A wet comprehensive recovery with acid solution purification process

Abstract

The present application relates to lithium battery recycling technical field, a kind of wet comprehensive recovery with acid solution purification process, comprising the following steps: S1, lithium battery ternary material broken material is crushed, then mixed with water to obtain slurry;S2, to the dissolution purification tower adds acid liquor, slurry, after stirring and mixing heating, SO2 is imported, and processing obtains leaching solution;S3, leaching solution is filtered and is added back to the dissolution purification tower by lifting pump, Na2S solution, NaClO3 solution are added, pH is adjusted, and after reaction, it is stationary;S4, leaching solution is filtered again and is added back to the dissolution purification tower by lifting pump, excess NaOH solution is added to make the nickel cobalt manganese coprecipitation in leaching solution, and mixed salt containing nickel cobalt manganese is obtained by filtration;The present application leaches the metal in lithium battery ternary material by dissolution purification tower, and also can precipitate leaching solution, separates the metal elements in leaching solution, reduces the recovery process, improves the leaching effect and precipitation purification effect of metal.

Description

Technical Field

[0001] The present invention belongs to the technical field of battery recycling, and in particular relates to an acid dissolution purification process for wet comprehensive recycling. Background Art

[0002] Waste lithium-ion batteries contain high-value chemicals such as carbonate organic solvents, lithium hexafluorophosphate, and metallic copper, cobalt, nickel, manganese, and lithium. Li, Co, and Ni are primarily used in cathode materials, accounting for 2-12%, 5-30%, and 0-10%, respectively. Cu and Al are primarily used in current collectors, accounting for 7-17% and 3-10%, respectively. Fe is used in the outer casing, accounting for approximately 0-25%. These batteries contain a variety of valuable, recyclable precious metals. The rational recycling of waste lithium batteries can help address resource scarcity.

[0003] Currently, there are numerous recycling technologies for used lithium-ion batteries, primarily focusing on pretreatment and recycling. Pretreatment, the pre-processing stage of lithium-ion batteries, primarily involves simple separation and material enrichment. Precious metals in used lithium-ion batteries are concentrated in the positive electrode. Therefore, recycling and utilization of used lithium-ion batteries primarily focuses on the positive electrode materials, which are also the core of resource recovery for used lithium-ion batteries. Key methods include bioleaching, solvent extraction, chemical precipitation, acid leaching, and electrochemical treatment. Currently, the most commonly used method is acid leaching, which extracts metals such as lithium, nickel, cobalt, and manganese from the battery's positive electrode materials as low-valent ions through an acid leaching reaction. Extraction, precipitation, and electrochemical methods are then used to further separate and purify the metal elements in the acid leaching solution. The current acid leaching process is lengthy and suffers from inadequate metal dissolution, resulting in low precious metal recovery rates and hindering the sustainable development of the industry. Summary of the Invention

[0004] In order to solve the deficiencies mentioned in the above-mentioned background technology, the purpose of the present invention is to provide an acid dissolution purification process for wet comprehensive recovery, in which the metals in the lithium battery ternary materials are leached through a dissolution purification tower, and the leachate can also be precipitated through the dissolution purification tower to separate the metal elements in the leachate, thereby reducing the recovery process and improving the metal leaching effect and precipitation purification effect.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] The present invention provides an acid dissolution purification process for wet comprehensive recovery, comprising the following steps:

[0007] S1. The lithium battery ternary material is further crushed into a particle size of 20-50 μm by a jet mill, and then the lithium battery ternary material is added to a pulping machine and mixed with water, and stirred to obtain a slurry;

[0008] S2. Add acid to the dissolution purification tower, then add the slurry to the dissolution purification tower, stir and mix evenly, heat to 70-90°C, introduce SO2 at a rate of 0.1-0.5 L / min, and treat for 3-5 hours to obtain a leachate;

[0009] S3, filtering the leachate through a filter, adding the filtrate back to the dissolution purification tower through a lift pump, adding Na2S solution and NaClO3 solution to the dissolution purification tower, and adjusting the pH to 11-12 with NaOH solution, reacting for 1-3 hours, and standing for 20-40 minutes after the reaction is completed;

[0010] S4. The leachate is filtered again through the filter, and the filtrate is added back to the dissolution purification tower through the lifting pump. Excessive NaOH solution is added to the dissolution purification tower to co-precipitate the nickel, cobalt and manganese in the leachate. The mixed salt containing nickel, cobalt and manganese is obtained by filtration, and the recovery of lithium battery ternary materials is completed.

