procedures to treat lithium-containing electrolytes, lithium-containing smelting tailings, and lithium-containing glass in industrial lithium-containing waste.

[0023] Preferably, the lithium-containing electrolyte is treated by a first pretreatment process to obtain the first material, and the first pretreatment process specifically includes: The battery crushed material is subjected to high-temperature drying treatment to obtain a first material, the temperature of the high-temperature drying treatment is 250° C. to 350° C., and the moisture content of the first material is less than 5%.

[0024] Specifically, lithium-containing electrolytes are usually recovered from industrial products such as batteries, and may contain more water and some volatile impurities when they exist in the form of battery crushed materials. High-temperature drying at 250°C to 350°C can effectively remove these water and volatile impurities. For example, battery electrolytes may contain organic solvents, which will evaporate in this temperature range, making the material purer and the first material obtained higher in quality, which is conducive to subsequent further processing and lithium extraction.

[0025] At the same time, high temperature drying can make the physical state of lithium-containing electrolytes more stable. The structure of the battery material after crushing is relatively loose, and drying can make the particle structure of the material more compact, preventing the material from agglomerating and absorbing moisture during subsequent storage, transportation or further processing, thereby ensuring the consistency and stability of the first material.

[0026] Preferably, the second pretreatment process is used to process the lithium-containing smelting tailings to obtain the second material, and the second pretreatment process specifically includes: Coarsely crushing the lithium-containing smelting tailings to obtain first smelting tailings; Performing a rough iron removal treatment on the first smelting tailings to obtain a second smelting tailings; The second smelting tailings are finely crushed to obtain a second material, which does not contain large pieces of magnetic iron.

[0027] Specifically, lithium-containing smelting tailings usually exist in large blocks or lumps, and the purpose of the coarse crushing treatment is to crush them into smaller particles, increase the surface area of ​​the material, and provide better conditions for subsequent processing steps. A coarse iron removal treatment of the first smelting tailings can remove iron impurities in the lithium-containing smelting tailings. The presence of iron impurities may affect the subsequent extraction of lithium and product quality, so it is necessary to perform iron removal treatment in the pretreatment stage. After coarse crushing and a coarse iron removal treatment, the second smelting tailings is further crushed to meet finer particle size requirements. Fine crushing can make the particles of the second smelting tailings more uniform, which is beneficial to subsequent processing and separation operations.

[0028] Preferably, the lithium-containing glass is processed by a third pretreatment process to obtain a third material, and the third pretreatment process specifically includes: The lithium-containing glass is subjected to low-temperature drying treatment to obtain glass waste, wherein the temperature of the low-temperature drying treatment is 80°C to 120°C; The waste glass is finely crushed to obtain a third material, and the moisture content of the third material is less than 5%.

[0029] Specifically, the low-temperature drying process is set at 80℃~120℃, which is a relatively low temperature range. It can effectively remove volatile substances such as moisture in lithium-containing glass and avoid excessive damage to the structure and composition of the glass. Fine crushing of waste glass can make the particles of the third material more uniform, increase its surface area, and facilitate subsequent processing and separation operations.

[0030] Furthermore, the step of using different pretreatment processes to treat the lithium-containing electrolyte, lithium-containing smelting tailings and lithium-containing glass in the industrial lithium-containing waste also includes: performing the second pretreatment process in the middle shift according to the production plan, and performing the first pretreatment process or the third pretreatment process in the morning and evening shifts.

[0031] Specifically, considering that the treatment process of lithium-containing smelting tailings is relatively complicated and requires more time and energy, arranging it in the middle shift can make full use of the production resources during this time period to ensure the smooth progress of the treatment process. Carrying out the second pretreatment process in the middle shift according to the production plan helps to improve production efficiency, ensure that the lithium-containing smelting tailings can be processed in time, and provide a stable supply of raw materials for subsequent processing steps.

