Extraction equipment for recycling waste lithium batteries to prepare manganese sulfate

Abstract

The present application belongs to the technical field of extraction equipment structure, and particularly relates to an extraction equipment for recycling waste lithium batteries to prepare manganese sulfate. The present application provides an extraction equipment for recycling waste lithium batteries to prepare manganese sulfate, which can separate and discharge in high resolution without a suction pump in the discharging operation of the upper extraction phase by setting a feeding pipe, a stirring shaft, a bottom stirring motor, a sleeve unit, a pipe column composite unit, a pushing column unit, a one-way stirring column unit, an extraction phase discharge pipe and an aqueous phase discharge pipe on the extraction kettle.

Description

Technical Field

[0001] This invention belongs to the technical field of extraction equipment structure, and particularly relates to an extraction equipment for the preparation of manganese sulfate from waste lithium batteries. Background Technology

[0002] During the recycling process of waste lithium batteries, battery black powder is obtained. The recycling value of this powder lies in its numerous metallic elements, including nickel, cobalt, manganese, copper, lithium, aluminum, and zinc. On the other hand, the aforementioned battery black powder will yield P204 copper-manganese liquid in subsequent processing. The main metallic elements included in P204 copper-manganese liquid are copper, calcium, zinc, and manganese.

[0003] Manganese sulfate can be prepared from P204 copper-manganese solution using Cyanex 272 extractant. The general preparation principle is as follows:

[0004] First, sodium sulfate is added to the P204 copper-manganese solution to remove calcium sulfate precipitate.

[0005] Second, add liquid alkali and barium sulfide to remove copper sulfide, zinc sulfide and barium sulfate precipitates;

[0006] Third, add hydrogen peroxide to oxidize excess sulfur ions;

[0007] Fourth, saponify the Cyanex 272 extractant using liquid alkali;

[0008] Fifth, saponification of Cyanex 272 extractant and manganese ions are used for extraction, leaving calcium ions in the aqueous phase;

[0009] Sixth, sulfuric acid is used to back-extract the extractant phase, followed by evaporation to finally obtain manganese sulfate crystals.

[0010] Therefore, in the process of preparing manganese sulfate crystals from P204 copper-manganese solution, extraction equipment is necessary.

[0011] Existing extraction equipment mainly consists of a vessel body and a stirring component. For example, Chinese utility model patent CN212783575U, published on March 23, 2021, discloses a continuous extraction device for extracting and recycling manganese sulfate from waste lithium batteries. This device includes an extraction unit body, a filter box fixedly connected to the top right side of the body, sliding grooves on both sides of the filter box, a retainer slidably connected to the inner cavity of the sliding groove, a filter screen slidably connected to the inner cavity of the retainer, and slots on both sides of the top of the inner wall of the filter box, with retaining blocks engaging within the inner cavity of the slots.

[0012] The continuous extraction device in this utility model patent puts the extract into the inner cavity of the filter box through the inlet. The filter screen slides downward due to gravity, which causes the spring to deform and stretch outward. The spring recovers its deformation due to its own elasticity and at the same time drives the filter screen to move upward, thus filtering the extract and indirectly improving the quality of the extraction operation.

[0013] However, this continuous extraction device has at least the following deficiency in the actual preparation of manganese sulfate crystals, which is also the technical problem that this invention aims to solve:

[0014] Like most existing conventional extraction equipment, this device can only achieve "heavy liquid exiting from the bottom and light liquid exiting from the top". Therefore, it needs to be equipped with a feed pump and a dedicated discharge pipeline for the manganese ion extraction phase and the calcium ion aqueous phase, which is relatively inefficient.

[0015] Of course, the premise and common sense of this process is that the heavy liquid cannot be discharged downwards first and then the light liquid, as this would greatly agitate the heavy and light liquids and reduce the degree of separation between the two phases in the extraction operation.

