Waste battery recycling manufacturing equipment and waste lithium battery valuable metal extraction process

Abstract

The application provides a waste battery recycling manufacturing device and a valuable metal extraction process for waste lithium batteries, relates to the technical field of waste battery recycling and regeneration, and comprises a precipitation tank, a generation tank, a blowing mechanism, a driving mechanism and a generation mixing mechanism. The blowing mechanism comprises a rotating frame and three extrusion wheels. The rotating frame is arranged in the interior of the generation tank. The three extrusion wheels are rotationally connected to the interior side of the rotating frame. The top of the driving mechanism is fixedly provided with three mounting seats. The rotating shaft is rotated to drive the rotating frame and the extrusion wheels to rotate. In the process of rapid rotation of the extrusion wheels, negative pressure is formed in the blowing hose, nitrogen is extracted, and is sprayed out at a position 10-20 cm below the filtrate, forming an "umbrella-shaped" airflow. Local over-acid areas are eliminated, local pH sudden drops are avoided, crystal etch pits caused by the local pH sudden drops are avoided, the growth environment of the crystal grains is optimized, the lithium recovery rate is improved, and the risk of reverse reaction of lithium carbonate is effectively avoided.

Description

Technical Field

[0001] This invention relates to the field of waste battery recycling technology, and in particular to waste battery recycling equipment and processes for extracting valuable metals from waste lithium batteries. Background Technology

[0002] Although the capacity of the positive electrode materials in waste batteries (such as lithium nickel cobalt manganese oxide NCM, lithium iron phosphate LFP, etc.) decays after multiple charge and discharge cycles, the chemical properties of the metal elements such as nickel, cobalt, manganese, and lithium are not completely destroyed. After standardized recycling, processing, and reuse processes, the extracted metal materials can be used to manufacture secondary batteries. This process not only achieves resource recycling but also reduces dependence on primary mineral resources, and has significant economic and environmental value.

[0003] In related technologies, the recycling and remanufacturing of waste batteries requires the introduction of carbon dioxide into the filtrate of the leachate from waste lithium batteries to generate lithium carbonate, which is needed for battery manufacturing. However, some existing remanufacturing equipment does not easily avoid the risk of reverse reaction of lithium carbonate when introducing carbon dioxide into the filtrate. When excessive carbon dioxide is introduced or the local pH decreases, soluble lithium bicarbonate is generated, causing the precipitated lithium carbonate to re-dissolve, resulting in a decrease in lithium recovery rate or a deterioration in crystal quality.

[0004] Therefore, it is necessary to provide waste battery recycling equipment and waste lithium battery valuable metal extraction processes to solve the above-mentioned technical problems. Summary of the Invention

[0005] This invention provides waste battery recycling equipment and a process for extracting valuable metals from waste lithium batteries, solving the technical problem that some existing recycling equipment in related technologies cannot avoid the risk of reverse reaction of lithium carbonate when carbon dioxide is introduced into the filtrate.

[0006] To solve the above-mentioned technical problems, the waste battery recycling equipment provided by the present invention includes a sedimentation tank, a generation tank, a purging mechanism, a driving mechanism, and a generation and mixing mechanism;

[0007] The purging mechanism includes a rotating frame and three extrusion wheels. The rotating frame is located inside the generating groove, and the three extrusion wheels are rotatably connected to the inner side of the rotating frame. The top of the driving mechanism is fixed with three mounting seats, and the inner side of each of the three mounting seats is provided with a purging hose.

[0008] The driving mechanism includes a mounting plate, a driving plate, and a driving gear. The mounting plate is fixedly connected to the inner wall of the generating groove. The driving gear is rotatably connected to the inner side of the mounting plate through a hollow rotating shaft. The driving gear is fixedly connected to the bottom of the driving plate through the hollow rotating shaft. Three sliding seats are slidably connected to the top of the mounting plate. The top of the three sliding seats is fixedly connected to the bottom of the three mounting seats respectively. Each of the three sliding seats has a sliding rod fixedly provided on its top. The three sliding rods are slidably connected to the inner side of the driving plate.

[0009] The generating mixing mechanism is used to mix carbon dioxide and filtrate to improve the generation efficiency of lithium carbonate.

[0010] Preferably, an electric telescopic rod is fixedly provided at the bottom of the mounting plate, and a gear plate is fixedly provided at the output end of the electric telescopic rod, the gear plate meshing with the drive gear.

[0011] Preferably, a pH sensor and a carbon dioxide sensor are vertically arranged on the inner side of the mounting plate for real-time monitoring of the pH value and carbon dioxide concentration in each area, and a solenoid valve and a flow meter are arranged on the surface of the purge hose.

[0012] Preferably, a sedimentation mixing mechanism is vertically rotatably connected to the inner side of the sedimentation tank. The sedimentation mixing mechanism includes a rotating rod vertically rotatably connected to the inner side of the sedimentation tank. Three sets of connecting frames are fixed on the surface of the rotating rod, and mixing frames are fixed on both sides of the three sets of connecting frames. A drive motor for driving the rotating rod to rotate is provided at the top of the sedimentation tank.