[0032] Specifically, the morning shift and the evening shift can choose to carry out the first pretreatment process (treatment of lithium-containing electrolytes) or the third pretreatment process (treatment of lithium-containing glass) according to actual conditions. This arrangement can make full use of the time of the morning and evening shifts and improve the utilization rate of equipment. At the same time, it can also reasonably allocate human resources according to the characteristics and treatment difficulty of different waste materials to ensure the efficient operation of the entire production process.

[0033] This step can coordinate different pre-treatment processes through reasonable time arrangement to avoid congestion and delays in the production process. Carrying out each process in different shifts helps to improve the operating efficiency of the equipment, reduce waiting time, and thus improve the smoothness of the entire production process.

[0034] S20, the first material, the second material and the third material are mixed and then sieved to obtain coarse powder material on the sieve and fine powder material under the sieve.

[0035] Specifically, step S20 also includes: The first material, the second material and the third material are mixed and then put into a drum screen for screening to obtain coarse powder material on the screen and fine powder material under the screen, and the particle size of the fine powder material under the screen is less than 6 mesh.

[0036] Specifically, the materials from three different sources are mixed and then screened with a drum screen in order to separate materials of different particle sizes. The coarse powder on the screen and the fine powder under the screen can be processed differently according to the subsequent process requirements.

[0037] In an embodiment of the present invention, after the first material, the second material and the third material are mixed and sieving, the method further includes: The coarse powder on the sieve is subjected to secondary coarse iron removal treatment to obtain coarse iron waste and lithium-containing return material; The lithium-containing return material, the second smelting tailings and the glass waste are mixed and then finely crushed.

[0038] Specifically, the coarse powder on the screen is subjected to a secondary rough iron removal treatment to further remove iron impurities in the coarse powder on the screen. The iron may not be completely removed in the previous treatment process, or new iron impurities may be introduced during the mixing and screening process. The secondary rough iron removal treatment can improve the purity of the coarse powder on the screen and reduce the impact of iron on subsequent processes.

[0039] Specifically, the lithium-containing return material, the second smelting tailings and the glass waste are mixed and then finely crushed. Such a mixture can make full use of the lithium resources in different materials and improve the resource recovery rate. The entire processing process forms a closed-loop system, and the process flow is optimized by classifying, mixing and reprocessing different materials. This method can improve production efficiency, reduce waste generation, and meet the requirements of sustainable development.

[0040] In the embodiment of the present invention, an electromagnetic self-unloading iron remover on a belt conveyor is used to perform primary rough iron removal and secondary rough iron removal respectively; wherein, through the action of electromagnetic force, the electromagnetic self-unloading iron remover can effectively absorb iron impurities in the material and separate them from the material. This iron removal method is more thorough than traditional manual or mechanical iron removal, and can improve the purity of the material; the electromagnetic self-unloading iron remover can automatically remove iron impurities in the material during the operation of the belt conveyor without manual intervention, which greatly improves production efficiency.

[0041] S30, performing fine iron removal treatment on the fine powder under the sieve to obtain magnetic waste and lithium-containing materials.

[0042] Specifically, step S30 also includes: The strong magnetic iron remover on the belt conveyor is used to remove the iron from the fine powder under the sieve to obtain magnetic waste and lithium-containing materials. When the fine powder under the sieve passes through the strong magnetic iron remover, the iron impurities in it are adsorbed on the iron remover to form magnetic waste. The lithium-containing materials that do not contain iron or have a low iron content continue to pass through the iron remover and are separated. This process realizes the further purification of the fine powder under the sieve, providing purer raw materials for the subsequent treatment of lithium-containing materials.

[0043] Specifically, the strong magnetic iron remover has a strong magnetic field strength, which can effectively absorb tiny iron impurities in fine powder and improve the iron removal effect. The strong magnetic iron remover is used in combination with a belt conveyor to achieve continuous operation and improve production efficiency. During the conveying process, the strong magnetic iron remover can automatically remove iron from the material without manual intervention.

[0044] S40, grinding and pulverizing the lithium-containing material to obtain lithium-containing powder.