[0016] Therefore, in summary, there is an urgent need for a new type of extraction equipment that can separate heavy and light liquids with high differentiation without a suction pump, and discharge both at the bottom in a concentrated manner, so as to be used in the preparation process of manganese sulfate crystals by combining P204 copper-manganese liquid with Cyanex 272 extractant. Summary of the Invention

[0017] This invention provides an extraction device for preparing manganese sulfate from waste lithium batteries. By setting up a feed pipe, stirring shaft, bottom stirring motor, sleeve unit, tubular composite unit, push column unit, unidirectional stirring column unit, extract phase discharge pipe, and aqueous phase discharge pipe on the extraction vessel, it is possible to: 1. separate and discharge the upper extract phase with high differentiation without the need for a suction pump; 2. discharge both the extract phase and the aqueous phase at the bottom of the extraction vessel and share a single discharge pipeline.

[0018] The technical solution adopted by the present invention to solve the above problems is: an extraction device for preparing manganese sulfate from waste lithium battery recycling, the structure of which includes an extraction vessel, a feed pipe, a stirring shaft set on the bottom plate of the extraction vessel, and a bottom stirring motor, and further includes a sleeve unit set on the bottom plate of the extraction vessel for overflowing and discharging the extract phase, a tubular composite unit set on the bottom plate of the extraction vessel and located between the stirring shaft and the sleeve unit for blocking the extract phase, a push column unit screwed onto the stirring shaft and inserted into the tubular composite unit for pressing down the sleeve unit, a unidirectional stirring column unit set at the upper end of the stirring shaft, an extract phase discharge pipe set on the bottom plate of the extraction vessel and located between the sleeve unit and the tubular composite unit, and an aqueous phase discharge pipe set on the bottom plate of the extraction vessel and located radially outside the sleeve unit.

[0019] A further preferred technical solution is that the extraction vessel includes a lower circular vessel and an upper circular vessel with a diameter smaller than that of the lower circular vessel, and the feed pipe is disposed on the top plate of the lower circular vessel.

[0020] A further preferred technical solution is that the sleeve unit includes a fixed cylinder disposed on the bottom surface of the extraction vessel, an annular groove disposed on the upper surface of the fixed cylinder, a lifting cylinder inserted into the annular groove, abutting the push column unit and used to block the extraction phase, and a lifting spring disposed in the annular groove and used to support the lifting cylinder.

[0021] A further preferred technical solution is that the sleeve unit further includes two annular sealing membranes respectively disposed on the upper surface of the fixed cylinder and the inner and outer annular surfaces of the lifting cylinder.

[0022] A further preferred technical solution is that the tubular composite unit includes a vertical cylinder disposed on the bottom surface of the extraction vessel and located between the stirring shaft and the fixed cylinder, and a vertical rod disposed on the vertical cylinder and inserted into the push column unit.

[0023] A further preferred technical solution is that the pushing column unit includes a ring screwed onto the stirring shaft on its inner ring surface, a limiting hole disposed on the ring and inserted into the vertical rod, and a vertical plate disposed on the ring and used to press down on the lifting cylinder.

[0024] A further preferred technical solution is that the pushing column unit further includes a sliding ring disposed on the lower end surface of the vertical plate and used to press the lifting cylinder downward.

[0025] A further preferred technical solution is that the unidirectional stirring column unit includes a unidirectional bearing disposed at the upper end of the stirring shaft and used to stop stirring when the pushing column unit presses down on the sleeve unit, an extension shaft disposed on the unidirectional bearing, a radial plate disposed on the extension shaft, a downward extension plate disposed on the radial plate, and a stirring column disposed on the downward extension plate.

[0026] A further preferred technical solution is that the unidirectional stirring column unit further includes a limiting cylinder disposed on the top surface of the extraction vessel and used to insert the extension shaft.

[0027] A further preferred technical solution is that the downward extending plate and the stirring column are both located on the radial outer side of the sleeve unit. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the structure of the present invention.

[0029] Figure 2 This is a schematic diagram of the shape of the extraction vessel in this invention.

[0030] Figure 3 This is a schematic diagram showing the position of the stirring shaft in this invention.

[0031] Figure 4 This is a schematic diagram of the position and structure of the sleeve unit in this invention.

[0032] Figure 5 This is a schematic diagram showing the position of the pushing column unit in this invention.