[0013] Preferably, a feeding mechanism is fixedly provided on the top of the sedimentation tank. The feeding mechanism includes an annular track fixedly provided on the top of the sedimentation tank. A slider is slidably connected to the surface of the annular track. An mounting plate is fixedly provided on the top of the slider. A feeding bin is fixedly provided on the top of the mounting plate. A drive plate is fixedly provided on the surface of the rotating rod. A connecting bolt is vertically slidably connected to the inner sides of the mounting plate and the drive plate.

[0014] The top of the sedimentation tank is provided with an annular through groove, and a bridge is fixedly provided on the top of the inner wall of the sedimentation tank. The rotating rod is rotatably connected to the bridge.

[0015] Preferably, the generating mixing mechanism includes a rotating shaft vertically rotatably connected to the inner side of the generating tank, two sets of stirring paddles are fixedly mounted on the surface of the rotating shaft, the peripheral side of the rotating shaft is fixedly connected to the rotating frame, a support base is fixedly mounted on the top of the generating tank, and a rotating motor for driving the rotating shaft to rotate is provided on the top of the support base.

[0016] Preferably, an air intake mechanism is fixedly provided at the bottom end of the rotating shaft. The air intake mechanism includes an air intake plate fixedly provided at the bottom end of the rotating shaft. Multiple nozzles are connected to the surface of the air intake plate. Multiple paddles are arranged in a circular array on the surface of the air intake plate. A conveying pipe is connected to the bottom of the inner wall of the generating tank.

[0017] Preferably, a support frame is fixedly provided at the bottom of the sedimentation tank, a discharge pipe is connected to the bottom of the sedimentation tank, and multiple support legs are fixedly provided at the bottom of the generating tank.

[0018] A process for extracting valuable metals from waste lithium batteries includes the following steps:

[0019] Step S1: Wash the carbon felt sheet with acetone and pure water to remove surface dirt, and dry it to obtain a clean carbon felt.

[0020] Step S2: Mix and stir polyacrylonitrile, super carbon black and N,N-dimethylformamide in a certain proportion until the slurry becomes viscous and uniform. Cut the carbon felt obtained in step S1 into a certain size, immerse it in the slurry and dry it to obtain polyacrylonitrile carbon felt.

[0021] Step S3: Place the polyacrylonitrile carbon felt obtained in step S2 into a water bath, add hydroxylamine hydrochloride, sodium carbonate and sodium hydroxide to carry out the hydroxylamine reaction. After the reaction is completed, dry it in a vacuum furnace to obtain a hydroxylamine oxime carbon felt.

[0022] Step S4: Place the amylopectin carbon felt obtained in step S3 in deionized water, add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and glutamic acid, react and dialyze at room temperature, then treat and dry in polyethylene glycol solution to obtain glutamic acid modified amylopectin carbon felt electrode.

[0023] Step S5: Place the positive electrode powder into a closed glass reactor containing sulfuric acid solution;

[0024] Step S6: Place the glass reactor from step S5 in a constant temperature magnetic stirrer, add an organic phase containing 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester and sulfonated kerosene, and equip it with glutamic acid modified ammonia oxime carbon felt as the anode and cathode, respectively.

[0025] Step S7: Connect the anode and cathode to the power supply respectively, place the ultrasonic probe between the anode and cathode, and then perform leaching, electrodeposition and extraction respectively;

[0026] Step S8: Filtration. The collected organic phase is back-extracted with sulfuric acid solution to obtain cobalt sulfate. The aqueous phase is then purged with carbon dioxide to obtain lithium carbonate.

[0027] Step S9: Use an eluent and apply a DC reverse bias voltage to the electrode containing high-purity nickel and manganese dioxide to perform desorption.

[0028] Compared with related technologies, the waste battery recycling equipment and waste lithium battery valuable metal extraction process provided by this invention have the following beneficial effects:

[0029] The gear plate moves forward, driving the drive gear and drive disc to rotate. Under the action of the slide rod, the three sliding seats drive the mounting base and the purge hose to move inward, so that the purge hose comes into contact with the extrusion wheel. The rotating shaft drives the rotating frame and the extrusion wheel to rotate. During the rapid rotation of the extrusion wheel, a negative pressure is formed in the purge hose, which extracts nitrogen gas and delivers it to a depth of 10-20 cm below the filtrate to form an "umbrella-shaped" airflow. This eliminates local over-acid areas, avoids crystal pitting caused by sudden drops in local pH, optimizes the growth environment of the crystal grains, improves the lithium recovery rate, and effectively avoids the risk of reverse reaction of lithium carbonate.

