Metal material recycling device and method for leaching fluorine beryllium thallium and lithium rubidium cesium in lithium slag

Abstract

The invention provides a metal material recycling device and a method for leaching fluorine beryllium thallium and lithium rubidium cesium in lithium slag. Relates to the field of metal material recycling, and comprises a leaching tank placed on the ground through four supporting frames, the top of the leaching tank is fixedly provided with a top cover, and the bottom of the leaching tank is fixedly provided with a bottom cover. According to the metal material recycling device and the leaching method for fluorine beryllium thallium and lithium rubidium cesium in the lithium slag, the ultrasonic generator is arranged to supply energy to the first ultrasonic transducer and the second ultrasonic transducer to generate ultrasonic waves, the ultrasonic waves generate microjet flow to impact the surface of minerals, acid liquor permeation and ion diffusion are accelerated, the leaching time is shortened, and the efficiency is improved; the surface of the lithium slag is not prone to passivation, the leaching rate of target metal ions is increased, the leaching liquid is pumped out through the water suction pump, manual contact with the leaching liquid in the next solid-liquid separation procedure is facilitated, dilute sulfuric acid is supplemented through the acid supplementing pipe, then the lithium slag is placed through the funnel, and the consistency and controllability of starting of the leaching reaction are guaranteed.

Description

Technical Field

[0001] This invention relates to the field of metal material recycling, and more particularly to metal material recycling equipment and methods for leaching fluorine, beryllium, thallium and lithium, rubidium and cesium from lithium slag. Background Technology

[0002] Metallic materials are the cornerstone of modern industry and social development, widely used in construction, transportation, electronics, machinery, and daily necessities. With rapid economic development and continuous improvement in social consumption levels, the output and scrap volume of metal products are increasing daily. The mining and smelting of primary metal mineral resources is a high-energy-consuming, high-polluting, and high-carbon-emission process. Moreover, many mineral resources are non-renewable and face the risk of depletion. Efficient recycling and reuse of scrap metals is of great strategic importance. Saving natural resources, reducing energy consumption, reducing environmental pollution, and reducing greenhouse gas emissions are key links in achieving a circular economy and sustainable development. Lithium slag is the solid waste after lithium extraction from spodumene or lepidolite. It contains scarce metals such as lithium, rubidium, and cesium, but is accompanied by toxic elements such as fluorine, beryllium, and thallium.

[0003] Existing metal recycling devices involve leaching activated lithium slag in a strong acid solution, followed by extraction of the leachate after leaching to obtain a leachate containing the target metal.

[0004] However, existing metal recycling devices have long leaching times during use, and the lithium slag surface is easily passivated, affecting ion release.

[0005] Therefore, it is necessary to provide metal material recycling equipment and leaching methods for fluorine, beryllium, thallium, lithium, rubidium, and cesium in lithium slag to solve the above-mentioned technical problems. Summary of the Invention

[0006] This invention provides a metal material recycling device and a method for leaching fluorine, beryllium, thallium, lithium, rubidium, and cesium from lithium slag, solving the problems of long leaching times, easy passivation of lithium slag surface, and impaired ion release during use.

[0007] To solve the above-mentioned technical problems, the present invention provides a metal material recycling device, comprising: a leaching tank placed on the ground by four support frames, a top cover fixedly installed on the top of the leaching tank, a bottom cover fixedly installed on the bottom of the leaching tank, and a funnel connected to the top of the top cover;

[0008] A pull-out mechanism, which is connected to the bottom of the bottom cover;

[0009] An ultrasonic generator, which is fixedly installed on the bottom of the base cover;

[0010] The first ultrasonic transducer mechanism is fixedly installed on the top of the bottom cover. The first ultrasonic transducer mechanism includes a first rotating shaft. The two ends of the first rotating shaft are respectively fixedly installed on the top of the bottom cover through two rotating brackets. A first support is fixedly installed on the surface of the first rotating shaft, and a first ultrasonic transducer is fixedly installed on the top of the first support.

[0011] The second ultrasonic transducer mechanism is fixedly installed on the top of the bottom cover. The second ultrasonic transducer mechanism includes a second rotating shaft. The two ends of the second rotating shaft are respectively fixedly installed on the top of the bottom cover through two rotating brackets. A second support is fixedly installed on the surface of the second rotating shaft, and a second ultrasonic transducer is fixedly installed on the top of the second support.

[0012] Preferably, the extraction mechanism includes a water extraction pipe connected to the bottom of the bottom cover, a water pump connected to the bottom end of the water extraction pipe, the water pump being installed on the ground, and a drain pipe connected to the output end of the water pump.