[0033] Figure 6 This is a top-down view of the structure of the push column unit in this invention.

[0034] Figure 7 This is a top-down view showing the position of the sleeve unit in this invention.

[0035] Figure 8 This is a schematic diagram of the unidirectional stirring column unit in this invention.

[0036] The meanings of the markings in the diagram are as follows:

[0037] Extraction phase liquid surface a, two-phase interface b;

[0038] Extraction vessel 11, feed pipe 12, stirring shaft 13, bottom stirring motor 14;

[0039] Sleeve unit 1, tubular composite unit 2, push column unit 3, unidirectional stirring column unit 4, extraction phase discharge pipe 5, aqueous phase discharge pipe 6;

[0040] Fixed cylinder 101, annular groove 102, lifting cylinder 103, lifting spring 104, annular sealing membrane 105, vertical cylinder 201, vertical rod 202, ring 301, limiting hole 302, vertical plate 303, sliding ring 304, one-way bearing 401, extension shaft 402, radial plate 403, downward extension plate 404, stirring column 405, limiting cylinder 406. Detailed Implementation

[0041] The following description is only a preferred embodiment of the present invention and is not intended to limit the scope of the present invention.

[0042] As attached Figure 1-8 As shown, an extraction device for preparing manganese sulfate from waste lithium batteries includes an extraction vessel 11, a feed pipe 12, a stirring shaft 13 mounted on the bottom plate of the extraction vessel 11, and a bottom stirring motor 14. It also includes a sleeve unit 1 mounted on the bottom plate of the extraction vessel 11 for overflowing the extractant phase, a tubular composite unit 2 mounted on the bottom plate of the extraction vessel 11 between the stirring shaft 13 and the sleeve unit 1 for blocking the extractant phase, a push column unit 3 screwed onto the stirring shaft 13 and inserted into the tubular composite unit 2 for pressing the sleeve unit 1 downwards, a unidirectional stirring column unit 4 mounted at the upper end of the stirring shaft 13, an extractant phase discharge pipe 5 mounted on the bottom plate of the extraction vessel 11 between the sleeve unit 1 and the tubular composite unit 2, and an aqueous phase discharge pipe 6 mounted on the bottom plate of the extraction vessel 11 and located radially outside the sleeve unit 1.

[0043] In this embodiment, the feed pipe 12 is used to add P204 copper-manganese solution (after calcium, copper, and zinc ions have been removed) and saponified Cyanex 272 extractant. The extract phase discharge pipe 5 yields an extract phase containing manganese ions, and the aqueous phase discharge pipe 6 yields an aqueous phase containing residual calcium ions. The Cyanex 272 extractant has a specific gravity of 0.92, therefore the extract phase is on top and the aqueous phase is at the bottom.

[0044] In addition, the extract phase is discharged first. The discharge principle is that the stirring shaft 13 converts its own rotation into the downward movement of the push column unit 3. The push column unit 3 then pushes the moving part of the sleeve unit 1 downward, so that the liquid level a of the extract phase is higher than the upper edge of the sleeve unit 1, and finally the discharge operation is effectively carried out.

[0045] The aqueous phase discharge is achieved by fully opening the valve on the aqueous phase discharge pipe 6 after all the extract phase has been discharged. In other words, the high-precision separation of the extract phase and aqueous phase relies on the precise lowering and stopping of the upper edge of the sleeve unit 1 at the two-phase interface b. Therefore, the bottom stirring motor 14 is a stepper motor capable of forward and reverse rotation, and its rotational movement has relatively high precision.

[0046] Furthermore, the tubular composite unit 2 has a "bottom tubing, top column" structure, and it has two main functions:

[0047] First, the extract phase is separated from the stirring shaft 13 to prevent the extract phase from being contaminated and leaked.

[0048] Secondly, it provides a circumferential limiting effect to the push column unit 3; otherwise, when the stirring shaft 13 rotates, the push column unit 3 can only rotate along with it instead of converting the rotation action into a lifting action.

[0049] It should be noted that the push column unit 3 will move vertically regardless of whether the stirring shaft 13 rotates forward or backward. Therefore, during extraction, the unidirectional stirring column unit 4 cannot rotate continuously in one direction. Otherwise, the push column unit 3 will either be too high and separate from the tubular composite unit 2, or too low and cause the liquid to flow out prematurely.

[0050] Therefore, the correct way to rotate the stirring shaft 13 is to alternate between forward and reverse rotation, ensuring that the upper edge of the sleeve unit 1 is at a suitable height, and the number of forward and reverse rotations is the same, so that the upper edge of the sleeve unit 1 can rise and fall within a safe range without adverse effects. At this time, the unidirectional stirring column unit 4 can only effectively stir for half the time.

[0051] After the saponified Cyanex 272 extractant and P204 copper-manganese solution are fully mixed, the stirring shaft 13 will no longer drive the unidirectional stirring column unit 4. Instead, the pushing column unit 3 will push the sleeve unit 1 downward.

[0052] Ultimately, while the stirring structure of this extraction device is indeed more complex than existing extraction stirring components, the benefit is the saving of a feed pump and its entire electrical control system. This benefit is enormous, making the increased complexity worthwhile.

[0053] The extraction vessel 11 includes a lower circular vessel and an upper circular vessel with a diameter smaller than that of the lower circular vessel. The feed pipe 12 is disposed on the top plate of the lower circular vessel.

[0054] In this embodiment, the extraction vessel 11, which is "smaller at the top and larger at the bottom", can save vessel material without affecting the stirring and extraction effect. This is because the maximum height of the material liquid level will not and cannot exceed the height of the highest upper edge of the sleeve unit 1, and the actual stirring position of the unidirectional stirring column unit 4 is also lower.

[0055] Therefore, the extraction vessel 11 can be composed of two cylindrical vessels of different sizes and a transition ring, and the feed pipe 12 is located on the transition ring.

[0056] The sleeve unit 1 includes a fixed cylinder 101 disposed on the bottom surface of the extraction vessel 11, an annular groove 102 disposed on the upper surface of the fixed cylinder 101, a lifting cylinder 103 inserted into the annular groove 102, abutting the push column unit 3 and used to block the extraction phase, and a lifting spring 104 disposed in the annular groove 102 and used to support the lifting cylinder 103.

[0057] In this embodiment, the bottom of the fixed cylinder 101 needs to be sufficiently sealed. It can be integrally formed with the bottom plate of the extraction vessel 11, or it can be welded later.

[0058] The annular groove 102 is circular in shape, and the downward pressing force of the push column unit 3 is greater than the elastic force of the lifting spring 104.

[0059] The sleeve unit 1 also includes two annular sealing films 105 respectively disposed on the upper surface of the fixed cylinder 101 and the inner and outer annular surfaces of the lifting cylinder 103.

[0060] In this embodiment, the two annular surfaces of the lifting cylinder 103 and the annular groove 102 need to be fully sealed to prevent liquid leakage. There are two main sealing methods: First, the lifting cylinder 103 is made of rubber with moderate elasticity. Through elastic locking, it can be lifted and lowered while maintaining a sufficient degree of sealing. Second, an annular sealing film 105 is bonded to both the inner and outer sides. In this case, the insertion structure of the lifting cylinder 103 itself does not have a sealing requirement.

[0061] The annular sealing film 105 is made of existing ordinary elastic rubber to ensure sufficient adhesion and sealing, chemical inertness, and to prevent it from affecting the normal lifting and lowering operation of the lifting cylinder 103.

[0062] The tubular composite unit 2 includes a vertical cylinder 201 disposed on the inner bottom surface of the extraction vessel 11 and located between the stirring shaft 13 and the fixed cylinder 101, and a vertical rod 202 disposed on the vertical cylinder 201 and inserted into the push column unit 3.

[0063] In this embodiment, the vertical cylindrical body 201 can be either a round or square cylinder. Its bottom surface and the inner bottom surface of the extraction vessel 11 also need to be fully sealed to prevent leakage of the extraction phase. Otherwise, the extraction phase may contaminate or damage the bottom stirring motor 14.

[0064] Therefore, the stirring shaft 13 and the bottom plate of the extraction vessel 11 only need to be properly connected, and there is no requirement for sealing.

[0065] In addition, there are two vertical rods 202, and their cross-sectional shapes can be circular or square.

[0066] The push column unit 3 includes a ring 301 screwed onto the stirring shaft 13 on its inner ring surface, a limiting hole 302 disposed on the ring 301 and inserted into the vertical rod 202, and a vertical plate 303 disposed on the ring 301 and used to press down on the lifting cylinder 103.

[0067] In this embodiment, the inner ring surface of the ring 301 is provided with a threaded section, and the limiting hole 302 is provided with a ball or lubricating oil, so the ring 301 will not come into contact with the liquid.

[0068] Furthermore, when the stirring shaft 13 rotates, the pushing column unit 3 can move up and down to ensure that after the extraction and stratification, the vertical plate 303 can slowly push the lifting cylinder 103 downward as needed, so that the manganese ion-containing extraction phase can slowly and completely flow into the area between the fixed cylinder 101 and the vertical cylinder 201 at the upper edge of the lifting cylinder 103, and finally be discharged at the extraction phase discharge pipe 5.

[0069] The push column unit 3 also includes a sliding ring 304 disposed on the lower end surface of the vertical plate 303 and used to press down the lifting cylinder 103.

[0070] In this embodiment, the sliding ring 304 is circular in shape. It replaces the vertical plate 303 and directly pushes the upper edge of the lifting cylinder 103. This is to avoid the "relatively sharp" vertical plate 303 scratching the upper edge of the lifting cylinder 103, and also to prevent the small protrusions and grooves on the upper edge of the lifting cylinder 103 from getting stuck on the vertical plate 303.

[0071] The unidirectional stirring column unit 4 includes a unidirectional bearing 401 located at the upper end of the stirring shaft 13 and used to stop stirring when the pushing column unit 3 presses down on the sleeve unit 1, an extension shaft 402 located on the unidirectional bearing 401, a radial plate 403 located on the extension shaft 402, a downward extension plate 404 located on the radial plate 403, and a stirring column 405 located on the downward extension plate 404.

[0072] In this embodiment, the one-way bearing 401 ensures that the stirring shaft 13 can only transmit power in one rotational direction. In other words, during extraction and stirring, the one-way stirring column unit 4 is not rotating for approximately half the time.

[0073] In addition, the total amount of P204 copper-manganese solution and saponified Cyanex 272 extractant added at one time cannot exceed the initial and highest upper edge height of the lifting cylinder 103, so the stirring column 405 can be concentrated at a relatively lower position on the downward extension plate 404.

[0074] The unidirectional stirring column unit 4 also includes a limiting cylinder 406 disposed on the inner top surface of the extraction vessel 11 and used to insert the extension shaft 402.

[0075] In this embodiment, the limiting cylinder 406 can reduce the left and right swing amplitude of the unidirectional stirring column unit 4, and prevent the downward extension plate 404 from hitting the fixed cylinder 101 and the stirring column 405 from hitting the inner ring surface of the extraction vessel 11.

[0076] The radial plate 403, the downward extending plate 404, and the stirring column 405 constitute a complete stirring structure, and 2-3 sets of this stirring structure are provided on the extending shaft 402.

[0077] The downward extension plate 404 and the stirring column 405 are both located on the radial outer side of the sleeve unit 1.

[0078] In this embodiment, the radially outer region of the sleeve unit 1 is first a stirring extraction zone, and then a calcium ion-containing aqueous phase discharge zone. The region between the sleeve unit 1 and the column composite unit 2 is a manganese ion-containing extraction phase discharge zone.

[0079] Therefore, correspondingly, the extraction phase discharge pipe 5 is located further inward and closer to the bottom stirring motor 14 than the aqueous phase discharge pipe 6.

[0080] The embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various modifications can be made without departing from the spirit of the present invention. These are non-inventive modifications and are protected by patent law as long as they fall within the scope of the claims of the present invention.