[0030] When this equipment is in operation, if a localized area of ​​excessive carbon dioxide is detected, the control system automatically sends a command to the solenoid valve on the nitrogen purging pipeline of the corresponding area to open the nitrogen pipeline. When the extrusion wheel rotates, nitrogen is released selectively through a single purging hose. This can quickly and accurately reduce the carbon dioxide concentration in the localized area of ​​excessive carbon dioxide, preventing lithium carbonate re-dissolution due to localized carbon dioxide excess, and improving the yield and purity of lithium carbonate precipitation. Compared to introducing nitrogen throughout the entire system, this method can more efficiently solve localized problems, reduce interference with other normal reaction areas, and reduce the overall amount of nitrogen used, thus lowering production costs. It also avoids the impact of introducing nitrogen throughout the entire reaction system, maintaining the stability of the reaction in other areas, and is beneficial to improving the controllability of the reaction and the stability of product quality. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on the structures shown in these drawings without creative effort.

[0032] Figure 1 The optimal structural schematic diagram provided for this invention;

[0033] Figure 2 This is a schematic diagram of the structure of the generated groove cross-section provided by the present invention;

[0034] Figure 3 This is a schematic diagram of the purging mechanism and driving mechanism provided by the present invention;

[0035] Figure 4 for Figure 3 The enlarged structural diagram at point A is shown below;

[0036] Figure 5 This is a schematic diagram of the installation disk provided by the present invention;

[0037] Figure 6 for Figure 5 The diagram shows the structural schematic of the bottom view of the mounting plate.

[0038] Figure 7 A schematic diagram showing the state in which the rotating frame of the present invention drives the extrusion wheel to rotate and extrudes the purge hose;

[0039] Figure 8 This is a structural schematic diagram of a cross-sectional view of a sedimentation tank provided by the present invention;

[0040] Figure 9 This is a schematic diagram of the feeding mechanism provided by the present invention;

[0041] Figure 10 This is a schematic diagram of the slider and mounting plate provided by the present invention;

[0042] Figure 11 This is a schematic diagram of the precipitation mixing mechanism provided by the present invention;

[0043] Figure 12 This is a schematic diagram of the intake mechanism provided by the present invention;

[0044] Figure 13 This is a schematic diagram of the structure of the mixing mechanism provided by the present invention.

[0045] Explanation of icon numbers:

[0046] 1. Sedimentation tank; 2. Formation tank;

[0047] 3. Purging mechanism; 31. Rotating frame; 32. Extrusion wheel; 33. Mounting base; 34. Purging hose;

[0048] 4. Drive mechanism; 41. Mounting plate; 42. Drive plate; 43. Drive gear; 44. Sliding seat; 45. Slide rod; 46. Electric telescopic rod; 47. Gear plate;

[0049] 5. Generating and mixing mechanism; 51. Rotating shaft; 52. Stirring paddle; 53. Support base; 54. Rotating motor;

[0050] 6. pH sensor; 7. Carbon dioxide sensor;

[0051] 8. Sedimentation and mixing mechanism; 81. Rotating rod; 82. Connecting frame; 83. Mixing frame; 84. Drive motor;

[0052] 9. Feeding mechanism; 91. Circular track; 92. Slider; 93. Mounting plate; 94. Feeding bin; 95. Drive plate; 96. Connecting bolt;

[0053] 10. Cable trays;

[0054] 11. Air intake mechanism; 111. Air intake disc; 112. Nozzle; 113. Paddle plate; 114. Delivery pipe;

[0055] 12. Support frame; 13. Discharge pipe; 14. Support leg.

[0056] The realization of the objective, functional features and advantages of the present invention will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0057] 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 a part of the embodiments of the present invention, and not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0058] This invention provides equipment for the recycling and manufacturing of waste batteries and a process for extracting valuable metals from waste lithium batteries.

[0059] First embodiment:

[0060] Please see Figures 1 to 7 Waste battery recycling equipment includes a sedimentation tank 1, a generation tank 2, a purging mechanism 3, a drive mechanism 4, and a generation and mixing mechanism 5;

[0061] The purging mechanism 3 includes a rotating frame 31 and three extrusion wheels 32. The rotating frame 31 is disposed inside the generating groove 2. The three extrusion wheels 32 are rotatably connected to the inner side of the rotating frame 31. The top of the driving mechanism 4 is fixed with three mounting seats 33. Each of the three mounting seats 33 is provided with a purging hose 34 on its inner side.

[0062] A pH sensor 6 and a carbon dioxide sensor 7 are vertically arranged on the inner side of the mounting plate 41 for real-time monitoring of the pH value and carbon dioxide concentration in each area. A solenoid valve and a flow meter are arranged on the surface of the purge hose 34.

[0063] Please combine Figure 3When the three mounting bases 33 are adjusted inward so that the extrusion wheel 32 contacts the purge hose 34 and extrudes the purge hose 34, the rotating shaft 51 rotates, driving the rotating frame 31 and the extrusion wheel 32 to rotate. During the rapid rotation of the extrusion wheel 32, a negative pressure is formed inside the purge hose 34, thereby extracting nitrogen. The extracted nitrogen is transported through the purge hose 34 to a depth of 10-20 cm below the filtrate and sprayed out, forming an "umbrella-shaped" airflow.