[0013] Preferably, the top of the top cover is connected to an acid replenishment mechanism, the acid replenishment mechanism includes an acid replenishment pipe, the acid replenishment pipe is connected to the top of the top cover, and the top end of the acid replenishment pipe is connected to an acid replenishment valve.

[0014] Preferably, a stirring mechanism is fixedly installed on the top of the top cover. The stirring mechanism includes a cylinder, which is fixedly installed on the top of the top cover. The output end of the cylinder passes through the top of the top cover and extends into the interior of the leaching tank. A stirring connecting sleeve is fixedly installed on the output end of the cylinder through a stirring bearing. A stirring shaft is fixedly installed at the bottom of the stirring connecting sleeve. Several sets of stirring blades are fixedly installed on the surface of the stirring shaft.

[0015] Preferably, a drive mechanism is fixedly installed on the top of one of the support frames. The drive mechanism includes a motor, a second bevel gear, and a third bevel gear. The motor is fixedly installed on the top of one of the support frames. The output shaft of the motor is fixedly connected to a transmission shaft. One end of the transmission shaft passes through one side of the leaching tank and extends into the interior. A first bevel gear is fixedly installed on the end of the transmission shaft located inside the leaching tank. The second bevel gear and the third bevel gear are fixedly installed on the surface of the stirring shaft. The first bevel gear meshes with the second bevel gear and the third bevel gear.

[0016] Preferably, a lifting mechanism is fixedly installed on the surface of the stirring shaft. The lifting mechanism includes a lifting bearing and a limiting plate. The lifting bearing is fixedly installed on the surface of the stirring shaft. A fixing plate is fixedly installed on the peripheral side of the lifting bearing through a lifting connecting sleeve. A vertical plate is fixedly installed on the bottom end of the fixing plate through a drive plate. The limiting plate is fixedly installed on the top of the bottom cover. The vertical plate is adapted to the limiting plate.

[0017] Preferably, a rotating mechanism is fixedly installed on the top of the bottom cover. The rotating mechanism includes a base, which is fixedly installed on the top of the bottom cover. A rotating shaft is rotatably installed inside the base. A first disc and a second disc are fixedly installed at both ends of the rotating shaft, respectively. A first convex shaft is fixedly installed on one side of the first disc, and the first convex shaft is adapted to be installed with the drive plate. Two second convex shafts are symmetrically fixedly installed on one side of the second disc. One of the second convex shafts is rotatably connected to a third disc via a connecting rod, and the third disc is fixedly installed at one end of the first rotating shaft. The other second convex shaft is rotatably connected to a fourth disc via a connecting rod, and the fourth disc is fixedly installed at one end of the second rotating shaft.

[0018] Preferably, a pH sensor is fixedly installed on the inner wall of the leaching tank, and two electrode plates are symmetrically fixedly installed on the inner wall of the leaching tank.

[0019] Preferably, two scraper mechanisms are symmetrically fixedly installed on one side of the leaching tank. Each scraper mechanism includes a motor, which is fixedly installed on one side of the leaching tank via a bracket. The output shaft of the motor is fixedly connected to a connecting shaft. One end of the connecting shaft passes through one side of the leaching tank and extends into the interior. A scraper is fixedly installed at the end of the connecting shaft located inside the leaching tank. The two scrapers are respectively adapted to and installed with the two electrode plates.

[0020] A method for leaching fluorine, beryllium, thallium, lithium, rubidium, and cesium from lithium slag includes the following steps:

[0021] S1: Lithium slag pretreatment and activation: Crush the lithium slag to 80-120 mesh, add it to a microwave reactor, and irradiate it at 2.45 GHz and 600-800 W for 5-10 minutes;

[0022] S2: Ultrasonic-electric field coupled leaching: The activated lithium slag is immersed in dilute sulfuric acid at pH 2.0-2.5, and ultrasonic waves of 20-40kHz are applied with a power density of 50-100W / L and a DC electric field voltage of 5-10V. The anode is a titanium-plated ruthenium electrode.

[0023] S3: Mechanical field enhanced mass transfer: During the leaching process, mechanical stirring is performed at 300-500 rpm, and the stirring direction is changed periodically every 5 minutes;

[0024] S4: Solid-liquid separation and neutralization: After pressure filtration, the leachate is neutralized to pH 7-8 with lime milk to solidify fluorine, beryllium, and thallium; the filtrate is enriched by ion exchange resin. , , .

[0025] Compared with related technologies, the metal material recycling device provided by the present invention has the following beneficial effects:

[0026] This invention provides a metal material recycling device. By activating an ultrasonic generator, power is supplied to the first and second ultrasonic transducers to generate ultrasonic waves. The ultrasonic waves generate micro-jets that impact the mineral surface, accelerating acid penetration and ion diffusion, shortening the leaching time and improving efficiency. This makes the lithium slag surface less prone to passivation and increases the leaching rate of the target metal ions. A water pump is set up to extract the leachate, facilitating the next solid-liquid separation process and avoiding manual contact with the leachate. Dilute sulfuric acid is first added through an acid replenishment pipe, and then the lithium slag is added through a funnel, ensuring the consistency and controllability of the leaching reaction initiation. Attached Figure Description

[0027] Figure 1 A schematic diagram of a preferred embodiment of the metal material recycling device provided by the present invention;

[0028] Figure 2 Another structural schematic diagram of a preferred embodiment of a metal material recycling device;

[0029] Figure 3 for Figure 2 The diagram shown is a structural schematic of the acid replenishment mechanism.

[0030] Figure 4 for Figure 2 The diagram shows the structure of the extraction mechanism;

[0031] Figure 5 for Figure 2 The diagram shows the structure of the first ultrasonic transducer.

[0032] Figure 6 for Figure 2 The diagram shows the structure of the second ultrasonic transducer.

[0033] Figure 7 This is a schematic diagram of the second embodiment of the metal material recycling device;

[0034] Figure 8 for Figure 7 The diagram shows the structure of the stirring mechanism.

[0035] Figure 9 for Figure 7 The diagram shows the structure of the drive mechanism.

[0036] Figure 10 for Figure 7 The diagram shows the installation of the rotating mechanism;

[0037] Figure 11 for Figure 10 The diagram shows the structure of the lifting mechanism.

[0038] Figure 12 for Figure 7 The diagram shows the structure of the rotating mechanism.

[0039] Figure 13 for Figure 12 Another schematic diagram of the rotating mechanism shown;

[0040] Figure 14 for Figure 7 The diagram shows the structure of the scraper mechanism.

[0041] The diagram is labeled as follows: 1. Leaching tank; 2. Top cover; 3. Bottom cover; 4. Acid replenishment mechanism; 401. Acid replenishment pipe; 402. Acid replenishment valve; 5. Extraction mechanism; 501. Water extraction pipe; 502. Water pump; 503. Drain pipe; 6. Stirring mechanism; 601. Cylinder; 602. Stirring bearing; 603. Stirring connecting sleeve; 604. Stirring shaft; 605. Stirring blade; 7. Drive mechanism; 701. Motor; 702. First bevel gear; 703. Second bevel gear; 704. Third bevel gear; 705. Transmission shaft; 8. Lifting mechanism; 801. Lifting bearing; 802. Lifting connecting sleeve; 803. Fixing plate; 804. Drive plate; 805. Vertical plate; 806. Limiting plate; 9. Rotation mechanism. 901. Base; 902. Rotating shaft; 903. Disc 1; 904. Protruding shaft 1; 905. Disc 2; 906. Protruding shaft 2; 907. Connecting rod 1; 908. Disc 3; 909. Connecting rod 2; 910. Disc 4; 10. Ultrasonic generator; 11. First ultrasonic transducer mechanism; 1101. First rotating shaft; 1102. First support; 1103. First ultrasonic transducer; 12. Second ultrasonic transducer mechanism; 1201. Second rotating shaft; 1202. Second support; 1203. Second ultrasonic transducer; 13. Funnel; 14. pH sensor; 15. Electrode plate; 16. Scraper mechanism; 1601. Motor; 1602. Connecting shaft; 1603. Scraper; 17. Support frame. Detailed Implementation

[0042] The present invention will be further described below with reference to the accompanying drawings and embodiments.

[0043] Metal material recycling equipment

[0044] First Embodiment

[0045] Please refer to the following: Figures 1-6 A metal material recycling device includes: a leaching tank 1 placed on the ground by four support frames 17, a top cover 2 fixedly installed on the top of the leaching tank 1, a bottom cover 3 fixedly installed on the bottom of the leaching tank 1, and a funnel 13 connected to the top of the top cover 2;

[0046] The extraction mechanism 5 is connected to the bottom of the bottom cover 3;

[0047] An ultrasonic generator 10 is fixedly installed on the bottom of the bottom cover 3;

[0048] A first ultrasonic transducer mechanism 11 is fixedly installed on the top of the bottom cover 3. The first ultrasonic transducer mechanism 11 includes a first rotating shaft 1101. The two ends of the first rotating shaft 1101 are respectively fixedly installed on the top of the bottom cover 3 through two rotating brackets. A first support 1102 is fixedly installed on the surface of the first rotating shaft 1101. A first ultrasonic transducer 1103 is fixedly installed on the top of the first support 1102.

[0049] The second ultrasonic transducer 12 is fixedly installed on the top of the bottom cover 3. The second ultrasonic transducer 12 includes a second rotating shaft 1201. The two ends of the second rotating shaft 1201 are fixedly installed on the top of the bottom cover 3 by two rotating brackets respectively. A second support 1202 is fixedly installed on the surface of the second rotating shaft 1201, and a second ultrasonic transducer 1203 is fixedly installed on the top of the second support 1202.

[0050] The extraction mechanism 5 includes a water extraction pipe 501, which is connected to the bottom of the bottom cover 3. The bottom end of the water extraction pipe 501 is connected to a water pump 502, which is located on the ground. The output end of the water pump 502 is connected to a drain pipe 503.

[0051] The top of the top cover 2 is connected to an acid replenishment mechanism 4, which includes an acid replenishment pipe 401. The acid replenishment pipe 401 is connected to the top of the top cover 2, and the top end of the acid replenishment pipe 401 is connected to an acid replenishment valve 402.

[0052] In actual use, the acid replenishment valve 402 is connected to an external dilute sulfuric acid solution tank.

[0053] The working principle of the metal material recycling device provided by this invention is as follows:

[0054] First, open the acid replenishment valve 402 and replenish dilute sulfuric acid into the leaching tank 1 through the acid replenishment pipe 401.

[0055] Then, after the dilute sulfuric acid is replenished, the activated lithium slag is manually placed into the dilute sulfuric acid through funnel 13.

[0056] Then, the ultrasonic generator 10 is activated to generate a high-frequency AC signal with a specific frequency, voltage and power. Ultrasonic waves are generated by the first ultrasonic transducer 1103 and the second ultrasonic transducer 1203. The ultrasonic waves generate micro-jets that impact the mineral surface, accelerating the penetration of dilute sulfuric acid solution and ion diffusion.

[0057] Finally, the water pump 502 is started to extract the leachate through the water pumping pipe 501 and discharge it through the drain pipe 503 for subsequent solid-liquid separation.

[0058] Compared with related technologies, the metal material recycling device provided by the present invention has the following beneficial effects:

[0059] By activating the ultrasonic generator 10, power is supplied to the first ultrasonic transducer 1103 and the second ultrasonic transducer 1203 to generate ultrasonic waves. The ultrasonic waves generate micro-jets that impact the mineral surface, accelerating acid penetration and ion diffusion, shortening the leaching time and improving the recovery efficiency. This makes the lithium slag surface less prone to passivation and increases the leaching rate of the target metal ions. A water pump 502 is set up to extract the leachate, which facilitates the next solid-liquid separation process and avoids manual contact with the leachate. Dilute sulfuric acid is first added through the acid replenishment pipe 401 and then the lithium slag is added through the funnel 13 to ensure the consistency and controllability of the leaching reaction startup.

[0060] Second Embodiment

[0061] Please refer to the following: Figures 7-14 Based on the metal material recycling apparatus provided in the first embodiment of this application, the second embodiment of this application proposes another metal material recycling apparatus. The second embodiment is merely a preferred embodiment of the first embodiment, and the implementation of the second embodiment will not affect the separate implementation of the first embodiment.

[0062] Specifically, the metal material recycling device provided in the second embodiment of this application differs in that a stirring mechanism 6 is fixedly installed on the top of the top cover 2. The stirring mechanism 6 includes a cylinder 601, which is fixedly installed on the top of the top cover 2. The output end of the cylinder 601 passes through the top of the top cover 2 and extends into the interior of the leaching tank 1. A stirring connecting sleeve 603 is fixedly installed on the output end of the cylinder 601 through a stirring bearing 602. A stirring shaft 604 is fixedly installed on the bottom of the stirring connecting sleeve 603. Several sets of stirring blades 605 are fixedly installed on the surface of the stirring shaft 604.

[0063] A drive mechanism 7 is fixedly installed on the top of one of the support frames 17. The drive mechanism 7 includes a motor 701, a second bevel gear 703, and a third bevel gear 704. The motor 701 is fixedly installed on the top of one of the support frames 17. The output shaft of the motor 701 is fixedly connected to a transmission shaft 705. One end of the transmission shaft 705 passes through one side of the leaching tank 1 and extends into the interior. A first bevel gear 702 is fixedly installed on the end of the transmission shaft 705 located inside the leaching tank 1. The second bevel gear 703 and the third bevel gear 704 are fixedly installed on the surface of the stirring shaft 604. The first bevel gear 702 meshes with the second bevel gear 703 and the third bevel gear 704.

[0064] A lifting mechanism 8 is fixedly installed on the surface of the stirring shaft 604. The lifting mechanism 8 includes a lifting bearing 801 and a limiting plate 806. The lifting bearing 801 is fixedly installed on the surface of the stirring shaft 604. A fixing plate 803 is fixedly installed on the peripheral side of the lifting bearing 801 through a lifting connecting sleeve 802. A vertical plate 805 is fixedly installed on the bottom end of the fixing plate 803 through a drive plate 804. The limiting plate 806 is fixedly installed on the top of the bottom cover 3. The vertical plate 805 is adapted to the limiting plate 806.

[0065] A rotating mechanism 9 is fixedly installed on the top of the bottom cover 3. The rotating mechanism 9 includes a base 901, which is fixedly installed on the top of the bottom cover 3. A rotating shaft 902 is rotatably installed inside the base 901. A first disk 903 and a second disk 905 are fixedly installed at both ends of the rotating shaft 902, respectively. A first convex shaft 904 is fixedly installed on one side of the first disk 903. The first convex shaft 904 is adapted to the drive plate 804. Two second convex shafts 906 are symmetrically fixedly installed on one side of the second disk 905. One of the second convex shafts 906 is rotatably connected to a third disk 908 through a connecting rod 907. The third disk 908 is fixedly installed at one end of the first rotating shaft 1101. The other second convex shaft 906 is rotatably connected to a fourth disk 910 through a connecting rod 909. The fourth disk 910 is fixedly installed at one end of the second rotating shaft 1201.

[0066] A pH sensor 14 is fixedly installed on the inner wall of the leaching tank 1, and two electrode plates 15 are symmetrically fixedly installed on the inner wall of the leaching tank 1.

[0067] Two scraper mechanisms 16 are symmetrically fixedly installed on one side of the leaching tank 1. Each scraper mechanism 16 includes a motor 1601, which is fixedly installed on one side of the leaching tank 1 via a bracket. The output shaft of the motor 1601 is fixedly connected to a connecting shaft 1602. One end of the connecting shaft 1602 passes through one side of the leaching tank 1 and extends into the interior. A scraper 1603 is fixedly installed at the end of the connecting shaft 1602 located inside the leaching tank 1. The two scrapers 1603 are respectively adapted to and installed with the two electrode plates 15.

[0068] In actual use, one of the two electrode plates 15 serves as the cathode and the other as the anode; the drive mechanism 7, the lifting mechanism 8, and the rotating mechanism 9 are all equipped with outer shells to prevent contact with dilute sulfuric acid.

[0069] The working principle of the metal material recycling device provided in this embodiment is as follows:

[0070] First, after the lithium slag is put into the leaching tank 1, the motor 701 is started. The motor 701 drives the transmission shaft 705 to rotate. The transmission shaft 705 drives the second bevel gear 703 to rotate through the first bevel gear 702. The second bevel gear 703 drives the stirring shaft 604 to rotate forward. The stirring shaft 604 drives the stirring blade 605 to mechanically stir the leaching solution. During the leaching process, mechanical stirring is carried out at 300-500 rpm.

[0071] Then, after stirring for five minutes, the rotation direction is switched to reverse stirring. At this time, the starting cylinder 601 drives the stirring shaft 604 to rise through the stirring bearing 602 and the stirring connecting sleeve 603. At this time, the motor 701 does not work, and the first bevel gear 702 and the second bevel gear 703 disengage. After the cylinder 601 stops rising, the first bevel gear 702 and the third bevel gear 704 engage. The motor 701 is started again, and the stirring shaft 604 drives the stirring blade 605 to reverse stirring.

[0072] Then, as the cylinder 601 drives the stirring shaft 604 to rise, the stirring shaft 604 drives the fixed plate 803 to rise via the lifting bearing 801 and the lifting connecting sleeve 802. The fixed plate 803 drives the drive plate 804 to rise. The vertical rise of the drive plate 804 is limited in the vertical direction by the vertical plate 805 and the limiting plate 806. At this time, the drive plate 804 drives the first cam shaft 904 to rotate. The first cam shaft 904 drives the rotating shaft 902 to rotate via the first disc 903. The rotation of the rotating shaft 902 drives the second disc 905 to rotate. The rotation of the second disc 905 drives the connecting rod 907 and the second connecting rod 909 respectively via the two second cam shafts 906. Linkage 1 907 and Linkage 2 909 respectively drive disk 3 908 and disk 4 910 to rotate. Disk 3 908 and disk 4 910 respectively drive the first rotating shaft 1101 and the second rotating shaft 1201 to rotate in opposite directions. At this time, the first ultrasonic transducer 1103 and the second ultrasonic transducer 1203 rotate in opposite directions, changing from facing the inner wall to facing the middle part of the leaching tank 1. When the stirring shaft 604 drives the first bevel gear 702 and the second bevel gear 703 to mesh again and rotate in the forward direction, the drive plate 804 drives the first ultrasonic transducer 1103 and the second ultrasonic transducer 1203 to rotate in the opposite direction again, resetting and switching back to facing the inner wall.

[0073] Finally, the pH value of the dilute sulfuric acid solution inside the leaching tank 1 is monitored in real time by the pH sensor 14, and the anode and cathode direct current are released through the two electrode plates 15 respectively. When scale forms on the two electrode plates 15 after a period of use, the motor 1601 is started and the scraper 1603 is driven to rotate back and forth through the connecting shaft 1602 to scrape away the impurities.

[0074] Compared with related technologies, the metal material recycling device provided in this embodiment has the following advantages:

[0075] By setting the cylinder 601 to drive the stirring shaft 604 to rise, the first bevel gear 702 is switched to mesh with the second bevel gear 703 and the third bevel gear 704 respectively, switching the rotation direction of the stirring blade 605 to perform forward and reverse stirring, generating turbulent shear force to destroy the passivation layer on the mineral surface and prevent... , , The secondary encapsulation, while avoiding excessively high local acid concentrations, is achieved by a motor 701 driving a first bevel gear 702, which in turn drives a second bevel gear 703 and a third bevel gear 704 to rotate. The stirring shaft 604 then automatically switches the meshing, enabling automatic switching between forward and reverse directions. This avoids the impact of direct reversal on the motor 701 and the transmission structure, reducing mechanical wear. The stirring shaft 604 drives the drive plate 804 to rise and fall, automatically switching the orientation angles of the first ultrasonic transducer 1103 and the second ultrasonic transducer 1203. This allows the direction of action to switch between facing the leaching tank wall and facing the center of the tank, achieving spatial adjustment of the ultrasonic field. This balances the cavitation effect of the tank's edge and center areas, enhancing particle dispersion and surface renewal. The process improves the leaching rate by automatically switching the stirring direction and adjusting the ultrasonic angle through the cylinder 601 and three bevel gears, eliminating the need for manual intervention, reducing operational intensity, and ensuring accurate execution and consistency of process steps. This facilitates standardized process control. The pH sensor 14 monitors in real time and works in conjunction with the DC current applied to the electrode plate 15 to dynamically adjust the chemical environment of the leachate. The electrode plate 15 is driven by the motor 1601 to rotate the scraper 1603 back and forth to remove scale, ensuring the continuous and stable operation of the electrochemical process, preventing process fluctuations caused by electrode failure, maintaining stable reaction conditions, reducing the frequency of manual cleaning, extending electrode life, and avoiding production continuity disruptions due to downtime for cleaning, thus reducing maintenance costs and downtime.

[0076] A method for leaching fluorine, beryllium, thallium, lithium, rubidium, and cesium from lithium slag

[0077] A method for leaching fluorine, beryllium, thallium, lithium, rubidium, and cesium from lithium slag includes the following steps:

[0078] S1: Lithium slag pretreatment and activation: Crush the lithium slag to 80-120 mesh, add it to a microwave reactor, and irradiate it at 2.45 GHz and 600-800 W for 5-10 minutes;

[0079] S2: Ultrasonic-electric field coupled leaching: The activated lithium slag is immersed in dilute sulfuric acid at pH 2.0-2.5, and ultrasonic waves of 20-40kHz are applied with a power density of 50-100W / L and a DC electric field voltage of 5-10V. The anode is a titanium-plated ruthenium electrode.

