Extraction equipment for recycling waste lithium batteries to prepare manganese sulfate

Abstract

The present application relates to the technical field of extraction equipment, and discloses an extraction equipment for recycling waste lithium batteries to prepare manganese sulfate, which comprises an extraction tank body provided with a cover plate at the upper end, the inner wall of the extraction tank body is divided into three single-stage chambers by grading partition plates arranged in front and back symmetry, and two baffle plates arranged in up-down staggered distribution are installed on one side of the inner wall of the single-stage chamber along the length direction of the single-stage chamber. The extraction equipment for recycling waste lithium batteries to prepare manganese sulfate can effectively solve the problems in the prior art that, when the mixed clarifying tank processes the leaching solution of waste lithium batteries, a single radial flow stirring paddle is used, the shearing is uneven, the mixing efficiency is low, the two-phase dispersion is poor and the particle size is wide, there is a lack of precise milk control mechanism, it is difficult to balance mixing and emulsification, the colloids and organic impurities in the leaching solution can form a dense protective film and a stable emulsion system, the clarifying chamber only relies on gravity sedimentation and has no demulsification means, the clarification is slow and the entrainment is heavy, the extractant is wasted and manganese is lost, the cost is increased, and the product purity is affected.

Description

Technical Field

[0001] This invention relates to the field of extraction equipment technology, specifically to an extraction device for the preparation of manganese sulfate from the recycling of waste lithium batteries. Background Technology

[0002] Manganese sulfate is a key raw material for preparing cathode materials for lithium-ion batteries. Recovering high-purity manganese sulfate from waste lithium batteries not only solves environmental pollution problems but also alleviates the shortage of manganese ore resources, achieving resource recycling. Among various preparation methods, solvent extraction has become the only mainstream industrial technology due to its excellent separation performance. The mixing and clarification tank is currently the mainstream extraction equipment in the manganese sulfate extraction process from waste lithium batteries. Its simple structure, high operational flexibility, and strong resistance to impurities make it suitable for the complex composition of the leachate. The typical working mode of the mixing and clarification tank is as follows: in the mixing chamber, mechanical stirring ensures full contact between the manganese-containing aqueous phase and the extractant, achieving selective extraction of manganese ions. Subsequently, the two phases enter the clarification chamber, where gravity naturally separates the phases, completing phase separation.

[0003] To address this issue, this application designs an extraction device for preparing manganese sulfate from recycled waste lithium batteries. Existing mixing and clarification tanks typically use a single radial flow stirring impeller to achieve two-phase mixing when processing leachate from waste lithium batteries. This method suffers from drawbacks such as uneven shear force distribution, low mixing efficiency, insufficient dispersion of the liquid and liquid phases, and a wide particle size distribution. Furthermore, it lacks a precise source-level emulsification control mechanism. Excessive stirring speed can lead to localized over-emulsification, forming a large number of difficult-to-separate nanoscale stable microemulsions. Conversely, insufficient stirring speed cannot guarantee the contact area required for mass transfer, making it difficult to achieve a balance between mixing efficiency and emulsification degree. Furthermore, the sulfuric acid leachate from waste lithium batteries contains a large amount of ferric hydroxide, aluminosilicate colloidal particles, and organic decomposition products. These impurities adsorb onto the surface of microdroplets to form a dense colloidal protective film, constructing a stable emulsion system and a third phase. Existing clarification chambers rely solely on gravity sedimentation for phase separation, lacking targeted demulsification methods and failing to disrupt the colloidal protective film structure, resulting in a long clarification time. At the same time, the entrainment of the two phases is prominent, leading to a large loss of extractant and the loss of manganese resources with the raffinate aqueous phase. This not only significantly increases operating costs but also affects the purity of the final manganese sulfate product. Summary of the Invention

[0004] To address the aforementioned shortcomings of existing technologies, this invention provides an extraction device for preparing manganese sulfate from recycled waste lithium batteries. This device effectively solves the problems of existing technologies where, in the mixing and clarification tank for treating waste lithium battery leachate, a single radial flow stirring paddle is used, resulting in uneven shearing, low mixing efficiency, poor two-phase dispersion with wide particle sizes, and a lack of precise emulsification control mechanisms, making it difficult to balance mixing and emulsification. Furthermore, colloidal and organic impurities in the leachate form a dense protective film and a stable emulsion system, while the clarification chamber relies solely on gravity settling without demulsification, leading to slow clarification, heavy entrainment, extractant loss, manganese loss, increased costs, and reduced product purity.

[0005] To achieve the above objectives, the present invention provides the following technical solution: This invention provides an extraction device for preparing manganese sulfate from waste lithium batteries, comprising: The extraction tank is equipped with a cover plate at the top. The inner wall of the extraction tank is divided into three single-stage chambers by a series of symmetrically distributed partitions. Two baffles are installed on one side of the inner wall of each single-stage chamber along its length. A T-shaped weir is installed on the side of the inner wall of each single-stage chamber away from the baffles. The baffles and T-shaped weirs in two adjacent single-stage chambers are arranged in opposite directions. A stirring and mixing section is provided on both the single-stage chambers and the cover plate. A microemulsion control section is provided on both the single-stage chambers and the stirring and mixing section. The mixing section includes a rotating shaft that is rotatably installed at the upper end of the cover plate. An axial flow airfoil blade is fixedly sleeved on the lower end of the outer wall of the rotating shaft. A servo motor for driving the rotating shaft to rotate is installed at the upper end of the cover plate. The microemulsion control unit includes orifice plates symmetrically installed on the inner wall of the single-stage chamber. Several rectangularly evenly distributed limiting rods are installed on the opposite ends of the two orifice plates. Several linearly evenly distributed guide plates are obliquely slidably sleeved on the outer wall of the limiting rods. The guide plates are composed of two detachable rectangular plates. Low-frequency vibration groups are set together on the baffle plate and the T-shaped weir plate.