[0011] Further preferably, the lithium battery ternary material is first alkaline washed at room temperature with a 1.5-2.5 mol / L NaOH solution before being added to the acid solution for leaching, the alkaline washing times are 1-3 times, and each washing time is 20-30 minutes.

[0012] Further preferably, the acid solution is a mixture of sulfuric acid and hydrogen peroxide, and the solid-liquid ratio of the lithium battery ternary material and the acid solution is 30-50 g / L.

[0013] Further preferably, the dissolution purification tower includes a tower body, a guide tube is vertically provided inside the tower body, the guide tube is fixedly connected to the inner wall of the tower body through a connecting rod, the upper and lower ends of the guide tube are rotatably connected to the guide assembly, a drive shaft is vertically passed through the guide tube, the drive shaft drives the guide assembly to rotate, the upper end of the tower body is fixedly connected to the overflow box, an overflow weir is provided inside the overflow box, the lower end of the overflow weir is fixedly connected to the inner wall of the tower body, the upper end of the drive shaft is rotatably connected to the overflow box, a rotary joint is fixedly installed on the top of the drive shaft, the drive shaft is a hollow shaft, an air inlet is provided on the surface of the drive shaft in the middle of the guide tube, the upper end of the drive shaft is engaged with the output shaft of the motor through a gear, a scraper assembly is fixedly installed on the surface of the drive shaft corresponding to the upper end of the overflow weir, a dosing pipe is fixedly installed on the upper end of the tower body wall, a feed port is fixedly installed on the lower end of the tower body side wall, a discharge port is fixedly installed on the bottom of the tower body, and a slag discharge port is fixedly installed on the lower end of the overflow box side wall.

[0014] Further preferably, the guide assembly includes an annular seat, the inner diameter and outer diameter of the annular seat are the same as those of the guide tube, the inner wall and outer wall of the annular seat are close to one end of the guide tube for fixing the first blade and the second blade respectively, the inclination angles of the first blade and the second blade are opposite, and the middle of the first blade is fixedly connected to the drive shaft.

[0015] Further preferably, the overflow tank has a diameter larger than the tower body, the overflow weir plate is a ring-shaped plate, and an outwardly extending mounting portion is arranged at the lower end of the overflow weir plate, the mounting portion has a circular arc-shaped cross section, and the mounting portion is fixedly connected to the inner wall of the tower body.

[0016] Further preferably, the scraping assembly comprises a sleeve, the driving shaft penetrates through the sleeve, the sleeve is fixedly connected to the driving shaft, the inner diameter of the sleeve is larger than the diameter of the driving shaft, the bottom end of the sleeve is provided with a sliding sleeve ring, the inner diameter of the top of the sliding sleeve ring is the same as the diameter of the driving shaft, and the outer diameter of the sliding sleeve ring is the same as the sleeve. A plurality of guide rods are fixedly arranged on the surface of the sliding sleeve ring, the upper ends of the guide rods penetrate through the side wall of the sleeve, the guide rods are in sliding connection with the sleeve, a spring is arranged in the gap between the inside of the sleeve and the driving shaft, the top of the sliding sleeve ring is connected to the top end of the sleeve through the spring, the outer wall of the sliding sleeve ring is fixedly provided with a scraping plate, the scraping plate is arranged in a quarter helix shape, the outer circle of the scraping plate is attached to the inner wall of the overflow weir plate, the upper end of the scraping plate is fixedly provided with a strip-shaped baffle, and the end of the strip-shaped baffle away from the sliding sleeve ring extends out of the overflow weir plate.

[0017] Further preferably, the dosing pipe is circular ring-shaped, the inner wall of the tower body is provided with a mounting groove corresponding to the dosing pipe, the dosing pipe is embedded in the mounting groove of the inner wall of the tower body, the inner diameter of the dosing pipe is the same as the inner diameter of the tower body, a plurality of dosing holes arranged in a ring array are formed in the inner wall of the dosing pipe, and an interface pipe is fixedly arranged on one side of the outer wall of the dosing pipe.

[0018] Further preferably, step S2 specifically comprises the following steps:

[0019] S201, the acid liquid is added into the tower body of the dissolution and purification tower through the feed inlet until the liquid level is higher than the top of the flow guide cylinder, the driving shaft is driven to rotate by the motor, the flow guide assembly at both ends of the flow guide cylinder is rotated, and the acid liquid in the tower body is brought into circular flow;

[0020] S202, the slurry is added into the outside of the flow guide cylinder through the dosing pipe, the acid liquid is added into the tower body of the dissolution and purification tower through the feed inlet until the liquid level is flush with the top of the overflow weir plate, the circular flow uniformly mixes the slurry and the acid liquid, and then the mixed liquid is heated to 70-90℃;

[0021] S203, the driving shaft is reversely driven by the motor to form reverse circular flow of the liquid in the tower body, SO2 is added into the middle of the flow guide cylinder through the rotary joint and the driving shaft, the SO2 and the liquid flow out from the bottom of the flow guide cylinder and then flow upward from the outside of the flow guide cylinder through the circular flow, the SO2 is introduced at a rate of 0.1-0.5 L / min, the lithium battery ternary material is dissolved after 3-5 hours of treatment, and part of the insoluble impurities float on the top of the overflow weir plate under the driving of the SO2 gas and are scraped to the overflow tank by the scraping assembly;

[0022] S204, the dissolution liquid is discharged from the discharge outlet at the bottom of the dissolution and purification tower and then filtered through the filter, and the insoluble impurities in the overflow tank are discharged through the slag discharge port.

[0023] Further preferably, in step S3 and step S4, the Na2S solution, NaClO3 solution and NaOH solution are all added to the outside of the guide tube through the dosing tube, and are evenly mixed with the dissolution solution through the circular flow formed by the rotation of the guide component.

[0024] Beneficial effects of the present invention:

[0025] The present invention uses a dissolution purification tower to leach metals from lithium battery ternary materials. It can also precipitate the leachate through the dissolution purification tower to separate the metal elements in the leachate, reducing the recovery process. Furthermore, a guide cylinder is provided in the dissolution purification tower. By controlling the rotation direction of the guide assembly, the direction of liquid circulation in the dissolution purification tower can be changed, so that different strategies can be adopted when adding liquid and adding gas to fully mix it with the original liquid, thereby improving the leaching and precipitation effects of the metal. Furthermore, an overflow box and an overflow weir are provided at the top of the dissolution purification tower. The scraper assembly at the top of the overflow weir can automatically remove insoluble impurities that float to the top of the liquid surface. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] The present invention will be further described below with reference to the accompanying drawings.

[0027] Figure 1 It is a schematic diagram of the overall structure of the dissolution purification tower of the present invention;

[0028] Figure 2 It is a schematic cross-sectional view of the dissolution purification tower of the present invention;

[0029] Figure 3 It is a schematic cross-sectional view of the guide tube of the dissolution purification tower of the present invention;

[0030] Figure 4 It is a structural schematic diagram of the diversion assembly of the dissolution purification tower of the present invention;

[0031] Figure 5 It is a structural schematic diagram of the overflow weir plate of the dissolution purification tower of the present invention;

[0032] Figure 6 It is a schematic cross-sectional view of the scraper assembly of the dissolution purification tower of the present invention;

[0033] Figure 7 This is a schematic structural diagram of the dosing pipe of the dissolution purification tower of the present invention;

[0034] Figure 8 It is a schematic diagram of the water flow direction of the two circulations of the dissolution purification tower of the present invention.

[0035] In the figure: 1-tower body, 2-guide tube, 3-connecting rod, 4-guide assembly, 5-overflow box, 6-overflow box, 7-overflow weir, 701-mounting part, 8-rotating joint, 9-motor, 10-scraper assembly, 11-dosing pipe, 1101-dosing hole, 1102-interface pipe, 12-feed port, 13-discharge port, 14-slag discharge port, 15-annular seat, 16-first blade, 17-second blade, 18-sleeve, 19-sliding collar, 20-guide rod, 21-spring, 22-scraper plate, 23-strip baffle. DETAILED DESCRIPTION

[0036] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0037] Example 1

[0038] A wet comprehensive recovery acid dissolution purification process comprises the following steps:

[0039] S1. The lithium battery ternary material crushed material is subjected to alkali washing at room temperature three times with a 1.5 mol / L NaOH solution, each time for 20 min, the washed lithium battery ternary material crushed material is dried and further crushed to a particle size of 50 μm by a jet mill, and then the lithium battery ternary material is added to a pulping machine and mixed with water, and stirred to obtain a slurry;

[0040] S2. Add a mixed acid solution of sulfuric acid and hydrogen peroxide to the dissolution purification tower, then add the slurry to the dissolution purification tower, control the solid-liquid ratio of the lithium battery ternary material and the acid solution to 30g / L, stir and mix evenly, heat to 90°C, and introduce SO2 at a rate of 0.1 L / min for 5h to obtain a leachate;

[0041] S3, the leachate is filtered through a filter, the filtrate is added back to the dissolution purification tower through a lift pump, Na2S solution and NaClO3 solution are added to the dissolution purification tower, and the pH is adjusted to 11-12 with NaOH solution, and the reaction is carried out for 1 hour. After the reaction is completed, it is allowed to stand for 40 minutes;

[0042] S4. The leachate is filtered again through the filter, and the filtrate is added back to the dissolution purification tower through the lifting pump. Excessive NaOH solution is added to the dissolution purification tower to co-precipitate the nickel, cobalt and manganese in the leachate. The mixed salt containing nickel, cobalt and manganese is obtained by filtration, and the recovery of lithium battery ternary materials is completed.

[0043] Example 2

[0044] A wet comprehensive recovery acid dissolution purification process comprises the following steps:

[0045] S1. The lithium battery ternary material crushed material is subjected to alkali washing at room temperature twice with a 2 mol / L NaOH solution, each time for 25 minutes, the washed lithium battery ternary material crushed material is dried and further crushed to a particle size of 35 μm by a jet mill, and then the lithium battery ternary material is added to a pulping machine and mixed with water, and stirred to obtain a slurry;

[0046] S2. Add a mixed acid solution of sulfuric acid and hydrogen peroxide to the dissolution purification tower, then add the slurry to the dissolution purification tower, control the solid-liquid ratio of the lithium battery ternary material and the acid solution to 40g / L, stir and mix evenly, heat to 80°C, and introduce SO2 at a rate of 0.3 L / min for 4h to obtain a leachate;

[0047] S3, the leachate is filtered through a filter, the filtrate is added back to the dissolution purification tower through a lift pump, Na2S solution and NaClO3 solution are added to the dissolution purification tower, and the pH is adjusted to 11-12 with NaOH solution, and the reaction is carried out for 2 hours. After the reaction is completed, it is allowed to stand for 30 minutes;

[0048] S4. The leachate is filtered again through the filter, and the filtrate is added back to the dissolution purification tower through the lifting pump. Excessive NaOH solution is added to the dissolution purification tower to co-precipitate the nickel, cobalt and manganese in the leachate. The mixed salt containing nickel, cobalt and manganese is obtained by filtration, and the recovery of lithium battery ternary materials is completed.

[0049] Example 3

[0050] A wet comprehensive recovery acid dissolution purification process comprises the following steps:

[0051] S1. The lithium battery ternary material crushed material is subjected to alkali washing at room temperature for 20 minutes using a 2.5 mol / L NaOH solution. The washed lithium battery ternary material crushed material is dried and further crushed to a particle size of 20 μm using a jet mill. The lithium battery ternary material is then added to a pulping machine and mixed with water, and the mixture is stirred to obtain a slurry.

[0052] S2. Add a mixed acid solution of sulfuric acid and hydrogen peroxide to the dissolution purification tower, then add the slurry to the dissolution purification tower, control the solid-liquid ratio of the lithium battery ternary material and the acid solution to 50g / L, stir and mix evenly, heat to 70°C, and introduce SO2 at a rate of 0.5 L / min for 3h to obtain a leachate;

[0053] S3, the leachate is filtered through a filter, the filtrate is added back to the dissolution purification tower through a lift pump, Na2S solution and NaClO3 solution are added to the dissolution purification tower, and the pH is adjusted to 11-12 with NaOH solution, and the reaction is carried out for 3 hours. After the reaction is completed, it is allowed to stand for 20 minutes;

[0054] S4. The leachate is filtered again through the filter, and the filtrate is added back to the dissolution purification tower through the lifting pump. Excessive NaOH solution is added to the dissolution purification tower to co-precipitate the nickel, cobalt and manganese in the leachate. The mixed salt containing nickel, cobalt and manganese is obtained by filtration, and the recovery of lithium battery ternary materials is completed.

[0055] The structure of the dissolution purification tower in Examples 1 to 3 of the present invention is as follows Figure 1-7 As shown, it includes a tower body 1, a guide tube 2 is vertically provided inside the tower body 1, the guide tube 2 is fixedly connected to the inner wall of the tower body 1 through a connecting rod 3, the upper and lower ends of the guide tube 2 are rotatably connected to the guide assembly 4, a drive shaft 5 is vertically passed through the guide tube 2, the drive shaft 5 drives the guide assembly 4 to rotate, the upper end of the tower body 1 is fixedly connected to the overflow box 6, the overflow box 6 is provided with an overflow weir plate 7, the lower end of the overflow weir plate 7 is fixedly connected to the inner wall of the tower body 1, the upper end of the drive shaft 5 is rotatably connected to the overflow box 6, and the overflow box 6 is provided with an overflow weir plate 7. A rotary joint 8 is fixedly installed on the top of the dynamic shaft 5. The driving shaft 5 is a hollow shaft. An air inlet hole is opened on the surface of the driving shaft 5 in the middle of the guide tube 2. The upper end of the driving shaft 5 is engaged with the output shaft of the motor 9 through a gear. A scraper assembly 10 is fixedly installed on the surface of the driving shaft 5 corresponding to the upper end of the overflow weir plate 7, a dosing pipe 11 is fixedly installed on the upper end of the inner wall of the tower body 1, a feed port 12 is fixedly installed on the lower end of the side wall of the tower body 1, a discharge port 13 is fixedly installed on the bottom of the tower body 1, and a slag discharge port 14 is fixedly installed on the lower end of the side wall of the overflow box 6.

[0056] The guide assembly 4 includes an annular seat 15, the inner diameter and outer diameter of the annular seat 15 are the same as those of the guide tube 2, and the inner wall and outer wall of the annular seat 15 are respectively fixedly installed with a first blade 16 and a second blade 17 near one end of the guide tube 2. The inclination angles of the first blade 16 and the second blade 17 are opposite, and the middle of the first blade 16 is fixedly connected to the drive shaft 5.

[0057] The overflow box 6 has a larger diameter than the tower body 1 . The overflow weir plate 7 is an annular plate. An outwardly extending mounting portion 701 is provided at the lower end of the overflow weir plate 7 . The mounting portion 701 has an arc-shaped cross section and is fixedly connected to the inner wall of the tower body 1 .

[0058] The scraper assembly 10 includes a sleeve 18, the drive shaft 5 passes through the sleeve 18, the sleeve 18 is fixedly connected to the drive shaft 5, the inner diameter of the sleeve 18 is larger than the diameter of the drive shaft 5, and a sliding ring 19 is provided at the bottom end of the sleeve 18. The inner diameter of the top of the sliding ring 19 is the same as the diameter of the drive shaft 5, and the outer diameter of the sliding ring 19 is the same as that of the sleeve 18. A plurality of guide rods 20 are fixedly mounted on the surface of the sliding collar 19. The upper ends of the guide rods 20 pass through the side wall of the sleeve 18. The guide rods 20 are slidably connected to the sleeve 18. A spring 21 is provided in the gap between the inside of the sleeve 18 and the drive shaft 5. The top of the sliding collar 19 is connected to the top of the sleeve 18 through the spring 21. A scraper plate 22 is fixedly mounted on the outer wall of the sliding collar 19. The scraper plate 22 is arranged in a quarter spiral shape. The outer ring of the scraper plate 22 fits against the inner wall of the overflow weir 7. A strip baffle 23 is fixedly mounted on the upper end of the scraper plate 22. The strip baffle 23 extends out of the overflow weir 7 at one end away from the sliding collar 19.

[0059] The dosing pipe 11 is in a circular shape. A mounting groove is provided on the inner wall of the tower body 1 corresponding to the dosing pipe 11. The dosing pipe 11 is embedded in the mounting groove on the inner wall of the tower body 1. The inner diameter of the dosing pipe 11 is the same as that of the tower body 1. A plurality of dosing holes 1101 arranged in a circular array are opened on the inner wall of the dosing pipe 11. An interface pipe 1102 is fixedly installed on the outer wall of one side of the dosing pipe 11.

