Regeneration and recovery method and recovery device of copper-containing battery negative electrode material

Abstract

The invention relates to the technical field of battery negative electrode material recovery, and discloses a regeneration recovery method and a recovery device of a copper-containing battery negative electrode material. The regeneration and recovery method comprises the following steps: step S1, primary screening of raw materials: enabling waste batteries or waste negative electrode materials generated in a production process to pass through a screen to remove obvious impurities and non-metallic materials so as to obtain recovered raw materials; step S2, aeration separation: feeding the recycled raw materials obtained in the step S1 into an aeration separation device, and after the aeration separation is finished, obtaining a liquid containing graphite and a precipitate which is a copper current collector; and S3, respectively recovering the liquid and the precipitate after aeration separation. The method is reasonable in design, high in separation efficiency, simple in technological process, good in technological process environmental friendliness and low in recovery cost.

Description

Technical Field

[0001] The invention relates to the technical field of battery negative electrode material recycling, in particular to a regeneration and recycling method and a recycling device for copper-containing battery negative electrode materials. Background Art

[0002] Waste batteries are the main source of copper-containing negative electrode plates. These batteries need to be recycled after their service life to recover valuable metal components. Recycling copper and graphite in waste batteries can not only reduce resource waste, but also reduce the production cost of new materials. At the same time, battery recycling is also conducive to reducing the pollution of waste to the environment and is an important sustainable development measure.

[0003] With the deepening of the concept of resource recycling, the recycling of metal resources contained in waste batteries, especially copper and graphite, has gradually become a research hotspot. In order to recycle these materials, they need to be separated from the battery. Common separation methods include mechanical crushing, acid leaching, etc., which can effectively separate copper foil and graphite. The separated copper foil and graphite need to be further separated to obtain a high-purity final product. Common separation methods usually use physical screening to put the mixture of copper foil and graphite into the screening equipment, set up multi-stage screens, separate materials of different particle sizes by vibration or rotation, and screen out copper flakes and graphite step by step. However, this screening method has low separation efficiency, complicated operation of setting up multi-stage screens, and is prone to environmental pollution.

[0004] The copper negative electrode material in waste batteries not only has a high recycling value, but is also highly regarded in many industrial applications because of its superior performance in chemical catalysis and material transfer. In particular, the oxidation treatment of copper, the copper oxide generated by it has excellent chemical stability and heterogeneous catalytic activity, and is widely used in high value-added fields such as catalytic reactions and electronic components. In the process of oxidizing pure copper to copper oxide, the existing technology generally faces limitations such as high energy demand, lagging oxidation efficiency and poor purity of the target product. The above technical bottlenecks not only inhibit the possibility of efficient conversion of copper resources into industrial-grade copper oxide, but also restrict the sustainable production of low-energy consumption and high-purity oxidation products during industrial promotion. In response to these problems, it is urgent to introduce a refined reaction control mechanism in the oxidation process design, and to achieve the optimal conversion of copper resources and a breakthrough improvement in product performance by rationally optimizing the energy transfer path. Summary of the invention

[0005] The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art and provide a method and a device for regenerating and recovering copper-containing battery negative electrode materials.

[0006] The technical solution adopted by the present invention to solve the technical problem is: a method for regenerating and recovering copper-containing battery negative electrode materials, which specifically includes the following steps:

[0007] Step S1, initial screening of raw materials, where waste negative electrode materials from waste batteries or produced during the production process are screened to remove obvious impurities and non-metallic materials to obtain recycled raw materials;

[0008] Step S2, aeration separation, the recycled raw material obtained in step S1 is put into an aeration separation device, and after the aeration separation is completed, the liquid is a graphite-containing liquid, and the precipitate is a copper current collector;

[0009] Step S3, respectively recovering the liquid and sediment after aeration separation;

[0010] Wherein, the liquid recovery comprises:

[0011] Step S4, sedimentation separation, the graphite-containing liquid obtained in step S2 enters a sedimentation tank, the upper clear liquid of the sedimentation tank flows back to the aeration tank, and the bottom of the sedimentation tank is graphite slurry;

[0012] Step S5, two-stage gasification, adding water to the graphite slurry obtained in step S4 and stirring, with a solid-liquid ratio of 1:1, entering a first-stage gasification device, with a first-stage gasification temperature of 300°C to 400°C, and a first-stage gasification time of 1h to 3h, to remove moisture and organic impurities to obtain dry graphite; then the dry graphite enters a second-stage gasification device, with a second-stage gasification temperature of 2800°C to 3000°C, and a second-stage gasification time of 2h to 4h, to remove metal impurities and obtain primary graphite;

[0013] Step S6, ball milling, putting the primary graphite obtained in step S5 into a ball mill, the ball milling time is 4 hours, the ball milling medium ratio is 1:3, the rotation speed is controlled at 150 rpm, and the particle size after crushing is required to reach D90<10 μm;

[0014] Step S7, repairing graphite, putting the ball-milled graphite into a repair furnace, introducing a hydrogen atmosphere, the repair temperature is 800°C, the repair time is 2 hours, and the hydrogen flow rate needs to be controlled at 100 ml / min during the repair process. After the repair is completed, the finished graphite is obtained;

[0015] The precipitate recovery comprises:

[0016] Step S8, dehydration, passing the precipitate obtained in step S2 through a dehydration device to remove excess water to obtain a primary copper current collector;

[0017] Step S9, crushing, the primary copper current collector obtained in step S8 is put into a crushing device, the crusher speed is 500 rpm, the crushing time is 30 minutes, and the particle size of the copper particles after crushing is less than or equal to 5 mm;

[0018] Step S10, oxidation treatment, copper particles are placed in an oxidation furnace and oxidized to obtain copper oxide;

[0019] Step S11, cooling and collecting to obtain finished copper oxide.

[0020] Furthermore, the step S2 aeration separation is specifically as follows: the recycled raw material obtained in step S1 is put into an aeration tank, pure water is added, the solid-liquid ratio is maintained at 1:2 to 1:4, the aeration equipment is started, and the air flow rate is 500L / min to 700L / min; during the aeration process, the stirring speed is 150rpm to 250rpm, the temperature is room temperature, the aeration time is 2h to 5h, and the aeration separation is completed.

[0021] Furthermore, the oxidation treatment in step S10 is specifically as follows: the crushed copper particles are loaded into an oxidation furnace, oxygen or air is introduced, the oxygen flow rate is maintained at 100L / min to 300L / min, the oxidation temperature is 450°C to 550°C, the oxidation time is 2h to 6h, and the oxidation reaction is completed to obtain copper oxide.

[0022] A recovery device using the above-mentioned regeneration and recovery method for copper-containing battery negative electrode materials, wherein a screen and an aeration separation device are sequentially arranged along the direction of material travel, and the aeration separation device is respectively connected to a liquid recovery component and a sediment recovery component; the liquid recovery component comprises a sedimentation tank, a two-stage gasification device, a ball mill, a repair furnace and a graphite collection tank which are sequentially arranged; the sediment recovery component comprises a dehydration device, a crushing device, an oxidation furnace, a cooling device and a copper oxide collection tank which are sequentially arranged; a water inlet pipe for facilitating the entry of pure water is arranged at the top of the aeration separation device, and a reflux pipe connected to the aeration separation device is arranged at the top of the sedimentation tank.

[0023] Furthermore, the aeration separation device includes an aeration tank, a partition is provided in the aeration tank to divide the aeration tank into an aeration zone and a sedimentation zone, a connecting hole connecting the aeration zone and the sedimentation zone is opened at the upper end of the partition, a feed pipe is provided at the upper end of the aeration tank, a water inlet pipe is provided at the lower end of the aeration tank, the feed pipe and the water inlet pipe are both connected to the aeration zone, an aeration component is provided in the aeration zone, and the aeration component is used to ventilate the aeration zone; a stirring component is provided on the aeration tank, and the stirring end of the stirring component extends into the aeration zone, a second extraction component for extracting separated graphite floating objects is provided at the upper end of the sedimentation zone, and a first extraction component for extracting separated copper sheets is provided at the lower end of the sedimentation zone.

[0024] Furthermore, the aeration assembly includes an air compressor, an air inlet pipe and a central guide tube. The central guide tube is arranged in the aeration area. The lower end of the central guide tube is connected to the air compressor through the air inlet pipe. The air compressor is arranged outside the lower end of the aeration tank.

[0025] Furthermore, the two-stage gasification equipment includes a first-stage gasification equipment, a transmission equipment and a second-stage gasification equipment which are connected in sequence. The first-stage gasification equipment includes a first gasification furnace, a furnace tube is rotatably arranged in the first gasification furnace, and the graphite mixture to be heated enters from one end of the furnace tube. A first heater is arranged around the inner wall of the first gasification furnace, and the first heater is located outside the furnace tube; the two-stage gasification equipment includes a second gasification furnace, a heating chamber is opened in the second gasification furnace, a furnace door for adding graphite after a first stage of gasification is arranged at the upper end of the second gasification furnace, and a second heater is arranged in the heating chamber; one end of the transmission equipment is connected to the other end of the furnace tube, and the other end of the transmission equipment is arranged above the furnace door, and the graphite after a first stage of gasification is discharged from the other end of the furnace tube and transported to the heating chamber of the second gasification furnace through the transmission equipment.

[0026] Furthermore, the first-stage gasification equipment also includes a driving assembly, a first mounting base and a first feed hopper, and the driving assembly and the first gasification furnace are both mounted on the first mounting base; the upper end of the driving assembly is sleeved on the other end of the furnace tube, the driving assembly is used to drive the furnace tube to rotate, and the first feed hopper is arranged on one end of the furnace tube.

[0027] Further, the oxidation furnace includes a crusher assembly, an oxidation furnace assembly and a cooling device, the oxidation furnace assembly includes a furnace body, a first driving mechanism and an air inlet pipe; the first driving mechanism is used to drive the furnace body to rotate, a plurality of stirring blades are spirally arranged on the inner wall of the furnace body, a heater is arranged in the furnace body, and valves for feeding and discharging are arranged on the side wall of the furnace body, at least a part of the crusher assembly is located above the valve, at least a part of the cooling device is located below the valve, and one end of the air inlet pipe is connected to the furnace body; the crusher assembly includes a crushing bin, a rotor and an impact component, a crushing chamber is formed in the crushing bin, the rotor is rotatably arranged in the crushing chamber, the impact component is arranged on the rotor and is used to collide with the material, a collision plate is arranged in the crushing chamber, the collision plate is arranged on one side of the rotor, and the material collides with the collision plate after colliding with the impact component.

[0028] Furthermore, the first driving mechanism includes a first driving motor, a first driving wheel, a first passive wheel, a first connecting shaft and a first belt. The first driving wheel is arranged on the motor shaft of the first driving motor. The first driving wheel and the first passive wheel are driven by the first belt. The two ends of the first connecting shaft are respectively connected to the first passive wheel and the furnace body.

[0029] The beneficial effects of the present invention are as follows: the present invention is reasonably designed and has the following advantages:

[0030] (1) The regeneration and recovery method has high separation efficiency, simple process flow, good environmental protection and low recovery cost;

[0031] (2) In the aeration separation device, the aeration tank is divided into an aeration zone and a sedimentation zone by setting a partition, and the stirring component and the aeration component are used to separate the copper sheet from the graphite powder in the copper-containing negative electrode plate raw material. After the aeration is completed, the liquid containing the graphite floating matter and the copper sheet enters the sedimentation zone through the connecting hole and precipitates in the sedimentation zone. After the precipitation, the graphite floating matter floats on the liquid surface, while the heavier copper sheet sinks to the bottom of the sedimentation zone, so that the copper sheet and the graphite powder can be fully separated;

[0032] (3) In the two-stage gasification equipment, the water in the graphite obtained by aeration separation is dried and the organic impurities are removed through the first gasification furnace, the first heater and the rotatable furnace tube, so that the graphite is kept in a dry state. By setting up a transmission device for cooling, the graphite after the first stage of gasification needs to be cooled to prevent thermal shock when directly entering the high-temperature second stage of gasification. The second gasification furnace and the second heater are used to further remove the excess metal impurities in the graphite, and a secondary graphitization treatment is performed to improve the purity and performance of the graphite; the water and organic impurities are removed at a lower temperature to avoid energy waste and unnecessary complexity of high-temperature treatment. By removing most of the impurities at a lower temperature first, the time and energy required for high-temperature treatment can be reduced, energy can be saved and costs can be reduced. The two-stage gasification process is more energy-efficient than a single high-temperature treatment. About 25% of energy; organic matter is removed at low temperature to avoid decomposition at high temperature to produce harmful gases such as dioxins, reduce air pollution and protect the environment; by gradually increasing the temperature, excessive sintering of materials or other forms of thermal damage can be avoided, and the quality of the final product can be improved; at high temperature, metal impurities can be completely removed, and at the same time, high temperature conditions help to optimize the crystal structure of graphite, improve its purity and performance; gradual heating can reduce the heat load and stress of equipment, extend the service life of equipment, and reduce maintenance and replacement costs; staged gasification can better control the reaction process and parameters of each treatment stage, ensure the stability and controllability of the treatment process, especially in the high temperature stage, to ensure the best treatment effect, and by gradually increasing the temperature in stages, the risk of sudden thermal reactions and equipment failures can be reduced, and the overall safety of the process can be improved;

[0033] (4) In the oxidation furnace, this oxidation device is used to first crush the pure copper obtained from the aeration separation. The crushed pure copper particles are more uniform, which increases the contact area between copper and the working gas and is beneficial to the subsequent oxidation treatment. The oxidation furnace is then preheated to ensure that a stable oxidation environment is achieved in the furnace. The crushed pure copper particles are evenly loaded into the furnace body. With the cooperation of the stirring blades, the copper particles are evenly distributed and the particles are heated more evenly to improve the oxidation efficiency. The oxidation treatment is carried out under this parameter to ensure that the pure copper particles are fully in contact with the working gas, so that the oxidation time is reduced from 8h to 4h, and the processing energy consumption is reduced from 800kWh to 400kWh, and the energy consumption is reduced by about 50%; the purity of copper oxide is increased from 95% to 99%, which has the advantages of low energy consumption, high oxidation efficiency and high purity of copper oxide. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0035] Figure 1 is a flow chart of the recovery method of the present invention;

[0036] Figure 2 It is a structural schematic diagram of the recovery device in the present invention;

[0037] Figure 3 It is a structural schematic diagram of the aeration separation device in the present invention;

[0038] Figure 4 yes Figure 3 A top view of

[0039] Figure 5 yes Figure 4 Sectional view at AA in the middle;

[0040] Figure 6 It is a schematic diagram of the separation principle of the aeration separation device in the present invention;

[0041] Figure 7 It is a structural schematic diagram of the two-stage gasification equipment in the present invention;

[0042] Figure 8 yes Figure 7 A partial cross-sectional view of

[0043] Fig. 9 It is a structural schematic diagram of a gasification device in the present invention;

[0044] Fig.10It is a structural schematic diagram of the two-stage gasification equipment in the present invention;

[0045] Fig.11 yes Fig.10 A cross-sectional view of

[0046] Fig.12 It is a structural schematic diagram of the oxidation furnace in the present invention;

[0047] Fig.13 yes Fig.12 A top view of

[0048] