CN219309020U

CN219309020U - Device for strengthening flotation separation of anode and cathode materials in waste lithium cobalt oxide battery

Info

Publication number: CN219309020U
Application number: CN202223444364.8U
Authority: CN
Inventors: 周圣健; 李文科; 张家顺
Original assignee: Hunan Wuchuang Recycling Technology Co ltd
Current assignee: Hunan Wuchuang Recycling Technology Co ltd
Priority date: 2022-12-22
Filing date: 2022-12-22
Publication date: 2023-07-07
Anticipated expiration: 2032-12-22

Abstract

The utility model provides a device for strengthening the flotation separation of anode and cathode materials in a waste lithium cobalt oxide battery, which comprises a reagent solution pretreatment system, a strengthening stirring system and a flotation separation system. The bottom discharge port of the reagent solution pretreatment system is connected with the enhanced stirring system through a material conveying device and a rubber tube, and the upper discharge port of the enhanced stirring system is connected with the flotation separation system through a material conveying device and a rubber tube. The device is coupled with a reagent solution pretreatment system, an enhanced stirring system and a flotation separation system, wherein the reagent solution pretreatment system emulsifies a flotation reagent through an ultrasonic generator to improve reagent action efficiency, and simultaneously, a cavitation pipe circularly treats the reagent solution to generate micro bubbles to enhance flotation separation of anode and cathode materials; the enhanced stirring system can fully mix the ore pulp medicaments; the organic combination of the three systems can be used for enhancing the flotation separation efficiency of the anode and cathode materials in the waste lithium cobalt oxide battery.

Description

Device for strengthening flotation separation of anode and cathode materials in waste lithium cobalt oxide battery

Technical Field

The utility model belongs to the technical field of recycling of waste lithium cobalt oxide batteries, and particularly relates to a device for strengthening flotation separation of positive and negative materials in waste lithium cobalt oxide batteries.

Background

The lithium cobaltate battery is generally composed of a positive electrode material, a negative electrode material, an electrolyte, a diaphragm, a current collector, a shell and the like, wherein the electrolyte contains extremely toxic substances, the positive electrode material contains a plurality of Li, co, mn, ni valuable metals, the negative electrode material is graphite, and if the negative electrode material is not treated, the problems of pollution, resource waste and the like caused by the non-treatment can seriously affect the sustainable development of the economic society. Therefore, innocent treatment of waste lithium cobaltate batteries and effective recycling of valuable metals in the waste lithium cobaltate batteries have become hot spots for research at home and abroad.

The recovery of the waste lithium cobalt oxide battery comprises the steps of pretreatment, material recovery, regeneration and the like. The pretreatment comprises discharging, disassembling, crushing, screening and the like of a battery, superfine anode and cathode material powder is obtained after the pretreatment, and valuable metal-containing anode material and cathode material graphite are further separated by a physical method (such as color selection, magnetic separation, flotation and the like), pyrometallurgy, a wet method (such as acid leaching, alkaline leaching, bioleaching and the like), fire-wet method combination and the like, wherein the flotation method is an important method for recycling waste lithium cobalt oxide battery materials.

In the prior art, the problems of low recovery rate, large medicament consumption, damage to the structure of the anode and cathode materials and the like exist in the process of separating the anode and cathode materials of the waste lithium cobaltate battery through floatation.

The bulletin number is: the Chinese patent of CN109713394A discloses a method for separating lithium cobaltate and graphite from waste electrode materials. The technical scheme of the utility model is as follows: discharging the waste lithium ion battery, naturally airing, then manually disassembling, crushing and screening positive and negative plates, uniformly mixing n-dodecane as a collector with ethanol in advance according to a certain proportion, grinding the mixed medicament and the materials together, floating the ground product, wherein the floating product is graphite tailings, and filtering, drying and roasting the floating sediment to obtain the lithium cobaltate with higher purity. However, the utility model needs to consume a large amount of n-dodecane and ethanol as collecting agents, the production cost is higher, and the subsequent flotation sediment needs to be roasted at high temperature, so that the lithium cobaltate and other metal structures can be damaged, and therefore, the utility model provides a device for strengthening the flotation separation of the anode material and the cathode material in the waste lithium cobaltate battery.