[0060] Based on the structure of the above-mentioned dissolution purification tower, the acid dissolution purification process step S2 for wet comprehensive recovery of the present invention may specifically include the following steps:

[0061] S201, add the acid solution into the tower body 1 of the dissolution purification tower through the feed port 12 until the liquid level is higher than the top of the guide tube 2, and drive the drive shaft 5 to rotate by the motor 9, so that the guide components 4 at both ends of the guide tube 2 rotate, driving the acid solution inside the tower body 1 to form a circulation, such as Figure 8 (a)

[0062] S202, adding the slurry to the outside of the guide tube 2 through the dosing pipe 11, and then adding the acid solution to the inside of the tower body 1 of the dissolution purification tower through the feed port 12. The acid solution passes through the inside of the tower body 1 until the liquid level is flush with the top of the overflow weir plate 7, and circulates to mix the slurry and the acid solution evenly, and then heats the mixed solution to 70-90°C;

[0063] S203, the motor 9 drives the drive shaft 5 to reverse, so that the liquid inside the tower body 1 forms a reverse circulation, such as Figure 8 As shown in (b), SO2 is then added to the middle of the guide tube 2 through the rotary joint 8 and the drive shaft 5. The SO2 and liquid flow out from the bottom of the guide tube 2 through the circulation and then flow upward from the outside of the guide tube 2. SO2 is introduced at a rate of 0.1-0.5 L / min. The treatment is carried out for 3-5 hours to dissolve the lithium battery ternary material. Some insoluble impurities float on the top of the overflow weir plate 7 driven by the SO2 gas and are scraped into the overflow box 6 by the scraper assembly 10;

[0064] S204 , the dissolution liquid is discharged from the discharge port 13 at the bottom of the dissolution purification tower and then filtered through a filter, and the insoluble impurities in the overflow box 6 are discharged through the slag discharge port 14 .

[0065] At the same time, based on the structure of the above-mentioned dissolution purification tower, the Na2S solution, NaClO3 solution, and NaOH solution in the acid-dissolution purification process steps S3 and S4 for wet comprehensive recovery of the present invention are all added to the outside of the guide tube 2 through the dosing tube 11, and are evenly mixed with the dissolution liquid through the circulation formed by the rotation of the guide component 4.

[0066] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0067] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention, and such changes and modifications fall within the scope of the invention as claimed.

Claims

1. A wet comprehensive recovery acid dissolution purification process, characterized in that: The following steps are involved: S1. The lithium battery ternary material is further crushed into a particle size of 20-50 μm by a jet mill, and then the lithium battery ternary material is added to a pulping machine and mixed with water, and stirred to obtain a slurry; S2. Add acid to the dissolution purification tower, then add the slurry to the dissolution purification tower, stir and mix evenly, heat to 70-90°C, introduce SO2 at a rate of 0.1-0.5 L / min, and treat for 3-5 hours to obtain a leachate; S3, filtering the leachate through a filter, adding the filtrate back to the dissolution purification tower through a lift pump, adding Na2S solution and NaClO3 solution to the dissolution purification tower, and adjusting the pH to 11-12 with NaOH solution, reacting for 1-3 hours, and standing for 20-40 minutes after the reaction is completed; S4. The leachate is filtered again through a filter, and the filtrate is fed back to the dissolution purification tower through a lift pump. Excessive NaOH solution is added to the dissolution purification tower to co-precipitate nickel, cobalt and manganese in the leachate. The mixed salt containing nickel, cobalt and manganese is obtained by filtration, thereby completing the recovery of lithium battery ternary materials; The top end of the driving shaft is fixedly provided with a driving member, and the lower end of the driving member is rotated to be connected with the driving member by the driving member. The guide assembly includes an annular seat, the inner diameter and outer diameter of the annular seat are the same as those of the guide tube, the inner wall and outer wall of the annular seat are close to one end of the guide tube for fixing the first blade and the second blade respectively, the inclination angles of the first blade and the second blade are opposite, and the middle of the first blade is fixedly connected to the drive shaft.