[0045] Specifically, step S40 also includes: The Raymond mill is used to grind and pulverize lithium-containing materials. The particle size of the lithium-containing powder is less than 180 meshes to meet the best extraction effect of lithium recovery in the leaching process. Among them, the Raymond mill has efficient and stable grinding performance and can grind the material to the required particle size. It uses the grinding roller to roll tightly on the grinding ring under the action of centrifugal force to crush the material into powder, and then separates the lithium-containing powder that meets the particle size requirements through the action of the fan and analyzer.

[0046] The technical solution of the present application is now further described in detail in conjunction with specific embodiments.

[0047] Embodiment 1: See also Figure 2 , Figure 2The process flow chart of the crushing method for industrial lithium-containing waste provided in Example 1 of the present invention is as follows: (1) Pretreatment process of lithium-containing electrolyte: The lithium-containing electrolyte is dried in a rotary kiln at 250℃350℃ for 1 hour, and the moisture content is reduced from 10% to 20% to below 5%. Then it enters the drum screen for screening with a mesh size of 6. The screened material is returned to the hammer crusher for fine crushing. The screened fine powder enters the intermediate silo and then enters the Raymond mill for powder making with a mesh size of 180.

[0048] (2) Pretreatment process of lithium-containing smelting slag: The lithium-containing smelting slag is coarsely crushed by a jaw crusher, and the material is then removed by an electromagnetic self-unloading iron remover to remove large magnetic iron pieces and enters a three-stage temporary storage bin. After fine crushing by a hammer crusher, the material enters a drum screen for screening with a mesh size of 6. The screened material is returned to the hammer crusher for fine crushing. An electric self-unloading iron remover is installed on the belt conveyor to remove large pieces of smelting waste slag and hard iron objects after being crushed. The fine powder is screened and enters the intermediate silo. A strong magnetic iron remover is installed on the belt conveyor to prevent iron parts from falling from the front-end crushing process equipment. The powder finally enters a Raymond mill for pulverizing with a mesh size of 180.

[0049] (3) Pretreatment process of lithium-containing glass: The lithium-containing glass is dried in a rotary kiln at 100°C for 1 hour and then enters the three-stage temporary storage bin. After being finely crushed by a hammer crusher, the material enters the drum screen for screening with a mesh size of 6. The screened material is returned to the hammer crusher for fine crushing, and the fine powdered material under the screen enters the intermediate silo. The powdered material finally enters the Raymond mill for powder making with a mesh size of 180.

[0050] (4) The three raw materials are pre-treated intermittently: Due to the large amount of debris inside the lithium-containing smelting tailings, the feeding production is carried out in the middle shift according to the production plan under the condition of sufficient lighting conditions and production personnel; the lithium-containing electrolyte or lithium-containing glass is crushed in the morning and evening shifts. At the same time, due to the smoothness of the glass surface, glass is produced to clean the inner cavity of the equipment after each lithium-containing smelting tailings or lithium-containing electrolyte has been running for one day.

[0051] (5) Particle size control of the three raw materials: In order to meet the particle size requirements of the back-end process, the hammer crusher screen plate, drum screen mesh size, and Raymond mill centrifugal fan frequency are controlled to meet the use requirements of the subsequent process.

[0052] (6) The whole working process of Raymond mill: the material of qualified size in the Raymond mill silo is controlled by the drum screen, and is evenly fed into the grinding chamber of the Raymond mill main machine by the electric vibrating feeder for grinding. The ground powder is carried away by the air flow blown into the mill by the centrifugal fan; after internal classification of the equipment, the lithium-containing powder that meets the particle size (180 mesh) is collected by the air cyclone powder collector, and the powder that does not meet the particle size re-enters the grinding chamber for grinding.

[0053] The present invention provides a method for crushing and treating industrial lithium-containing waste, which can achieve the purpose of compatibility of production lines for crushing and treating lithium-containing electrolytes, lithium-containing glass, and lithium-containing smelting tailings, and can simultaneously meet the crushing needs of non-standard lithium-containing waste represented by lithium-containing electrolytes, lithium-containing glass, and lithium-containing smelting tailings; the process has strong applicability, simple operation, small footprint, high initial investment cost, but high production line start-up rate.

[0054] It should be noted that the above embodiments all belong to the same inventive concept, and the description of each embodiment has its own focus. For matters that are not described in detail in some embodiments, reference may be made to the description in other embodiments.

[0055] The above embodiments only express the implementation methods of the present invention, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for those of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for crushing industrial lithium-containing waste, characterized in that: include: The lithium-containing electrolyte, the lithium-containing smelting tailings and the lithium-containing glass in the industrial lithium-containing waste are treated by different pretreatment processes to obtain a first material, a second material and a third material respectively; The first material, the second material and the third material are mixed and then sieved to obtain coarse powder material on the sieve and fine powder material under the sieve; The fine powder under the sieve is subjected to fine iron removal treatment to obtain magnetic waste and lithium-containing materials; Grinding and powdering the lithium-containing material to obtain lithium-containing powder; The moisture content of the first material and the third material is less than 5%, and the second material does not contain large pieces of magnetic iron.

2. The method for crushing industrial lithium-containing waste according to claim 1, characterized in that: The lithium-containing electrolyte is treated by a first pretreatment process to obtain the first material, and the first pretreatment process specifically includes: The first material is obtained by subjecting the battery crushed material to high temperature drying treatment, wherein the temperature of the high temperature drying treatment is 250° C. to 350° C.

3. The method for crushing industrial lithium-containing waste according to claim 2, characterized in that: The second material is obtained by treating the lithium-containing smelting tailings with a second pretreatment process, wherein the second pretreatment process specifically comprises: Coarsely crushing the lithium-containing smelting tailings to obtain first smelting tailings; Performing a rough iron removal treatment on the first smelting tailings to obtain second smelting tailings; The second smelting tailings are finely crushed to obtain the second material.

4. The method for crushing industrial lithium-containing waste according to claim 3, characterized in that: The lithium-containing glass is processed by a third pretreatment process to obtain the third material, and the third pretreatment process specifically includes: The lithium-containing glass is subjected to low-temperature drying treatment to obtain glass waste, wherein the temperature of the low-temperature drying treatment is 80° C. to 120° C.; The glass waste is finely crushed to obtain the third material.

5. The method for crushing industrial lithium-containing waste according to claim 4, characterized in that: The step of using different pretreatment processes to treat the lithium-containing electrolyte, lithium-containing smelting tailings and lithium-containing glass in industrial lithium-containing waste also includes: performing the second pretreatment process in the middle shift according to the production plan, and performing the first pretreatment process or the third pretreatment process in the morning and evening shifts.

6. The method for crushing industrial lithium-containing waste according to claim 4, characterized in that: After the first material, the second material and the third material are mixed and sieving, the following further comprises: The coarse powder on the sieve is subjected to secondary coarse iron removal treatment to obtain coarse iron waste and lithium-containing return material; The lithium-containing return material, the second smelting tailings and the glass waste are mixed and then subjected to the fine crushing treatment.

7. The method for crushing industrial lithium-containing waste according to claim 6, characterized in that: The electromagnetic self-unloading iron remover on the belt conveyor is used to perform the primary rough iron removal process and the secondary rough iron removal process respectively.

8. The method for crushing industrial lithium-containing waste according to claim 7, characterized in that: The strong magnetic iron remover on the belt conveyor is used to carry out fine iron removal treatment on the fine powder under the sieve.

9. The method for crushing industrial lithium-containing waste according to claim 7, characterized in that: The particle size of the fine powder obtained after the screening process is less than 6 mesh.

10. The method for crushing industrial lithium-containing waste according to claim 1, characterized in that: The lithium-containing material is ground and powdered using a Raymond mill, and the particle size of the lithium-containing powder is less than 180 meshes.

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