[0006] Furthermore, the mixing section also includes a connecting frame installed on the inner wall of the single-stage chamber and on the baffle plate on the lower side. The connecting frame consists of several circumferentially distributed extension rods and annular sleeves. A guide tube is installed on the inner wall of the annular sleeve. Both the upper and lower ends of the guide tube are gradually expanding inlets, and spiral guide vanes are installed on the inner wall of the guide tube.

[0007] Furthermore, the microemulsion control unit also includes a receiving groove located at the opposite ends of two rectangular plates on the guide plate. The receiving groove has two openings, one upper and one lower. A positioning strip is slidably installed on the inner wall of the receiving groove. The positioning strip is also fixedly sleeved on the outer wall of the corresponding two limit rods. The two ends of the positioning strip are respectively connected to the inner wall of the corresponding receiving groove by compression springs. Several corrugated grooves with linear and uniform distribution are opened on both ends of the guide plate.

[0008] Furthermore, the low-frequency vibration assembly includes a positioning tube symmetrically rotated and installed through the T-shaped weir plate, and a support rod symmetrically rotated and installed through the upper baffle plate. The support rod has a stepped shaft structure, with the outer wall of the smaller diameter section of the support rod slidably connected to the inner wall of the corresponding positioning tube. The larger diameter section of the support rod is connected to the positioning tube by a compression spring. A docking plate is installed at the end of the two support rods near the rotating shaft. The docking plate has an arc-shaped structure. A mounting plate is fixedly fitted on the outer wall of the rotating shaft corresponding to the docking plate. Two sets of contact balls with different diameters are staggered on the outer wall of the mounting plate. Each set of contact balls consists of several contact balls evenly distributed in a circle.

[0009] Furthermore, the low-frequency vibration group also includes a support sleeve plate that is fixedly sleeved on the outer wall of the front and rear support rods. The lower end of the support sleeve plate is equipped with a connecting seat corresponding to several guide plates. The lower end of the connecting seat is equipped with several linearly and evenly distributed hammer rods, and the lower end of the hammer rods moves against the corresponding guide plates.

[0010] Furthermore, the two baffles are staggered left and right. The baffle on the lower side is T-shaped, and the baffle on the upper side is rectangular. The lower baffle and the inner wall of the single-stage chamber are both equipped with a submerged chamber baffle, which is also T-shaped. The upper end of the horizontal section of the submerged chamber baffle has fan-shaped holes symmetrically opened at the front and back of the vertical section. The T-shaped weir plate is composed of a rectangular partition plate, a light phase weir, and a heavy phase weir. The upper end of the light phase weir has a toothed structure.

[0011] Furthermore, a heavy phase collection pipe is installed on the inner wall of the single-stage chamber on the side of the heavy phase weir corresponding to the T-shaped weir plate. An adjustment pipe is installed inside the heavy phase collection pipe. The adjustment pipe consists of a threaded section and a stepped shaft section. The threaded section of the adjustment pipe is threadedly connected to the cover plate. The outer wall of the larger diameter end of the stepped shaft section is movably attached to the inner wall of the heavy phase collection pipe. The outer wall of the stepped shaft section is symmetrically provided with flow ports at the top and bottom.

[0012] Furthermore, through holes are symmetrically opened on the vertical section of the submersible partition corresponding to the single-stage chamber inner wall, and through holes are opened on the light phase weir and heavy phase weir corresponding to the T-shaped weir plate on the single-stage chamber inner wall, and the regulating pipe is connected to the through hole of the corresponding heavy phase weir.

[0013] Furthermore, each of the front and rear single-stage chambers is equipped with an input pipe at its lower end. The input pipe is connected to one of the through holes in the corresponding submersible chamber partition. In the front single-stage chamber, the through hole corresponding to the heavy phase weir on the T-shaped weir plate is connected to an output pipe. In the rear single-stage chamber, the through hole corresponding to the light phase weir on the T-shaped weir plate is also connected to an output pipe. The remaining through holes in the two adjacent single-stage chambers are connected by a connecting pipe.

[0014] The technical solution provided by this invention has the following advantages compared with the prior art: This invention provides an extraction device for preparing manganese sulfate from recycled waste lithium batteries. In the enhanced mixing and source emulsification stage, an axial circulation enhanced mixing mechanism is formed by axial airfoil blades, a guide tube, and spiral guide vanes. The two-phase fluid is drawn in from the gradually expanding inlet at the lower end of the guide tube and discharged from the gradually expanding outlet at the upper end after being uniformly sheared by the spiral guide vanes, forming an up-and-down circulating flow. In the swirl elimination and low-frequency pre-demulsification stage, the swirling turbulence at the mixing chamber outlet is converted into a uniform laminar flow by a swirl elimination orifice plate near the mixing chamber. The rotating shaft drives two sets of contact balls of different diameters, which are staggered on the mounting plate, to strike the docking plate in sequence, pushing the two support rods in front and behind to make linear reciprocating motion, causing the hammer rod to intermittently strike the guide plate to generate low-frequency small-amplitude vibration. This application achieves efficient dispersion of two phases and precise control of emulsification through the above steps, reducing the difficulty of subsequent separation from the source, while avoiding the generation of secondary emulsification. It also specifically destroys the colloidal protective film on the surface of microdroplets, transforming stable microemulsions into free droplets that are easy to aggregate, effectively improving the efficiency of single-stage extraction and shortening the clarification time.