2. The acid-dissolving purification process for wet comprehensive recovery according to claim 1, characterized in that: The lithium battery ternary material is first alkali-washed at room temperature with a 1.5-2.5 mol / L NaOH solution before being added with acid solution for leaching. The alkali washing times are 1-3 times, and each washing time is 20-30 minutes.

3. The acid dissolution purification process for wet comprehensive recovery according to claim 1, characterized in that: The acid solution is a mixture of sulfuric acid and hydrogen peroxide, and the solid-liquid ratio of the lithium battery ternary material and the acid solution is 30-50g / L.

4. The acid dissolution purification process for wet comprehensive recovery according to claim 1, characterized in that: The overflow box has a diameter larger than the tower body, the overflow weir plate is an annular plate, and a mounting portion extending outward is provided at the lower end of the overflow weir plate. The cross section of the mounting portion is arc-shaped, and the mounting portion is fixedly connected to the inner wall of the tower body.

5. The acid dissolution purification process for wet comprehensive recovery according to claim 1, characterized in that: The scraper assembly includes a sleeve, the drive shaft passes through the sleeve, the sleeve is fixedly connected to the drive shaft, the inner diameter of the sleeve is larger than the diameter of the drive shaft, a sliding collar is provided at the bottom end of the sleeve, the inner diameter of the top of the sliding collar is the same as the diameter of the drive shaft, the outer diameter of the sliding collar is the same as the sleeve, a plurality of guide rods are fixedly installed on the surface of the sliding collar, the upper end of the guide rod passes through the side wall of the sleeve, the guide rod is slidably connected to the sleeve, a spring is provided in the gap between the inside of the sleeve and the drive shaft, the top of the sliding collar is connected to the top of the sleeve through the spring, a scraper plate is fixedly installed on the outer wall of the sliding collar, the scraper plate is arranged in a quarter spiral shape, the outer ring of the scraper plate is in contact with the inner wall of the overflow weir plate, and a strip baffle is fixedly installed on the upper end of the scraper plate, and the strip baffle extends out of the overflow weir plate away from the end of the sliding collar.

6. The acid dissolution purification process for wet comprehensive recovery according to claim 1, characterized in that: The dosing pipe is in a circular shape, and a mounting groove is provided on the inner wall of the tower body corresponding to the dosing pipe. The dosing pipe is embedded in the mounting groove on the inner wall of the tower body. The inner diameter of the dosing pipe is the same as the inner diameter of the tower body. A plurality of dosing holes arranged in a circular array are opened on the inner wall of the dosing pipe, and an interface pipe is fixedly installed on the outer wall of one side of the dosing pipe.

7. The acid dissolution purification process for wet comprehensive recovery according to claim 1, characterized in that: The step S2 specifically includes the following steps: S201, adding acid liquid into the tower body of the dissolution purification tower through the feed port until the liquid level is higher than the top of the guide tube, and rotating the drive shaft by the motor to rotate the guide components at both ends of the guide tube, thereby driving the acid liquid inside the tower body to form a circulation; S202, adding the slurry to the outside of the guide tube through the dosing pipe, and then adding the acid solution to the inside of the dissolution purification tower through the feed port. The acid solution is passed through the inside of the tower until the liquid level is flush with the top of the overflow weir plate, and the slurry and the acid solution are evenly mixed. Then, the mixed solution is heated to 70-90°C; S203. The motor drives the drive shaft to reverse, so that the liquid inside the tower body forms a reverse circulation. Then, SO2 is added to the middle of the guide tube through the rotary joint and the drive shaft. The SO2 and liquid flow out from the bottom of the guide tube through the circulation and then flow upward from the outside of the guide tube. SO2 is introduced at a rate of 0.1-0.5 L / min. The treatment is carried out for 3-5 hours to dissolve the lithium battery ternary material. Some insoluble impurities float on the top of the overflow weir plate driven by the SO2 gas and are scraped into the overflow box by the scraper assembly; S204, the dissolution liquid is discharged from the discharge port at the bottom of the dissolution purification tower and filtered through a filter, and the insoluble impurities in the overflow box are discharged through the slag discharge port.

8. The acid dissolution purification process for wet comprehensive recovery according to claim 1, characterized in that: In step S3 and step S4, the Na2S solution, NaClO3 solution and NaOH solution are all added to the outside of the guide tube through the dosing tube, and are evenly mixed with the dissolution solution through the circular flow formed by the rotation of the guide component.

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