[0080] S3: Mechanical field enhanced mass transfer: During the leaching process, mechanical stirring is performed at 300-500 rpm, and the stirring direction is changed periodically every 5 minutes;

[0081] S4: Solid-liquid separation and neutralization: After pressure filtration, the leachate is neutralized to pH 7-8 with lime milk to solidify fluorine, beryllium, and thallium; the filtrate is enriched by ion exchange resin. , , .

[0082] In practical use, in S1, the microwave thermal effect causes the polar molecules within the mineral lattice (such as the Si-O bonds in silicate structures) to vibrate violently, generating microcracks, disrupting the stable structures of fluorapatite, beryl, etc., and releasing... , , The active sites; in S2, ultrasonic cavitation effect: generates micro-jets to impact the mineral surface, accelerating acid penetration and ion diffusion; electric field driven: anodic oxidation reaction ( Maintaining the acidity of the system, the cathodic reduction reaction ( Prevent heavy metals (such as Deposition at the cathode; selective inhibition: and generate precipitation( ), Hydrolyzes to at pH>2 ( ),Tl + Migrating to the cathode region by the electric field and reduced to ( In step S3, turbulent shear force destroys the passivation layer on the mineral surface, preventing... , , The secondary encapsulation simultaneously prevents excessively high local acid concentrations from causing harmful elements to dissolve; in S4, the reaction is: neutralization: Thallium curing: .

[0083] First Embodiment

[0084] Leaching from sulfuric acid system

[0085] Raw materials: Lithium mica residue (Li 0.8%, Rb 0.2%, Cs 0.1%, F 3.5%, Be 0.05%, Tl 0.01%).

[0086] Procedure: After microwave activation (700W, 8 minutes), add pH 2.3. The solution (liquid-solid ratio 5:1) was subjected to 30kHz ultrasound (80W / L) and an 8V electric field, stirred at 400rpm, and leached for 2 hours.

[0087] Results: The leaching rates of Li, Rb, and Cs were 92.1%, 85.6%, and 78.3%, respectively, while the leaching rates of F, Be, and Tl were only 3.2%, 1.8%, and 0.5%, respectively.

[0088] Second Embodiment

[0089] Leaching in hydrochloric acid system

[0090] Raw materials: Lithium spodumene slag (Li 1.2%, Rb 0.15%, Cs 0.08%, F 2.8%, Be 0.03%, Tl 0.005%).

[0091] Procedure: After microwave activation (650W, 10 minutes), add pH 2.0. The solution (liquid-solid ratio 4:1) was subjected to 25kHz ultrasound (60W / L) and a 6V electric field, stirred at 350rpm, and leached for 1.5 hours.

[0092] Results: The leaching rates of Li, Rb, and Cs were 94.5%, 88.2%, and 80.1%, respectively, while the leaching rates of F, Be, and Tl were only 2.7%, 1.2%, and 0.3%, respectively.

[0093] Compared with related technologies, the leaching method for fluorine, beryllium, thallium, lithium, rubidium, and cesium in lithium slag provided by this invention has the following beneficial effects:

[0094] Multi-field synergistic mechanism: microwave pre-activation + ultrasonic-electric field in-situ regulation to achieve enhanced mineral dissociation and reaction kinetics; low-acid directional leaching: through precise pH / Eh control, selective dissolution of Li / Rb / Cs is achieved, inhibiting the leaching of harmful elements; environmental protection and economy: acid consumption is reduced by 40%, and the amount of harmful solid waste is reduced by 90%, making it suitable for industrial promotion.

[0095] The above description is merely an embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural or procedural transformations made based on the content of the present invention specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the patent protection scope of the present invention.