[0064] Preferably, the extraction end of the purge hose 34 is connected to a nitrogen cylinder, the purge hose 34 is made of fluororubber, and the surface of the extrusion roller 32 is provided with a ceramic coating.

[0065] Preferably, the generation tank 2 is divided into three areas by pH sensor 6 and carbon dioxide sensor 7, and the pH value and carbon dioxide concentration of each area are monitored in real time. Once the pH value of a certain area is lower than the set threshold or the carbon dioxide concentration is higher than the set value, the area can be determined as a local excess area.

[0066] The solenoid valve can quickly open or close according to the instructions of the monitoring system to precisely control the flow of nitrogen. The flow meter is used to regulate and monitor the flow of nitrogen to ensure that nitrogen can be introduced at a suitable flow rate in areas of local excess. When a local excess area is detected, the control system automatically sends a command to the solenoid valve on the nitrogen purging pipeline in the corresponding area to open the nitrogen pipeline and regulate the nitrogen flow rate at the same time.

[0067] The driving mechanism 4 includes a mounting plate 41, a driving plate 42, and a driving gear 43. The mounting plate 41 is fixedly connected to the inner wall of the generating groove 2. The driving gear 43 is rotatably connected to the inner side of the mounting plate 41 through a hollow rotating shaft. The driving gear 43 is fixedly connected to the bottom of the driving plate 42 through a hollow rotating shaft. Three sliding seats 44 are slidably connected to the top of the mounting plate 41. The tops of the three sliding seats 44 are respectively fixedly connected to the bottoms of the three mounting seats 33. Each of the three sliding seats 44 has a sliding rod 45 fixedly provided on its top. The three sliding rods 45 are slidably connected to the inner side of the driving plate 42.

[0068] An electric telescopic rod 46 is fixedly provided at the bottom of the mounting plate 41, and a gear plate 47 is fixedly provided at the output end of the electric telescopic rod 46. The gear plate 47 meshes with the drive gear 43.

[0069] Please combine Figures 3 to 7: Start the electric telescopic rod 46. The electric telescopic rod 46 retracts and drives the gear plate 47 to move forward. The movement of the gear plate 47 drives the drive gear 43 to rotate. The rotation of the drive gear 43 drives the drive disc 42 to rotate. Under the action of the slide rod 45, the three sliding seats 44 slide inward on the top of the mounting plate 41. The movement of the sliding seats 44 drives the three mounting seats 33 and the blow hose 34 to move inward, so that the blow hose 34 comes into contact with the extrusion wheel 32.

[0070] The generating mixing mechanism 5 is used to mix carbon dioxide and filtrate to promote the generation efficiency of lithium carbonate.

[0071] In this embodiment, unlike existing battery regeneration equipment, this equipment moves forward via gear plate 47, driving drive gear 43 and drive disk 42 to rotate. Under the action of slide rod 45, three sliding seats 44 drive mounting seat 33 and purge hose 34 to move inward, causing purge hose 34 to contact extrusion wheel 32. The rotating shaft 51 rotates, driving rotating frame 31 and extrusion wheel 32 to rotate. During the rapid rotation of extrusion wheel 32, a negative pressure is formed inside purge hose 34, thereby extracting nitrogen gas and delivering it to a depth of 10-20 cm below the filtrate to form an "umbrella-shaped" airflow. This eliminates local over-acid areas, avoids crystal pitting caused by sudden pH drops, optimizes the growth environment of crystal grains, improves lithium recovery rate, and effectively avoids the risk of reverse reaction of lithium carbonate.

[0072] When this equipment is in operation, if a localized excess area is detected, the control system automatically sends a command to the solenoid valve on the nitrogen purging pipeline of the corresponding area to open the nitrogen pipeline. When the extrusion wheel 32 rotates, nitrogen is released selectively through a single purging hose 34. This can quickly and accurately reduce the carbon dioxide concentration in the localized excess area, preventing lithium carbonate re-dissolution due to localized carbon dioxide excess, and improving the yield and purity of lithium carbonate precipitation. Compared with overall nitrogen purging, this method can solve localized problems more efficiently, reduce interference with other normal reaction areas, reduce the overall nitrogen consumption, lower production costs, and avoid the impact of overall nitrogen purging on the entire reaction system, maintaining the stability of the reaction in other areas. This is beneficial for improving the controllability of the reaction and the stability of product quality.

[0073] Second embodiment:

[0074] Please see Figures 8 to 11 The sedimentation tank 1 is vertically rotatably connected to a sedimentation mixing mechanism 8. The sedimentation mixing mechanism 8 includes a rotating rod 81 vertically rotatably connected to the inside of the sedimentation tank 1. Three sets of connecting frames 82 are fixed on the surface of the rotating rod 81. Mixing frames 83 are fixed on both sides of the three sets of connecting frames 82. A drive motor 84 for driving the rotating rod 21 to rotate is provided on the top of the sedimentation tank 1.

[0075] Please combine Figure 11 Start the drive motor 84. The drive motor 84 rotates and drives the rotating rod 81 to rotate. The rotation of the rotating rod 81 drives the mixing frame 83 to rotate through the connecting frame 82. The rotation of the mixing frame 83 mixes the sodium carbonate and the leachate, and finally generates nickel carbonate precipitate. After filtration, the precipitate is obtained.

[0076] The top of the sedimentation tank 1 is fixedly provided with a feeding mechanism 9. The feeding mechanism 9 includes an annular track 91 fixedly provided on the top of the sedimentation tank 1. A slider 92 is slidably connected to the surface of the annular track 91. An mounting plate 93 is fixedly provided on the top of the slider 92. A feeding bin 94 is fixedly provided on the top of the mounting plate 93. A drive plate 95 is fixedly provided on the surface of the rotating rod 81. A connecting bolt 96 is vertically slidably connected to the inner sides of the mounting plate 93 and the drive plate 95.

[0077] The top of the sedimentation tank 1 is provided with an annular through groove, and the top of the inner wall of the sedimentation tank 1 is fixed with a bridge frame 10. The rotating rod 81 is rotatably connected to the bridge frame 10.

[0078] Please combine Figure 9 When the rotating rod 81 rotates, it will simultaneously drive the drive plate 95 to rotate. The rotation of the drive plate 95 causes the slider 92 to slide on the surface of the circular track 91 through the connecting bolt 96. During the movement of the slider 92, the feeding bin 94 is driven to move in a circular motion through the mounting plate 93, thereby performing circular feeding.

[0079] In this embodiment, the rotation of the drive motor 84 drives the rotating rod 81, the connecting frame 82, and the mixing frame 83 to rotate, mixing sodium carbonate and the leachate to generate nickel carbonate precipitate. When the rotating rod 81 rotates, it also drives the drive plate 95 to rotate. Under the action of the slider 92 and the mounting plate 93, the feeding bin 94 feeds sodium carbonate along the annular track 91. The annular feeding makes the sodium carbonate more evenly dispersed. Combined with the stirring of the mixing frame 83, it avoids excessively high local concentration, reduces side reactions, improves the purity of nickel carbonate precipitate, reduces process intervals during synchronous operation, accelerates the contact reaction speed between sodium carbonate and leachate, shortens the precipitation formation time, and thus improves the production efficiency of lithium carbonate.

[0080] Third embodiment:

[0081] Please see Figure 2 , Figure 12 and Figure 13The generating mixing mechanism 5 includes a rotating shaft 51 that is vertically rotatably connected to the inner side of the generating tank 2. Two sets of stirring paddles 52 are fixedly provided on the surface of the rotating shaft 51. The peripheral side of the rotating shaft 51 is fixedly connected to the rotating frame 31. A support base 53 is fixedly provided on the top of the generating tank 2. A rotating motor 54 for driving the rotating shaft 51 to rotate is provided on the top of the support base 53.

[0082] Please combine Figure 13 Start the rotating motor 54. The rotating motor 54 rotates and drives the rotating shaft 51 to rotate. The rotating shaft 51 rotates and drives the two sets of stirring paddles 52 to rotate. The rotation of the stirring paddles 52 generates shear force, which mixes the carbon dioxide and the filtrate.

[0083] An air intake mechanism 11 is fixedly provided at the bottom end of the rotating shaft 51. The air intake mechanism 11 includes an air intake plate 111 fixedly provided at the bottom end of the rotating shaft 51. A plurality of nozzles 112 are connected to the surface of the air intake plate 111. A plurality of paddles 113 are arranged in a ring array on the surface of the air intake plate 111. A conveying pipe 114 is connected to the bottom end of the air intake plate 111. The conveying pipe 114 is rotatably connected to the bottom of the inner wall of the generating tank 2.

[0084] Please combine Figure 12 When the rotating shaft 51 rotates, it simultaneously drives the bottom air intake plate 111 to rotate. Carbon dioxide is introduced into the air intake plate 111 through the delivery pipe 114. The carbon dioxide enters the filtrate through the nozzle 112. The rotation of the air intake plate 111 causes carbon dioxide to be introduced into the generating tank 2 in a rotary manner. When the air intake plate 111 rotates, the paddle plate 113 will rotate at the same time, thereby shearing the carbon dioxide bubbles and turning large bubbles into small bubbles.

[0085] The bottom of the sedimentation tank 1 is fixedly provided with a support frame 12, and the bottom of the sedimentation tank 1 is connected to a discharge pipe 13. The bottom of the generating tank 2 is fixedly provided with multiple support legs 14.

[0086] In this embodiment, the air intake plate 111 rotates synchronously with the rotating shaft 51, allowing carbon dioxide to enter the filtrate through the nozzle 112 in a rotating trajectory. Combined with the shearing force of the stirring paddle 52, carbon dioxide can be rapidly diffused in the generation tank 2, avoiding the accumulation of carbon dioxide in local areas. The synergy of rotating air intake and stirring can make the carbon dioxide concentration more uniform in the tank, avoiding excessive local pH reduction and reducing the risk of resolution.

[0087] When the air intake disc 111 rotates, the paddle 113 rotates synchronously, forming mechanical shear on the large carbon dioxide bubbles that have just been discharged from the nozzle 112, breaking them into micron-sized small bubbles. The specific surface area of ​​the small bubbles is much larger than that of the large bubbles, which can significantly improve the dissolution rate and solubility of carbon dioxide in the filtrate, allowing more carbon dioxide to participate in the reaction, thereby improving the conversion rate of lithium carbonate and increasing the precipitation yield. The uniform distribution of carbon dioxide and the slow and controllable reaction allow lithium carbonate crystals to grow in an orderly manner, reducing impurity encapsulation and improving product purity.

[0088] Fourth embodiment:

[0089] A process for extracting valuable metals from waste lithium batteries includes the following steps:

[0090] Step S1: Wash the carbon felt sheet with acetone and pure water to remove surface dirt, and dry it to obtain a clean carbon felt.

[0091] Step S2: Mix and stir polyacrylonitrile, super carbon black and N,N-dimethylformamide in a certain proportion until the slurry becomes viscous and uniform. Cut the carbon felt obtained in step S1 into a certain size, immerse it in the slurry and dry it to obtain polyacrylonitrile carbon felt.

[0092] Step S3: Place the polyacrylonitrile carbon felt obtained in step S2 into a water bath, add hydroxylamine hydrochloride, sodium carbonate and sodium hydroxide to carry out the hydroxylamine reaction. After the reaction is completed, dry it in a vacuum furnace to obtain a hydroxylamine oxime carbon felt.

[0093] Step S4: Place the amylopectin carbon felt obtained in step S3 in deionized water, add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and glutamic acid, react and dialyze at room temperature, then treat and dry in polyethylene glycol solution to obtain glutamic acid modified amylopectin carbon felt electrode.

[0094] Step S5: Place the positive electrode powder into a closed glass reactor containing sulfuric acid solution;

[0095] Step S6: Place the glass reactor from step S5 in a constant temperature magnetic stirrer, add an organic phase containing 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester and sulfonated kerosene, and equip it with glutamic acid modified ammonia oxime carbon felt as the anode and cathode, respectively.

[0096] Step S7: Connect the anode and cathode to the power supply respectively, place the ultrasonic probe between the anode and cathode, and then perform leaching, electrodeposition and extraction respectively;

[0097] Step S8: Filtration. The collected organic phase is back-extracted with sulfuric acid solution to obtain cobalt sulfate. The aqueous phase is then purged with carbon dioxide to obtain lithium carbonate.

[0098] Step S9: Use an eluent and apply a DC reverse bias voltage to the electrode containing high-purity nickel and manganese dioxide to perform desorption.

[0099] In this embodiment, the synthesis method of glutamic acid-modified amylopectin carbon felt is simple, possessing high complexing ability, high selectivity, and hydrophilicity, enhancing metal adsorption and immobilization, and exhibiting a larger surface area for metal deposition. Carboxyl, amino, imide, and hydroxyl groups can specifically bind to metal ions. This material has a unique spatial structure, forming a nanopocket with multiple functional groups for selectively capturing metal ions.

[0100] Ultrasonic treatment of the solution generates cavitation bubbles. The collapse of these cavitation bubbles produces high temperature and pressure, which has mechanical effects such as reducing diffusion resistance, accelerating dissolution, and damaging the surface of reactants. Introducing an electric field enhances the effect of ultrasonic cavitation on cathode powder in sulfuric acid solution. The electroreduction-ultrasonic synergistic method can destroy the layered structure of cathode powder, renew the powder particle surface, and has advantages such as flexible operation, low energy consumption, and no toxic gas emissions. It is an excellent alternative to calcination-leaching, which can increase the pore volume, reduce the particle size, and increase the specific surface area of ​​cathode powder, thereby significantly accelerating the leaching process of lithium, nickel, cobalt, and manganese. The exposed layered structure is electroreduced, and Ni is formed after leaching. 2+ Co 2+ Mn 2 + and Li + A mixture of ions, releasing Co 2+ Captured by the extractant, while simultaneously providing most of the protons to the aqueous phase, while Ni 2+ Mn 2+ Ions are electrochemically adsorbed and reduced and oxidized into high-purity nickel and manganese dioxide on the cathode and anode surfaces, respectively, thereby achieving simultaneous recovery of nickel and manganese without intermediate separation steps. This directly realizes the integrated selective leaching-deposition-extraction process, avoiding the consumption of reducing agents and the generation of by-products. The electrolyte can be recycled, reducing the consumption of chemical reagents and wastewater discharge.

[0101] This method is simple to operate, low in cost, has a high selective recovery rate, simplifies the process, greatly shortens the metal productization process, enables the extractant to self-saponify, avoids the introduction of impurity ions and solvent loss, and allows the modified electrode and extractant to be recycled, thus greatly improving economic efficiency.

[0102] Please refer to the reference again. Figures 1 to 13 The working principle of the waste battery recycling equipment provided by this invention is as follows:

[0103] Step S1: Start the drive motor 84. The drive motor 84 rotates and drives the rotating rod 81 to rotate. The rotation of the rotating rod 81 drives the mixing frame 83 to rotate through the connecting frame 82. The rotation of the mixing frame 83 mixes the sodium carbonate and the leachate to generate nickel carbonate precipitate. After filtration, the precipitate is obtained.

[0104] When the rotating rod 81 rotates, it will simultaneously drive the drive plate 95 to rotate. The rotation of the drive plate 95 causes the slider 92 to slide on the surface of the circular track 91 through the connecting bolt 96. During the movement of the slider 92, the feeding bin 94 is driven to move in a circular motion through the mounting plate 93, thereby performing circular feeding.

[0105] Step S2: The filtered filtrate is transported to the generating tank 2. The electric telescopic rod 46 is activated. The electric telescopic rod 46 retracts, causing the gear plate 47 to move forward. The movement of the gear plate 47 in turn drives the drive gear 43 to rotate. The rotation of the drive gear 43 drives the drive disk 42 to rotate. Under the action of the slide rod 45, the three sliding seats 44 slide inward on the top of the mounting disk 41. The movement of the sliding seats 44 drives the three mounting seats 33 and the purge hose 34 to move inward, so that the purge hose 34 comes into contact with the extrusion wheel 32.

[0106] Start the rotating motor 54. The rotating motor 54 rotates and drives the rotating shaft 51 to rotate. The rotating shaft 51 rotates and drives the two sets of stirring paddles 52 to rotate. When the rotating shaft 51 rotates, it also drives the bottom air intake plate 111 to rotate. Carbon dioxide is introduced into the air intake plate 111 through the delivery pipe 114. The carbon dioxide enters the filtrate through the nozzle 112. The rotation of the air intake plate 111 rotates the carbon dioxide into the generating tank 2. When the air intake plate 111 rotates, the paddle 113 will rotate at the same time, thereby shearing the carbon dioxide bubbles and turning large bubbles into small bubbles.

[0107] In step S3, the rotating shaft 51 drives the rotating frame 31 and the extrusion wheel 32 to rotate. During the rapid rotation of the extrusion wheel 32, a negative pressure is formed in the purge hose 34, thereby extracting nitrogen gas. The extracted nitrogen gas is transported through the purge hose 34 to a depth of 10-20 cm below the filtrate and sprayed out, forming an "umbrella-shaped" airflow.

[0108] Step S4: When a local excess area is detected, the control system automatically sends a command to the solenoid valve on the nitrogen purging pipeline of the corresponding area to open the nitrogen pipeline and regulate the nitrogen flow rate. When the extrusion wheel 32 rotates, nitrogen is released through a single purging hose 34 to quickly and accurately reduce the carbon dioxide concentration in the local excess area and avoid lithium carbonate re-dissolution due to local carbon dioxide excess.

[0109] The above description is only a preferred embodiment of the present invention and does not limit the patent scope of the present invention. All equivalent structural transformations made under the concept of the present invention using the contents of the present invention specification and drawings, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.