[0015] In the microemulsion coalescence and serpentine flow channel separation stage, a serpentine flow channel is formed by two baffles, several inclined guide plates, and two orifice plates arranged in an alternating manner. This forces the two-phase fluids to flow slowly along a preset path. Utilizing the guide plates with adsorption affinity for light phase droplets, the exposed large light phase droplets spread and coalesce in the corrugated groove to form a continuous light phase liquid film. In the fine separation and continuous extraction stage, a T-shaped weir plate divides the rear half of the single-stage chamber into a light phase collection area and a heavy phase collection area. The light phase overflows uniformly into the light phase collection area through the toothed structure at the upper end of the light phase weir, while the heavy phase smoothly enters the heavy phase collection area through the rectangular flow port on the lower side of the heavy phase weir. The two-phase fluids are transported countercurrently between adjacent single-stage chambers through a connecting pipe. Through the above steps, this application can effectively avoid fluid short-circuiting, prolong the residence time of the two phases in the clarification zone, significantly increase the droplet coalescence rate, and simultaneously achieve precise separation and continuous countercurrent extraction of the two phases, reducing the two-phase entrainment rate. Attached Figure Description

[0016] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without any creative effort.

[0017] Figure 1 This is a first-view three-dimensional structural diagram in an embodiment of the present invention; Figure 2 This is a schematic diagram of the second-view three-dimensional structure in an embodiment of the present invention; Figure 3This is a schematic diagram of a partial three-dimensional cross-section of the extraction tank in an embodiment of the present invention; Figure 4 This is a three-dimensional structural diagram of the stirring and mixing section and the microemulsion control section in an embodiment of the present invention; Figure 5 This is a top view schematic diagram of the extraction tank and grading partition in an embodiment of the present invention; Figure 6 This is a schematic diagram of a partial three-dimensional cross-section of the T-shaped weir plate, the heavy phase collection pipe, and the regulating pipe in an embodiment of the present invention; Figure 7 This is a schematic diagram showing the three-dimensional separation of the submersible partition, the mixing section, and the microemulsion control section in an embodiment of the present invention; Figure 8 This is a schematic diagram of a three-dimensional partial cross-section of the microemulsion control unit in an embodiment of the present invention; Figure 9 This is a schematic diagram of the three-dimensional separation of the guide plate and the positioning strip in an embodiment of the present invention; Figure 10 This is a schematic diagram of the three-dimensional separation of the low-frequency vibration group in an embodiment of the present invention; Figure 11 This is a top view schematic diagram of the docking plate and mounting plate in an embodiment of the present invention.

[0018] The labels in the diagram represent: 1. Extraction tank; 11. Cover plate; 2. Classification baffle; 21. Baffle plate; 22. Submerged chamber baffle; 23. T-shaped weir plate; 24. Heavy phase collection pipe; 25. Regulating pipe; 26. Through hole; 27. Connecting pipe; 28. Input pipe; 29. ​​Output pipe; 3. Stirring and mixing section; 31. Rotating shaft; 32. Axial flow airfoil blade; 33. Connecting frame; 34. Guide tube; 35. 36. Spiral guide vane; 4. Servo motor; 5. Microemulsion control unit; 6. Orifice plate; 7. Limiting rod; 8. Guide plate; 9. Receiving groove; 10. Positioning strip; 11. Corrugated groove; 12. Low-frequency vibration group; 13. Positioning tube; 14. Support rod; 15. Connecting plate; 16. Mounting plate; 17. Contact ball; 18. Supporting sleeve; 19. Connecting seat; 20. Striking hammer rod. Detailed Implementation

[0019] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.

[0020] The present invention will be further described below with reference to embodiments.

[0021] Example: Please see Figures 1-11 This invention provides a technical solution: an extraction device for preparing manganese sulfate from waste lithium batteries, comprising: An extraction tank 1 with a cover plate 11 installed at the top is divided into three single-stage chambers by a symmetrically distributed partition plate 2 on the inner wall of the extraction tank 1. Two baffles 21 with alternating vertical distribution are installed on one side of the inner wall of the single-stage chamber along its length direction. A T-shaped weir plate 23 is installed on the side of the inner wall of the single-stage chamber away from the baffles 21. The baffles 21 and T-shaped weir plates 23 in two adjacent single-stage chambers are arranged with opposite orientations. A stirring and mixing section 3 is provided on both the single-stage chamber and the cover plate 11. A microemulsion control section 4 is provided on both the single-stage chamber and the stirring and mixing section 3. The mixing section 3 includes a rotating shaft 31 that is rotatably installed on the upper end of the cover plate 11. An axial flow airfoil blade 32 is fixedly sleeved on the lower end of the outer wall of the rotating shaft 31. A servo motor 36 for driving the rotating shaft 31 to rotate is installed on the upper end of the cover plate 11. The microemulsion control unit 4 includes perforated plates 41 symmetrically installed on the inner wall of the single-stage chamber. Several rectangularly evenly distributed limiting rods 42 are installed on the opposite ends of the two perforated plates 41. Several linearly evenly distributed guide plates 43 are obliquely slidably sleeved on the outer wall of the limiting rods 42. The guide plates 43 are composed of two detachable rectangular plates. Low-frequency vibration groups 47 are jointly provided on the baffle plate 21 and the T-shaped weir plate 23.

[0022] The mixing section 3 also includes a connecting frame 33 installed on the inner wall of the single-stage chamber and on the baffle plate 21 located on the lower side. The connecting frame 33 consists of several circumferentially distributed extension rods and annular sleeves. A guide tube 34 is installed on the inner wall of the annular sleeve. Both the upper and lower ends of the guide tube 34 are gradually expanding inlet ports, and a spiral guide vane 35 is installed on the inner wall of the guide tube 34.

[0023] The microemulsion control unit 4 also includes a receiving groove 44 located on the opposite ends of two rectangular plates on the guide plate 43. The receiving groove 44 has two openings, one upper and one lower. A positioning strip 45 is slidably installed on the inner wall of the receiving groove 44. The positioning strip 45 is also fixedly sleeved on the outer wall of the corresponding two limiting rods 42. The two ends of the positioning strip 45 are respectively connected to the inner wall of the corresponding receiving groove 44 by compression springs. Several corrugated grooves 46 are linearly and evenly distributed on both ends of the guide plate 43.

[0024] The low-frequency vibration group 47 includes a positioning tube 471 that is symmetrically rotated and installed on the T-shaped weir plate 23. A support rod 472 is symmetrically rotated and installed on the baffle plate 21 on the upper side. The support rod 472 has a stepped shaft structure. The outer wall of the smaller diameter section of the support rod 472 is slidably connected to the inner wall of the corresponding positioning tube 471. The larger diameter section of the support rod 472 is connected to the positioning tube 471 by a compression spring. The two support rods 472 are connected to a docking plate 473 at one end near the rotating shaft 31. The docking plate 473 has an arc-shaped structure. A mounting plate 474 is fixedly sleeved on the outer wall of the rotating shaft 31 corresponding to the docking plate 473. Two sets of contact balls 475 with different diameters are staggered on the outer wall of the mounting plate 474. Each set of contact balls 475 consists of several contact balls 475 evenly distributed in a circle.

[0025] The low-frequency vibration group 47 also includes a support sleeve 476 that is fixedly sleeved on the outer wall of the front and rear support rods 472. The lower end of the support sleeve 476 is equipped with a connecting seat 477 corresponding to several guide plates 43. The lower end of the connecting seat 477 is equipped with several linearly and evenly distributed hammer rods 478. The lower end of the hammer rods 478 moves against the corresponding guide plate 43.

[0026] The two baffles 21 are also staggered from left to right. The baffle 21 on the lower side is T-shaped and the baffle 21 on the upper side is rectangular. The lower baffle 21 and the inner wall of the single-stage chamber are both equipped with a submerged chamber baffle 22. The submerged chamber baffle 22 is also T-shaped. The upper end of the horizontal section of the submerged chamber baffle 22 is symmetrically provided with fan-shaped holes corresponding to the front and rear of the vertical section. The T-shaped weir plate 23 is composed of a rectangular partition plate, a light phase weir and a heavy phase weir. The upper end of the light phase weir has a toothed structure.

[0027] A heavy phase collection pipe 24 is installed on the inner wall of the single-stage chamber, corresponding to the side of the heavy phase weir on the T-shaped weir plate 23. An adjustment pipe 25 is installed inside the heavy phase collection pipe 24. The adjustment pipe 25 consists of a threaded section and a stepped shaft section. The threaded section of the adjustment pipe 25 is threadedly connected to the cover plate 11. The outer wall of the larger diameter end of the stepped shaft section is movably attached to the inner wall of the heavy phase collection pipe 24, and flow ports are symmetrically opened on the upper and lower parts of the outer wall of the stepped shaft section.

[0028] The single-stage chamber has through holes 26 symmetrically opened at the front and back of the vertical section corresponding to the submersible partition 22 on the inner wall. The light phase weir and heavy phase weir corresponding to the T-shaped weir plate 23 on the inner wall of the single-stage chamber also have through holes 26, and the regulating pipe 25 is connected to the through hole 26 of the corresponding heavy phase weir.

[0029] Both the front and rear single-stage chambers are equipped with input pipes at their lower ends. The input pipes are connected to one of the through holes in the corresponding submersible chamber partition. In the front single-stage chamber, the through hole 26 corresponding to the heavy phase weir on the T-shaped weir plate 23 is connected to the output pipe 29. In the rear single-stage chamber, the through hole 26 corresponding to the light phase weir on the T-shaped weir plate 23 is also connected to the output pipe 29. The remaining through holes 26 in the two adjacent single-stage chambers are connected by the connecting pipe 27.

[0030] In practice: First, the three single-stage chambers in this application are sequentially connected to form a three-stage countercurrent extraction structure. For ease of description, each single-stage chamber is precisely divided into two independent functional areas—a mixing chamber and a clarification chamber—by internal partitions according to the liquid-liquid extraction process logic. The mixing chamber is located in the front half of the single-stage chamber and is formed by the inner wall of the single-stage chamber, the staged partition 2, the upper rectangular baffle 21, the lower T-shaped baffle 21, and the submerged chamber partition 22. Its core function is to achieve efficient dispersion and thorough mixing and mass transfer of the heavy and light phases. The clarification chamber is located in the single-stage chamber. The rear half of the chamber is formed by the inner wall of the single-stage chamber, the stage partition 2, the upper rectangular baffle 21, and the T-shaped weir 23. Its core function is to achieve gravity separation and phase clarification of the two phases after mixing. In addition, the T-shaped weir 23 can divide the rear half of the single-stage chamber into a light phase collection area and a heavy phase collection area. The light phase collection area is used to collect the load light phase, and its bottom inner wall is provided with a through hole 26 that is connected to the connecting pipe 27 or the output pipe 29. The heavy phase collection area is used to collect the raffinate heavy phase, and its outlet is directly and sealed to the heavy phase collection pipe 24.

[0031] The stirring and mixing section 3 is used to achieve efficient dispersion and uniform mixing of the heavy and light phases, providing sufficient and controllable contact area for manganese ion extraction and mass transfer. It can control emulsification at the source by adjusting the shear force, avoiding excessive emulsification that would significantly increase the difficulty of subsequent separation. The microemulsion control section 4 is used to perform microdroplet polymerization and coarse separation on the mixed two-phase fluid. It works in conjunction with the low-frequency vibration group 47 to achieve pre-demulsification of stable microemulsions. In addition, the low-frequency vibration group 47 can specifically destroy the colloidal protective film on the surface of microdroplets, fundamentally solving the industry problem of stable emulsification caused by colloidal particles in waste lithium battery leachate.

[0032] It is worth emphasizing that the low-frequency vibration group 47 adopts a purely mechanical linkage structure. When the rotating shaft 31 drives the mounting plate 474 to rotate synchronously, the two sets of abutting balls 475 of different diameters arranged alternately on the mounting plate 474 will hit the corresponding docking plate 473 in sequence, pushing the two front and rear support rods 472 to make linear reciprocating motion. Then, through the striking hammer rod 478, the guide plate 43 is intermittently struck, causing the guide plate 43 to generate low-frequency small-amplitude vibration. At the same time, it will not cause the polymerized droplets to break up again, and effectively destroys the colloidal protective film on the surface of the microdroplets, so as to achieve the pre-demulsification of stable microemulsion.

[0033] Based on the processing volume of the waste lithium battery leachate, the manganese ion concentration, and the extraction process requirements, the initial heavy phase liquid level of each stage chamber needs to be adjusted through the regulating pipe 25 to maintain the initial position of the two-phase interface in each clarification zone at a suitable height. It should be noted that the axial airfoil blades 32, the guide tube 34, and the spiral guide blades 35 in the stirring and mixing section 3 can jointly form an axial circulation enhanced mixing mechanism. Whenever the servo motor 36 drives the rotating shaft 31 to rotate, the rotating shaft 31 will drive the axial airfoil blades 32 to rotate synchronously to generate a strong axial flow, which draws the two-phase fluid from the gradually expanding inlet at the lower end of the guide tube 34, and discharges it from the gradually expanding outlet at the upper end after being uniformly sheared by the spiral guide blades 35, forming an up-and-down circulating flow. Compared with the traditional radial flow stirring impeller, this effectively improves the two-phase mixing efficiency and the shear force distribution is more uniform, which can effectively avoid the generation of a large number of difficult-to-separate nanoscale microemulsions due to local over-emulsification.

[0034] It should also be noted that the orifice plate 41 and the guide plate 43 can together form a swirling elimination-coalescence separation mechanism. The orifice plate 41 near the mixing chamber is a swirling elimination orifice plate 41, which can convert the swirling turbulence at the mixing chamber outlet into a uniform laminar flow, avoiding secondary emulsification. The guide plate 43 is made of polypropylene, which has excellent adsorption affinity for organic phase droplets. The corrugated grooves 46 on its two end faces can increase the contact area between the droplets and the end faces of the guide plate 43, promoting the collision and coalescence of small droplets. Furthermore, the two baffles 21, several inclined guide plates 43, and two orifice plates 41 are arranged in an alternating manner to form a serpentine flow channel, which can force the two-phase fluid to flow slowly along a preset path, effectively avoiding short-circuiting and prolonging the residence time of the fluid in the clarification zone.

[0035] In the initial state, several servo motors 36 are all in a stopped state, several regulating pipes 25 in several single-stage chambers are all at a preset initial height, and the valves on the through holes 26, connecting pipes 27, input pipes 28, and output pipes 29 are all in a closed state; several guide plates 43 are in an initial equilibrium position under the action of compression springs, and the lower end of the hammer rod 478 maintains slight contact with the upper end face of the corresponding guide plate 43; the compression springs on the positioning tube 471 and the support rod 472 are in a natural extension and contraction state, and the outer wall of the smaller diameter section of the support rod 472 always maintains the same height as the inner wall of the positioning tube 471. The shaft is in a sliding fit state, and the mating plate 473 and the smallest diameter contact ball 475 on the mounting plate 474 maintain slight contact. At the same time, the external feed pump and extractant pump are both stopped, and several single-stage chambers are empty. There is no fluid overflow in the light phase weir and heavy phase weir of the T-shaped weir plate 23, and there is no two-phase interface in the clarification zone. It should be noted that the guide plate 43 adopts a detachable structure. The guide plate 43 with different surface modification materials and corrugated groove 46 parameters can be replaced according to the properties and emulsification degree of the feed liquid to be treated, so as to further optimize the separation effect and facilitate cleaning and maintenance.

[0036] In the counter-current feeding stage, the valves on the input pipe 28, connecting pipe 27, and output pipe 29 are opened sequentially. Simultaneously, several servo motors 36 are activated, causing the rotating shaft 31 to drive the axial-flow airfoil blades 32 to rotate at a uniform speed. Next, the external feed pump is activated to pump the pretreated waste lithium battery sulfuric acid leachate (heavy phase) through the input pipe 28 of the front single-stage chamber into the submerged chamber partition 22 of the first-stage single-stage chamber. Simultaneously, the external extractant pump is activated to pump the extractant (light phase) through the input pipe 28 of the rear single-stage chamber into the submerged chamber partition 22 of the third-stage single-stage chamber. During this process… The heavy phase will flow from the first stage to the third stage, and the light phase will flow from the third stage to the first stage, forming a three-stage countercurrent extraction system. This continues until the liquid levels in several single-stage chambers rise to a preset height and the interface between the two phases stabilizes at a suitable height, completing the equipment's feeding preparation. During the feeding process, the feed fluid will first enter the submerged chamber for buffering to avoid direct impact on the stirring area and cause liquid surface fluctuations, ensuring the stability of the two-phase feed. The lower baffle 21 and the submerged chamber partition 22 work together to form an independent feed buffer space, effectively preventing the occurrence of feed short circuits and ensuring that the two-phase fluids can all enter the mixing chamber for thorough mixing.

[0037] In the enhanced mixing and source control stage, the two-phase fluid entering the single-stage chamber will first flow into the mixing chamber through the corresponding fan-shaped hole at the upper end of the submerged chamber partition 22 under the strong axial flow generated by the synchronous rotation of the axial airfoil blade 32 and the rotating shaft 31. Then, it will be drawn into the guide tube 34 through the gradually expanding inlet at the lower end of the guide tube 34. As the two-phase fluid flows upward in the guide tube 34, it will collide and shear with the helical guide vanes 35 to disperse it. The dispersed two-phase fluid will continue to be discharged from the gradually expanding outlet at the upper end of the guide tube 34. A portion of the two-phase fluid will form an up-and-down circulating flow under the guidance of the guide tube 34, achieving full mixing in the mixing zone of the single-stage chamber. During the mixing and mass transfer process, another portion of the two-phase fluid will flow into the clarification chamber through the channel between the two corresponding baffles 21 under the obstruction of the baffles 21. The degree of emulsification can be controlled by the axial airfoil blades 32 to achieve source emulsification control. This ensures that the two-phase fluids have sufficient contact area for extraction and mass transfer, while avoiding excessive emulsification that produces a large number of stable microemulsions that are difficult to separate. This fundamentally reduces the separation difficulty in the subsequent clarification chamber. Furthermore, the strong axial circulation generated by the combination of the axial airfoil blades 32 and the guide tube 34 effectively improves the mixing efficiency. The spiral guide blades 35 can also provide uniform and controllable shear force and dispersion effect, increase the contact area between the two phases, and effectively improve the single-stage extraction efficiency.

[0038] In the swirling elimination and low-frequency pre-demulsification stage, after the mixed two-phase fluid flows out of the mixing chamber outlet (the channel between the upper rectangular baffle 21 and the lower T-shaped baffle 21), it first enters the clarification chamber through the orifice plate 41 near the mixing chamber. The straight hole structure on the orifice plate 41 can transform the swirling turbulence at the mixing chamber outlet into a uniform laminar flow state, greatly reducing the secondary emulsification phenomenon caused by turbulence, and creating good conditions for subsequent clarification and separation. After the swirling elimination treatment, the two-phase fluid will continue to flow towards the T-shaped weir plate 23. Since the inclination direction of the guide plate 43 is consistent with the liquid flow direction (both are inclined upwards), when the two-phase fluid passes through the guide plate 43, the overall flow will tend to be upward.

[0039] It should be noted that in the original microemulsion flowing out of the mixing chamber, each droplet surface is coated with a dense colloidal film formed by ferric hydroxide and aluminosilicate colloidal particles from the leachate of waste lithium batteries. When the droplets hit the guide plate 43, they will bounce off directly and cannot coalesce effectively. At this time, due to the rotation of the rotating shaft 31, the mounting plate 474 rotates synchronously. The two sets of abutment balls 475 of different diameters arranged alternately on the outer wall of the mounting plate 474 will hit the docking plate 473 in sequence. This causes the docking plate 473 to drive the two front and rear support rods 472 to slide back and forth along the inner wall of the corresponding positioning tube 471. The two front and rear support rods 472 will jointly drive the corresponding support sleeve 476 to move back and forth synchronously. The support sleeve 476 will drive several connecting seats 477 and striking hammer rods 47. 8. The synchronous reciprocating movement causes several hammer rods 478 to intermittently strike the corresponding guide plate 43. Since the guide plate 43 is composed of two detachable rectangular plates, it is connected to the corresponding positioning strip 45 by compression springs for elastic position limitation. At the same time, it is also slidably sleeved on the outer wall of the corresponding limiting rod 42. At this time, the guide plate 43 generates low-frequency small-amplitude vibration along the straight direction of the limiting rod 42. The low-frequency small-amplitude vibration generated by the intermittent striking will cause the droplets and the solid colloidal particles attached to the surface to move relative to each other, breaking and detaching the dense colloidal film wrapped on the surface of the droplets, stabilizing the microemulsion into exposed free droplets, and greatly increasing the probability of these free droplets colliding with each other under the action of vibration, rapidly agglomerating into large droplets, completing the pre-demulsification of the stable microemulsion.

[0040] During the microemulsion coalescence and serpentine flow separation stage, the staggered arrangement of the two orifice plates 41 and several guide plates 43 in the clarification chamber forces the two-phase fluid to flow slowly along the serpentine channel, causing the fluid to change direction multiple times. This increases the probability of collisions between droplets and between droplets and guide plates 43, effectively avoiding short-circuiting and prolonging the residence time of the two-phase fluid in the clarification chamber, providing sufficient time for droplet coalescence and growth. As the two-phase fluid continues to flow towards the T-shaped weir plate 23, it passes through several synchronously vibrating guide plates 43 in sequence, completing the pre-demulsification process. Stable microemulsions are almost nonexistent in the fluid, and almost all droplets aggregate into large droplets. Simultaneously, the guide plates 43 have a strong adsorption affinity for light phase droplets. When exposed large light phase droplets flow through and collide with the guide plates 43, they will be adsorbed by the end face of the guide plates 43 and spread within the corrugated groove 46. The light phase liquid film is formed by coalescence. The corrugated groove 46 design increases the contact area between the light phase droplets and the end face of the guide plate 43. At the same time, local eddies are formed in the groove, which further promotes the collision and coalescence of fine droplets. The coalesced light phase liquid film will float upward along the inclined guide plate 43 to the upper side of the clarification chamber and converge. The heavy phase droplets will form a continuous heavy phase liquid film along the end face of the guide plate 43 and sink downward to the bottom of the clarification chamber and converge, completing the coarse separation of the two phases and the coalescence of most droplets. Through the fluid treatment design of source emulsification control in the mixing chamber and enhanced demulsification in the clarification chamber, the guide plate 43 undertakes the functions of coarse separation and coalescence of most droplets. The low-frequency vibration group 47 pre-demulsifies the stubborn and stable microemulsions generated in the mixing chamber, providing the guide plate 43 group with two phase fluids that are easier to separate. The two work together to effectively improve the speed of droplet aggregation and growth and shorten the clarification time of the two phase fluids.