Claims

1. A kind of extraction equipment for the preparation of manganese sulfate with waste lithium battery recycling, structure includes extraction kettle (11), feed pipe (12), the stirring shaft (13) being set on the bottom plate of the extraction kettle (11), and bottom stirring motor (14), it is characterized by: Also included are a sleeve unit (1) disposed on the bottom plate of the extraction kettle (11) and used for overflow discharging of the extraction phase, a pipe column composite unit (2) disposed on the bottom plate of the extraction kettle (11) and located between the stirring shaft (13) and the sleeve unit (1) and used for blocking the extraction phase, a pushing column unit (3) screwed on the stirring shaft (13) and inserted with the pipe column composite unit (2) and used for pressing down the sleeve unit (1), a one-way stirring column unit (4) disposed at the upper end position of the stirring shaft (13), an extraction phase discharge pipe (5) disposed on the bottom plate of the extraction kettle (11) and located between the sleeve unit (1) and the pipe column composite unit (2), and a water phase discharge pipe (6) disposed on the bottom plate of the extraction kettle (11) and located radially outside the sleeve unit (1), The sleeve unit (1) includes a fixed cylinder (101) disposed on the inner bottom surface of the extraction kettle (11), an annular groove (102) disposed on the upper surface of the fixed cylinder (101), a lifting cylinder (103) inserted on the annular groove (102) and abutting against the pushing column unit (3) and used for blocking the extraction phase, and a jacking spring (104) disposed in the annular groove (102) and used for supporting the lifting cylinder (103), The pipe column composite unit (2) includes a vertical cylinder (201) disposed on the inner bottom surface of the extraction kettle (11) and located between the stirring shaft (13) and the fixed cylinder (101), and a vertical rod (202) disposed on the vertical cylinder (201) and inserted with the pushing column unit (3), The one-way stirring column unit (4) includes a one-way bearing (401) disposed at the upper end position of the stirring shaft (13) and used for stopping stirring when the pushing column unit (3) presses down the sleeve unit (1), an extension shaft (402) disposed on the one-way bearing (401), a radial plate (403) disposed on the extension shaft (402), a downward extending plate (404) disposed on the radial plate (403), and a stirring column (405) disposed on the downward extending plate (404).

2. The extraction equipment for recovering and preparing manganese sulfate from waste lithium batteries according to claim 1, characterized in that: The extraction kettle (11) includes a lower circular kettle and an upper circular kettle with a smaller diameter than the lower circular kettle, and the feed pipe (12) is disposed on the top plate of the lower circular kettle.

3. The extraction equipment for recovering and preparing manganese sulfate from waste lithium batteries according to claim 1, characterized in that: The sleeve unit (1) further includes two annular sealing membranes (105) respectively disposed on the upper surface of the fixed cylinder (101) and the inner and outer annular surfaces of the lifting cylinder (103).

4. The extraction equipment for recovering and preparing manganese sulfate from waste lithium batteries according to claim 1, characterized in that: The pushing column unit (3) includes a circular ring (301) screwed on the inner annular surface of the stirring shaft (13), a limiting hole (302) disposed on the circular ring (301) and inserted with the vertical rod (202), and a vertical plate (303) disposed on the circular ring (301) and used for pressing down the lifting cylinder (103).

5. The extraction apparatus for recovering and preparing manganese sulfate from waste lithium batteries according to claim 4, characterized in that: The pushing column unit (3) further comprises a sliding ring (304) arranged on the lower end surface of the vertical plate (303) and used for pressing the lifting cylinder (103) downward.

6. The extraction equipment for recovering and preparing manganese sulfate from waste lithium batteries according to claim 1, characterized in that: The one-way stirring column unit (4) further comprises a limiting cylinder (406) arranged on the inner top surface of the extraction kettle (11) and used for inserting the extension shaft (402).

7. The extraction equipment for recovering and preparing manganese sulfate from waste lithium batteries according to claim 1, characterized in that: The downward extension plate (404) and the stirring column (405) are both arranged on the radial outer side of the sleeve unit (1).

Images