Claims

1. Waste battery recycling equipment, characterized in that, It includes a sedimentation tank, a generation tank, a purging mechanism, a drive mechanism, and a generation and mixing mechanism; The purging mechanism includes a rotating frame and three extrusion wheels. The rotating frame is located inside the generating groove, and the three extrusion wheels are rotatably connected to the inner side of the rotating frame. The top of the driving mechanism is fixed with three mounting seats, and the inner side of each of the three mounting seats is provided with a purging hose. The driving mechanism includes a mounting plate, a driving plate, and a driving gear. The mounting plate is fixedly connected to the inner wall of the generating groove. The driving gear is rotatably connected to the inner side of the mounting plate through a hollow rotating shaft. The driving gear is fixedly connected to the bottom of the driving plate through the hollow rotating shaft. Three sliding seats are slidably connected to the top of the mounting plate. The top of the three sliding seats is fixedly connected to the bottom of the three mounting seats respectively. Each of the three sliding seats has a sliding rod fixedly provided on its top. The three sliding rods are slidably connected to the inner side of the driving plate. The generating mixing mechanism is used to mix carbon dioxide and filtrate to improve the generation efficiency of lithium carbonate. An electric telescopic rod is fixedly installed at the bottom of the mounting plate, and a gear plate is fixedly installed at the output end of the electric telescopic rod, the gear plate meshing with the drive gear; A pH sensor and a carbon dioxide sensor are vertically installed on the inner side of the mounting plate to monitor the pH value and carbon dioxide concentration of each area in real time. A solenoid valve and a flow meter are installed on the surface of the purge hose. The generating mixing mechanism includes a rotating shaft that is vertically rotatably connected to the inner side of the generating tank. Two sets of stirring paddles are fixedly mounted on the surface of the rotating shaft. The circumferential side of the rotating shaft is fixedly connected to the rotating frame. A support base is fixedly mounted on the top of the generating tank. A rotating motor for driving the rotating shaft to rotate is mounted on the top of the support base. An air intake mechanism is fixedly provided at the bottom end of the rotating shaft. The air intake mechanism includes an air intake plate fixedly provided at the bottom end of the rotating shaft. Multiple nozzles are connected to the surface of the air intake plate. Multiple paddles are arranged in a circular array on the surface of the air intake plate. A conveying pipe is connected to the bottom end of the air intake plate. The conveying pipe is rotatably connected to the bottom of the inner wall of the generating tank. When the three mounting brackets are adjusted inward so that the extrusion wheel contacts the purge hose and extrudes the purge hose, the rotating shaft drives the rotating frame and the extrusion wheel to rotate. During the rapid rotation of the extrusion wheel, a negative pressure is formed inside the purge hose, thereby extracting nitrogen gas.

2. The waste battery recycling equipment according to claim 1, characterized in that, A sedimentation mixing mechanism is vertically rotatably connected to the inner side of the sedimentation tank. The sedimentation mixing mechanism includes a rotating rod that is vertically rotatably connected to the inner side of the sedimentation tank. Three sets of connecting frames are fixed on the surface of the rotating rod, and mixing frames are fixed on both sides of the three sets of connecting frames. A drive motor for driving the rotating rod to rotate is provided at the top of the sedimentation tank.

3. The waste battery recycling equipment according to claim 2, characterized in that, The top of the sedimentation tank is fixedly provided with a feeding mechanism. The feeding mechanism includes an annular track fixedly provided at the top of the sedimentation tank. A slider is slidably connected to the surface of the annular track. An installation plate is fixedly provided at the top of the slider. A feeding bin is fixedly provided at the top of the installation plate. A drive plate is fixedly provided on the surface of the rotating rod. A connecting bolt is vertically slidably connected to the inner sides of the installation plate and the drive plate. The top of the sedimentation tank is provided with an annular through groove, and a bridge is fixedly provided on the top of the inner wall of the sedimentation tank. The rotating rod is rotatably connected to the bridge.

4. The waste battery recycling equipment according to claim 1, characterized in that, The bottom of the sedimentation tank is fixedly equipped with a support frame, and the bottom of the sedimentation tank is connected to a discharge pipe. The bottom of the generating tank is fixedly equipped with multiple support legs.

5. A process for extracting valuable metals from waste lithium batteries, characterized in that, The extraction process includes the waste battery recycling equipment and the following steps as described in any one of claims 1-4: Step S1: Wash the carbon felt sheet with acetone and pure water to remove surface dirt, and dry it to obtain a clean carbon felt. Step S2: Mix and stir polyacrylonitrile, super carbon black and N,N-dimethylformamide in a certain proportion until the slurry becomes viscous and uniform. Cut the carbon felt obtained in step S1 into a certain size, immerse it in the slurry and dry it to obtain polyacrylonitrile carbon felt. Step S3: Place the polyacrylonitrile carbon felt obtained in step S2 into a water bath, add hydroxylamine hydrochloride, sodium carbonate and sodium hydroxide to carry out the hydroxylamine reaction. After the reaction is completed, dry it in a vacuum furnace to obtain a hydroxylamine oxime carbon felt. Step S4: Place the amylopectin carbon felt obtained in step S3 in deionized water, add 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and glutamic acid, react and dialyze at room temperature, then treat and dry in polyethylene glycol solution to obtain glutamic acid modified amylopectin carbon felt electrode. Step S5: Place the positive electrode powder into a closed glass reactor containing sulfuric acid solution; Step S6: Place the glass reactor from step S5 in a constant temperature magnetic stirrer, add an organic phase containing 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester and sulfonated kerosene, and equip it with glutamic acid modified ammonia oxime carbon felt as the anode and cathode, respectively. Step S7: Connect the anode and cathode to the power supply respectively, place the ultrasonic probe between the anode and cathode, and then perform leaching, electrodeposition and extraction respectively; Step S8: Filtration. The collected organic phase is back-extracted with sulfuric acid solution to obtain cobalt sulfate. The aqueous phase is then purged with carbon dioxide to obtain lithium carbonate. Step S9: Use an eluent and apply a DC reverse bias voltage to the electrode containing high-purity nickel and manganese dioxide to perform desorption.

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