Disclosure of Invention

Aiming at the technical problems, the utility model adopts the following technical scheme: the device comprises a reagent solution pretreatment system, an enhanced stirring system and a flotation separation system, wherein a discharge hole at the bottom of the reagent solution pretreatment system is connected with the enhanced stirring system through a material conveying device and a rubber tube, and a discharge hole at the upper part of the enhanced stirring system is connected with the flotation separation system through the material conveying device and the rubber tube.

The agent solution pretreatment system consists of a material conveying device, a cavitation pipe, a rubber pipe, a stirrer motor I, a stirring barrel I, a single-layer four-blade stirring paddle, an ultrasonic lining plate and an ultrasonic generator, wherein the material conveying device, the cavitation pipe and the rubber pipe form a cavitation system, the cavitation system is arranged on the stirring barrel I, the stirrer motor I controls the single-layer four-blade stirring paddle to operate, the ultrasonic lining plate is arranged on the inner wall of the stirring barrel I and is connected with the ultrasonic generator, and a discharge hole at the bottom of the stirring barrel I is connected with the reinforced stirring system through the material conveying device and the rubber pipe.

The reinforced stirring system consists of a stirrer motor II, a stirring barrel II and a double-layer four-blade stirring paddle, wherein the stirrer motor II controls the double-layer four-blade stirring paddle to operate, and a discharge hole at the bottom of the stirring barrel II is connected with the flotation separation system through a material conveying device and a rubber pipe.

The flotation separation system consists of a flotation machine air suction pipe, a flotation machine motor, a flotation machine scraping plate, a bearing body, a flotation machine central cylinder, a flotation machine impeller, a flotation machine cover plate and a flotation machine groove body, wherein the flotation machine air suction pipe, the flotation machine impeller and the flotation machine cover plate are arranged on the flotation machine central cylinder, the flotation machine groove body is fixed with the flotation machine central cylinder through the bearing body, and the flotation machine motor drives the flotation machine scraping plate, the flotation machine impeller and the flotation machine air suction pipe to operate.

Further, the rotating speed of the single-layer four-blade stirring paddle is 500r/min.

Further, the volume of the stirring barrel I is 1L.

Further, the power of the ultrasonic generator is 300-3000 w.

Further, the frequency of the ultrasonic generator is 20-100 kHz.

Further, the flotation dispersant is sodium hexametaphosphate, and the dosage is 100-1200 g/t; the floatation inhibitor is starch or carboxymethyl cellulose, and the dosage is 20-1800 g/t; the flotation collector is kerosene or diesel oil, and the dosage is 50-800 g/t; the flotation foaming agent is methyl isobutyl carbinol (MIBC) with the dosage of 10-200 g/t.

Further, the concentration of ore pulp in the stirring barrel II is 10% -20%.

Further, the rotating speed of the double-layer four-blade stirring paddle is 100r/min.

Further, the volume of the stirring barrel II is 5L.

Further, the volume of the flotation machine tank body is 4L.

Further, the flotation stirring rotation speed is 235r/min, and the flotation operation time is 15min.

Further, the concentration of the flotation pulp is 5% -15%.

Compared with the prior art, the utility model has the beneficial effects that: (1) The ultrasonic treatment can effectively emulsify hydrocarbon oil collecting agents, enhance the selective adsorption capacity of the flotation agents on the surface of the anode and cathode mixed material, and reduce the dosage of the flotation agents; (2) The agent solution can generate a large number of micro bubbles under the closed-circuit cavitation, so that the hydrophobicity of the surface of graphite is enhanced, and micro graphite particles are aggregated into clusters through the bridging action among bubbles, so that the collision probability between the negative electrode material graphite and flotation bubbles is increased, and meanwhile, the entrainment of positive electrode material in a foam product is reduced; (3) The positive and negative electrode mixed material ore pulp and the medicament can be fully mixed in the reinforced stirring system; (4) The utility model can effectively improve the separation efficiency of the superfine anode and cathode mixed materials in the waste lithium cobaltate battery, and obtain high-quality final anode and cathode products.

Drawings

Fig. 1 is a schematic diagram of the overall structure of the present utility model.

Reference numerals: 1-material conveying device, 2-cavitation pipe, 31-stirrer motor I, 41-stirring barrel I, 51-single-layer four-blade stirring paddle, 32-stirrer motor II, 42-stirring barrel II, 52-double-layer four-blade stirring paddle, 6-ultrasonic lining board, 7-ultrasonic generator, 8-valve, 9-rubber pipe, 10-flotation machine air suction pipe, 11-flotation machine motor, 12-flotation machine scraper, 13-bearing body, 14-flotation machine central cylinder, 15-flotation machine impeller, 16-flotation machine cover plate and 17-flotation machine tank.

Detailed Description

The technical scheme of the utility model is further described below by means of specific embodiments in combination with specific contents of the drawings.

As shown in figure 1, the utility model discloses a device for strengthening the flotation separation of anode and cathode materials in a waste lithium cobalt oxide battery, which comprises a material conveying device 1, a cavitation tube 2, a stirrer motor I31, a stirring barrel I41, a single-layer four-blade stirring paddle 51, a stirrer motor II 32, a stirring barrel II 42, a double-layer four-blade stirring paddle 52, an ultrasonic lining plate 6, an ultrasonic generator 7, a valve 8, a rubber tube 9, a flotation machine suction tube 10, a flotation machine motor 11, a flotation machine scraper 12, a bearing body 13, a flotation machine central cylinder 14, a flotation machine impeller 15, a flotation machine cover plate 16 and a flotation machine tank 17.

As shown in figure 1, the pretreatment system of the traditional Chinese medicine solution in the embodiment comprises a material conveying device 1, a cavitation tube 2, a stirrer motor I31, a stirring barrel I41, a single-layer four-blade stirring paddle 51, an ultrasonic lining plate 6 and an ultrasonic generator 7, wherein a medicine enters the stirring barrel I41 through the top of the stirring barrel I41, the volume of the stirring barrel I is 1L, the rotation speed of the single-layer four-blade stirring paddle 51 is controlled by the stirrer motor I31, the rotation speed of the single-layer four-blade stirring paddle 51 is 500r/min, the emulsification treatment is carried out on the medicine aqueous solution by an ultrasonic system consisting of the ultrasonic lining plate 6 and the ultrasonic generator 7, the power of the ultrasonic generator is 300-3000 w, the working frequency of the ultrasonic generator is 20-100 kHz, the medicine is 100-1200 g/t dispersant sodium hexametaphosphate, 20-1800 g/t inhibitor starch or carboxymethyl cellulose, and 50-800 g/t collector kerosene or diesel oil respectively; 10-200 g/t of foaming agent methyl isobutyl carbinol (MIBC), and simultaneously, the emulsifying agent solution is processed by a closed-circuit cavitation system consisting of a cavitation pipe 2, a material conveying device 1 and a rubber pipe 9 to generate a large number of micro bubbles, a valve 8 is arranged at a discharge hole at the lower part of a stirring barrel I41, and the emulsifying agent solution containing the micro bubbles is further conveyed to an enhanced stirring system by the material conveying device 1 and the rubber pipe 9.

As shown in fig. 1, the enhanced stirring system in this embodiment comprises a stirrer motor II 32, a stirring barrel II 42 and a double-layer four-leaf stirring paddle 52, wherein ore pulp is fed through a feeding port at the bottom of the stirring barrel II 42, the volume of the stirring barrel II is 5L, the concentration of the ore pulp is 10% -20%, an emulsified medicament solution containing fine bubbles is fed through a feeding port at the middle part of the stirring barrel II 42, the rotation speed of the double-layer four-leaf stirring paddle 52 is controlled by the stirrer motor II 32 to uniformly mix the ore pulp and the medicament, the rotation speed of the double-layer four-leaf stirring paddle 52 is 100r/min, a valve 8 is arranged at a discharging port above the stirring barrel II 42, and the slurry containing the fine bubbles is further conveyed to a flotation separation system through a material conveying device 1 and a rubber tube 9.

As shown in fig. 1, the flotation separation system in this embodiment includes a flotation machine suction pipe 10, a flotation machine motor 11, a flotation machine scraper 12, a bearing body 13, a flotation machine center tube 14, a flotation machine impeller 15, a flotation machine cover plate 16, and a flotation machine tank 17, wherein the volume of the flotation machine tank 17 is 4L, the concentration of flotation pulp is controlled to be 5% -15%, the rotation speed of the flotation machine impeller is 235r/min, the flotation machine scraper 12 is started after aeration and flotation operation is performed, the flotation time is 15min, and the slurry containing fine bubbles is separated in the flotation separation system.

The device is mainly used for improving the flotation separation efficiency of the superfine anode and cathode mixed materials of the waste lithium cobalt oxide battery, and the specific operation process is as follows.

Firstly, enabling a medicament to enter the stirring barrel I41 through the top of the stirring barrel I41, controlling the rotating speed of a single-layer four-blade stirring paddle 51 to enable the medicament to be fully dispersed by adjusting the rotating speed of the stirring paddle I31, emulsifying a medicament aqueous solution by an ultrasonic system consisting of an ultrasonic lining plate 6 and an ultrasonic generator 7, wherein the working frequency of the ultrasonic generator is 20-100 kHz, the medicament is 100-1200 g/t of dispersant sodium hexametaphosphate, 20-1800 g/t of inhibitor starch or carboxymethyl cellulose and 50-800 g/t of collector kerosene or diesel oil respectively; 10-200 g/t of foaming agent methyl isobutyl carbinol (MIBC), and simultaneously, the emulsifying agent solution is processed by a closed-circuit cavitation system consisting of a cavitation pipe 2, a material conveying device 1 and a rubber pipe 9 to generate a large number of micro bubbles, a valve 8 is arranged at a discharge hole at the lower part of a stirring barrel I41, and the emulsifying agent solution containing the micro bubbles is conveyed into a stirring barrel II 42 of an enhanced stirring system by the material conveying device 1 and the rubber pipe 9.

And secondly, inputting an emulsifying agent containing micro-bubbles into a stirring barrel II 42 through a material conveying device 1 and a rubber pipe 9, inputting slurry of a positive-negative electrode mixed material of a waste lithium cobalt oxide battery through a feeding port at the bottom of the stirring barrel II 42, wherein the concentration of the slurry is 10% -20%, regulating the rotating speed of a double-layer four-blade stirring paddle 52 through a stirrer motor II 32, and enabling the slurry to be uniformly mixed with the agent, wherein a valve 8 is arranged at a discharging port at the bottom of the stirring barrel II 42, and conveying the mixed slurry containing the micro-bubbles into a flotation machine tank 17 through the material conveying device 1 and the rubber pipe 9.

And (III) enabling the mixed slurry to enter the flotation machine tank body 17 through a feed inlet at the bottom of the flotation machine tank body 17 for size mixing, controlling the concentration of the flotation slurry to be 5% -15%, controlling the rotating speed of a flotation machine impeller to be 235r/min, starting a flotation machine scraping plate 12 after air inflation, performing flotation operation for 15min, wherein concentrate foam obtained by flotation is graphite negative electrode material, and tailings left in the flotation machine tank body 17 are positive electrode material.

Claims

1. The utility model provides a device of positive negative pole material flotation separation in strengthening old and useless lithium cobaltate battery, includes medicament solution pretreatment systems, its characterized in that: the device comprises a chemical solution pretreatment system, a material conveying device (1), a rubber pipe, a reinforced stirring system, a flotation separation system and a flotation separation system, wherein a discharge port at the bottom of the chemical solution pretreatment system is connected with the reinforced stirring system through the material conveying device (1) and the rubber pipe;

the agent solution pretreatment system consists of a material conveying device (1), a cavitation pipe (2), a rubber pipe, a stirrer motor I (31), a stirring barrel I (41), a single-layer four-blade stirring paddle (51), an ultrasonic lining plate (6) and an ultrasonic generator (7), wherein the material conveying device (1), the cavitation pipe (2) and the rubber pipe form a cavitation system, the cavitation system is arranged on the stirring barrel I (41), the stirrer motor I (31) controls the single-layer four-blade stirring paddle (51) to operate, the ultrasonic lining plate (6) is arranged on the inner wall of the stirring barrel I and is connected with the ultrasonic generator (7), and a discharge hole at the bottom of the stirring barrel I (41) is connected with the reinforced stirring system through the material conveying device (1) and the rubber pipe;

the enhanced stirring system consists of a stirrer motor II (32), a stirring barrel II (42) and a double-layer four-leaf stirring paddle (52), wherein the stirrer motor II (32) controls the double-layer four-leaf stirring paddle (52) to operate, and a discharge hole at the bottom of the stirring barrel II (42) is connected with the flotation separation system through a material conveying device (1) and a rubber tube;

the flotation separation system consists of a flotation machine air suction pipe (10), a flotation machine motor (11), a flotation machine scraping plate (12), a bearing body (13), a flotation machine central cylinder (14), a flotation machine impeller (15), a flotation machine cover plate (16) and a flotation machine groove body (17), wherein the flotation machine air suction pipe (10), the flotation machine impeller (15) and the flotation machine cover plate (16) are arranged on the flotation machine central cylinder (14), the flotation machine groove body (17) is fixed with the flotation machine central cylinder (14) through the bearing body (13), and the flotation machine motor (11) drives the flotation machine scraping plate (12), the flotation machine impeller (15) and the flotation machine air suction pipe (10) to operate.

2. The device for strengthening the flotation separation of the anode and cathode materials in the waste lithium cobaltate battery according to claim 1, wherein the rotating speed of the single-layer four-blade stirring paddle (51) is 500r/min.

3. The device for strengthening the flotation separation of the anode and cathode materials in the waste lithium cobalt oxide battery according to claim 1, wherein the volume of the stirring barrel I (41) is 1L.

4. The device for strengthening the flotation separation of the anode and cathode materials in the waste lithium cobalt oxide battery according to claim 1, wherein the power of the ultrasonic generator (7) is 300-3000 w.

5. The device for strengthening the flotation separation of the anode and cathode materials in the waste lithium cobaltate batteries according to claim 1, wherein the frequency of the ultrasonic generator (7) is 20-100 kHz.

6. The device for strengthening the flotation separation of the anode and cathode materials in the waste lithium cobaltate battery according to claim 1, wherein the flotation dispersant is sodium hexametaphosphate, and the dosage is 100-1200 g/t; the floatation inhibitor is starch or carboxymethyl cellulose, and the dosage is 20-1800 g/t; the flotation collector is kerosene or diesel oil, and the dosage is 50-800 g/t; the flotation foaming agent is methyl isobutyl carbinol, and the dosage is 10-200 g/t.

7. The device for strengthening the flotation separation of the anode and cathode materials in the waste lithium cobalt oxide battery according to claim 1, wherein the concentration of the ore pulp in the stirring barrel II (42) is 10-20%.

8. The device for strengthening the flotation separation of the anode and cathode materials in the waste lithium cobaltate battery according to claim 1, wherein the rotating speed of the double-layer four-blade stirring paddle (52) is 100r/min.

9. The device for strengthening the flotation separation of the anode and cathode materials in the waste lithium cobalt oxide battery according to claim 1, wherein the volume of the stirring barrel II (42) is 5L.

10. The device for strengthening the flotation separation of the anode and cathode materials in the waste lithium cobalt oxide battery according to claim 1, wherein the volume of the flotation cell body (17) is 4L.

11. The device for strengthening the flotation separation of the anode and cathode materials in the waste lithium cobalt oxide battery according to claim 1, wherein the flotation stirring rotation speed is 235r/min, and the flotation operation time is 15min.

12. The device for strengthening the flotation separation of the anode and cathode materials in the waste lithium cobalt oxide battery according to claim 1, wherein the concentration of the flotation pulp is 5% -15%.