[0041] In the two-phase fine separation and continuous extraction stage, the two-phase fluid, after coarse separation by several guide plates 43, enters the clarification separation zone on the left side of the T-shaped weir plate 23. Under the action of gravity, the final fine phase separation occurs, forming a clear upper light phase layer and a clear lower heavy phase layer. The two-phase interface is stable in the middle region of the T-shaped weir plate 23. At this time, the height of the less dense light phase layer (extractant loaded with manganese ions) corresponds to the height of the weir crest of the light phase weir, allowing the light phase fluid to pass through the toothed structure at the upper end of the light phase weir. The light phase overflows uniformly to the right side of the light phase collection zone. During this process, the smooth guide surface of the toothed structure allows the light phase to flow out uniformly in a thin film, avoiding droplet entrainment caused by excessive local flow velocity. The denser heavy phase (raffinate phase) will flow downward to the bottom of the single-stage chamber and smoothly enter the heavy phase collection zone through the rectangular flow port on the lower side of the heavy phase weir. The design of the lower edge of the flow port of the heavy phase weir being flush with the bottom plate ensures that the heavy phase fluid at the bottom of the clarification chamber can be completely discharged into the heavy phase collection zone, without creating dead zones or sediment accumulation.

[0042] It is worth emphasizing that after the heavy phase fluid smoothly enters the heavy phase collection area through the rectangular flow port on the lower side of the heavy phase weir, the heavy phase fluid will enter the regulating pipe 25 through the flow port opened on the upper side of the outer wall of the regulating pipe 25, and then enter the heavy phase collection pipe 24 through the flow port opened on the lower side of the outer wall of the regulating pipe 25, and finally be discharged through the corresponding connecting pipe 27.

[0043] Subsequently, the light phase fluid in the first-stage single-stage chamber continues to flow into the second-stage single-stage chamber below the submerged chamber partition 22 through the through hole 26 and connecting pipe 27 in the light phase collection area. The loaded organic phase of the second stage then flows into the third-stage single-stage chamber in the same manner, and is finally discharged from the light phase collection area output pipe 29 of the third-stage single-stage chamber, entering the subsequent back-extraction process. The heavy phase fluid in the third-stage single-stage chamber flows into the second-stage single-stage chamber below the submerged chamber partition 22 through the heavy phase collection pipe 24 and connecting pipe 27. The raffinate aqueous phase of the second stage then flows into the first-stage single-stage chamber in the same manner, and is finally discharged from the heavy phase collection pipe 24 output pipe 29 of the first-stage single-stage chamber, entering the subsequent impurity removal process. The two-phase fluid is transported countercurrently between adjacent single-stage chambers through the connecting pipe 27, ensuring that each stage can achieve sufficient contact between the fresh light phase fluid and the high-concentration heavy phase fluid, as well as sufficient contact between the high-concentration loaded light phase fluid and the low-concentration heavy phase fluid, maximizing the driving force of extraction mass transfer.

[0044] During the liquid level regulation and stable operation phase, when the flow rate, concentration, or phase ratio of the liquid to be treated changes during the operation of the mixing and clarification tank, the adjustment can be made by rotating the threaded section of the regulating pipe 25, causing the regulating pipe 25 to move up and down along the inner wall of the heavy phase collection pipe 24. This allows for real-time adjustment of the effective liquid level of the heavy phase in the clarification and separation zone of each stage chamber. Since the total internal volume of the single-stage chamber is fixed, the total feed flow rate and total discharge flow rate of the two-phase fluids maintain a dynamic balance. Therefore, the total liquid level (heavy phase liquid level + light phase liquid level) in the clarification chamber remains constant. Under this constraint, The two phase levels exhibit an inverse relationship. When the regulating pipe 25 moves upward, the liquid level of the heavy phase fluid in the heavy phase collection zone rises, while the liquid level of the light phase falls. When the regulating pipe 25 moves downward, the liquid level of the heavy phase fluid in the heavy phase collection zone falls, while the liquid level of the light phase rises. By adjusting the regulating pipes 25 in the three single-stage chambers respectively, the two-phase interface in each stage clarification chamber is kept at a suitable height, ensuring the two-phase separation effect and continuous and stable operation. At the same time, by precisely controlling the height of the two-phase interface, the phenomenon of light phase flowing out from the heavy phase weir or heavy phase flowing out from the light phase weir can be avoided, further reducing the two-phase entrainment rate.

[0045] The above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions will not cause the essence of the corresponding technical solutions to deviate from the protection scope of the technical solutions of the embodiments of the present invention.

Claims

1. An extraction device for preparing manganese sulfate from waste lithium batteries, characterized in that, include: An extraction tank (1) with a cover plate (11) installed at the top is divided into three single-stage chambers by a series of symmetrically distributed partitions (2) on the inner wall of the extraction tank (1). Two baffles (21) are installed on one side of the inner wall of the single-stage chamber along its length direction. A T-shaped weir plate (23) is installed on the side of the inner wall of the single-stage chamber away from the baffles (21). The baffles (21) and T-shaped weir plates (23) in two adjacent single-stage chambers are arranged in opposite directions. A stirring and mixing section (3) is provided on both the single-stage chamber and the cover plate (11). A microemulsion control section (4) is provided on both the single-stage chamber and the stirring and mixing section (3). The mixing section (3) includes a rotating shaft (31) that is rotatably installed on the upper end of the cover plate (11). An axial flow airfoil blade (32) is fixedly sleeved on the lower end of the outer wall of the rotating shaft (31). A servo motor (36) for driving the rotating shaft (31) to rotate is installed on the upper end of the cover plate (11). The microemulsion control unit (4) includes perforated plates (41) symmetrically installed on the inner wall of the single-stage chamber. Several rectangularly evenly distributed limiting rods (42) are installed on the opposite ends of the two perforated plates (41). Several linearly evenly distributed guide plates (43) are slidably sleeved on the outer wall of the limiting rods (42). The guide plates (43) are composed of two detachable rectangular plates. Low-frequency vibration groups (47) are jointly provided on the baffle plate (21) and the T-shaped weir plate (23). The low-frequency vibration group (47) includes a positioning tube (471) symmetrically rotated and installed on the T-shaped weir plate (23), and a support rod (472) symmetrically rotated and installed on the baffle plate (21) on the upper side. The support rod (472) has a stepped shaft structure. The outer wall of the smaller diameter section of the support rod (472) is slidably connected to the inner wall of the corresponding positioning tube (471). The larger diameter section of the support rod (472) and the positioning tube (471) are connected by a... The compression springs are connected, and the two support rods (472) are connected together at one end of the shaft (31) with a docking plate (473). The docking plate (473) has an arc-shaped structure. The outer wall of the shaft (31) is fixedly fitted with a mounting plate (474) corresponding to the docking plate (473). The outer wall of the mounting plate (474) is staggered with two sets of abutting balls (475) of different diameters. Each set of abutting balls (475) consists of several abutting balls (475) evenly distributed in a circle. The low-frequency vibration group (47) also includes a support sleeve (476) fixedly sleeved on the outer wall of the front and rear support rods (472). The lower end of the support sleeve (476) is equipped with a connecting seat (477) corresponding to several guide plates (43). The lower end of the connecting seat (477) is equipped with several linearly and evenly distributed hammer rods (478). The lower end of the hammer rods (478) moves against the corresponding guide plate (43).

2. The extraction equipment for preparing manganese sulfate from waste lithium batteries according to claim 1, characterized in that: The mixing section (3) also includes a connecting frame (33) installed on the inner wall of the single-stage chamber and on the baffle plate (21) on the lower side. The connecting frame (33) consists of several circumferentially distributed extension rods and annular sleeves. A guide tube (34) is installed on the inner wall of the annular sleeve. Both the upper and lower ends of the guide tube (34) are gradually expanding inlet ports, and a spiral guide vane (35) is installed on the inner wall of the guide tube (34).

3. The extraction equipment for preparing manganese sulfate from waste lithium batteries according to claim 1, characterized in that: The microemulsion control unit (4) also includes a receiving groove (44) located on the guide plate (43) with two rectangular plates at opposite ends. The receiving groove (44) has two openings, one above the other. A positioning strip (45) is slidably installed on the inner wall of the receiving groove (44). The positioning strip (45) is simultaneously fixedly sleeved on the outer wall of the corresponding two limiting rods (42). The two ends of the positioning strip (45) are respectively connected to the inner wall of the corresponding receiving groove (44) by compression springs. Several corrugated grooves (46) are linearly and uniformly distributed on both ends of the guide plate (43).

4. The extraction equipment for preparing manganese sulfate from waste lithium batteries according to claim 1, characterized in that: The two baffles (21) are also staggered from left to right. The baffle (21) on the lower side is T-shaped and the baffle (21) on the upper side is rectangular. The baffle (21) on the lower side and the single-stage chamber wall are jointly equipped with a submerged chamber baffle (22). The submerged chamber baffle (22) is also T-shaped. The upper end of the horizontal section of the submerged chamber baffle (22) is symmetrically provided with fan-shaped holes corresponding to the front and back of the vertical section. The T-shaped weir plate (23) is composed of a rectangular partition plate, a light phase weir and a heavy phase weir. The upper end of the light phase weir has a toothed structure.

5. The extraction equipment for preparing manganese sulfate from waste lithium batteries according to claim 1, characterized in that: A heavy phase collection pipe (24) is installed on the inner wall of the single-stage chamber corresponding to the heavy phase weir on the side of the T-shaped weir plate (23). An adjustment pipe (25) is provided inside the heavy phase collection pipe (24). The adjustment pipe (25) consists of a threaded section and a stepped shaft section. The threaded section of the adjustment pipe (25) is threadedly connected to the cover plate (11). The outer wall of the larger diameter end of the stepped shaft section is movably attached to the inner wall of the heavy phase collection pipe (24), and flow ports are symmetrically opened on the upper and lower sides of the outer wall of the stepped shaft section.

6. The extraction equipment for preparing manganese sulfate from waste lithium batteries according to claim 4, characterized in that: The single-stage chamber has through holes (26) symmetrically opened in the vertical section corresponding to the submersible partition (22) on the inner wall of the chamber. The light phase weir and heavy phase weir corresponding to the T-shaped weir plate (23) on the inner wall of the single-stage chamber have through holes (26) respectively, and the regulating pipe (25) is connected to the through hole (26) of the corresponding heavy phase weir.

7. The extraction equipment for preparing manganese sulfate from waste lithium batteries according to claim 6, characterized in that: Both the front and rear single-stage chambers are provided with input pipes (28) at their lower ends. The input pipes (28) are connected to one of the through holes (26) of the corresponding submersible partition (22). In the front single-stage chamber, the through hole (26) of the heavy phase weir on the T-shaped weir plate (23) is connected to the output pipe (29). In the rear single-stage chamber, the through hole (26) of the light phase weir on the T-shaped weir plate (23) is also connected to the output pipe (29). The remaining through holes (26) in the two adjacent single-stage chambers are connected by connecting pipes (27).

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