Claims

1. A metal material recycling device characterized by comprising: The utility model provides an improved leaching tank, which comprises a leaching tank placed on the ground by four supporting frames, a top cover fixedly installed on the top of the leaching tank, a bottom cover fixedly installed on the bottom of the leaching tank, a funnel communicated with the top of the top cover, an extraction mechanism communicated with the bottom of the bottom cover, an ultrasonic generator fixedly installed on the bottom of the bottom cover, a first ultrasonic transducer mechanism fixedly installed on the top of the bottom cover, a second ultrasonic transducer mechanism fixedly installed on the top of the bottom cover, the extraction mechanism comprising a water pumping pipe communicated with the bottom of the bottom cover, a water pump communicated with the bottom end of the water pumping pipe, a drain pipe communicated with the output end of the water pump, the top of the top cover being communicated with an acid supplement mechanism comprising an acid supplement pipe communicated with the top of the top cover, the top end of the acid supplement pipe being communicated with an acid supplement valve, the top of the top cover being fixedly installed with a stirring mechanism comprising a gas cylinder fixedly installed on the top of the top cover, the output end of the gas cylinder penetrating through the top of the top cover and extending into the leaching tank, the output end of the gas cylinder being fixedly installed with a stirring connecting sleeve through a stirring bearing, the bottom of the stirring connecting sleeve being fixedly installed with a stirring shaft, the surface of the stirring shaft being fixedly installed with a plurality of groups of stirring blades, the top of one of the supporting frames being fixedly installed with a driving mechanism comprising a motor, a second bevel gear and a third bevel gear, the output shaft of the motor being fixedly connected with a transmission shaft, one end of the transmission shaft penetrating through one side of the leaching tank and extending into the leaching tank, the first bevel gear being fixedly installed on the end of the transmission shaft inside the leaching tank, the second bevel gear and the third bevel gear being fixedly installed on the surface of the stirring shaft, the first bevel gear being engaged with the second bevel gear and the third bevel gear, the surface of the stirring shaft being fixedly installed with a lifting mechanism comprising a lifting bearing and a limiting plate, the lifting bearing being fixedly installed on the surface of the stirring shaft, the circumferential surface of the lifting bearing being fixedly installed with a fixed plate through a lifting connecting sleeve, the bottom end of the fixed plate being fixedly installed with a vertical plate through a driving plate, the limiting plate being fixedly installed on the top of the bottom cover, the vertical plate being installed in fit with the limiting plate. ​ ​ ​ ​ ​ 2. The metal material recycling apparatus according to claim 1, characterized by ​ 3. The metal material recycling apparatus according to claim 1, characterized by ​ 4. The metal material recycling apparatus according to claim 1, characterized by ​ 5. The metal material recycling apparatus according to claim 4, characterized by ​ 6. The metal material recycling apparatus according to claim 4, characterized by ​ 7. The metal material recycling apparatus according to claim 6, characterized by The top of the bottom cover is fixedly installed with a rotating mechanism, the rotating mechanism comprises a base, the base is fixedly installed on the top of the bottom cover, a rotating shaft is rotatably installed in the base, disc one and disc two are fixedly installed on both ends of the rotating shaft, a convex shaft one is fixedly installed on one side of the disc one, the convex shaft one is installed in the driving plate, two convex shaft twos are fixedly installed on one side of the disc two in pairs, one of the convex shaft twos is rotatably connected with disc three through connecting rod one, the disc three is fixedly installed on one end of the first rotating shaft, the other convex shaft two is rotatably connected with disc four through connecting rod two, and the disc four is fixedly installed on one end of the second rotating shaft.

8. The metal material recycling apparatus according to claim 1, characterized by The inner wall of the leaching tank is fixedly installed with a pH sensor, and two electrode plates are fixedly installed on the inner wall of the leaching tank in pairs.

9. The metal material recycling apparatus according to claim 8, characterized by Two scraper mechanisms are fixedly installed on one side of the leaching tank in pairs, the scraper mechanism comprises a motor, the motor is fixedly installed on one side of the leaching tank through a support, the output shaft of the motor is fixedly connected with a connecting shaft, one end of the connecting shaft penetrates through one side of the leaching tank and extends into the interior, and a scraper is fixedly installed on one end of the connecting shaft in the leaching tank, and two scrapers are installed in the driving plate in pairs.

10. A method for leaching fluorine beryllium thallium and lithium rubidium cesium in lithium slag, wherein the metal material recycling device according to any one of claims 1-9 is required to be used, characterized in that, The method comprises the following steps: S1: lithium slag pretreatment and activation: the lithium slag is crushed to 80-120 mesh, and is added into a microwave reactor, and is irradiated at 2.45GHz and 600-800W for 5-10 minutes; S2: ultrasonic-electric field coupling leaching: the activated lithium slag is immersed in dilute sulfuric acid, the pH is 2.0-2.5, 20-40kHz ultrasonic waves are applied, the power density is 50-100W / L, and the direct current electric field voltage is 5-10V, and the titanium plating ruthenium electrode is used as the anode; S3: mechanical field strengthening mass transfer: mechanical stirring is carried out at 300-500rpm during the leaching process, and the stirring direction is periodically switched every 5 minutes; S4: solid-liquid separation and neutralization: after the leaching solution is separated by pressure filtration, the filter residue is neutralized to pH 7-8 with lime milk to solidify fluorine, beryllium and thallium; the filtrate is enriched by ion exchange resin 、 、 .

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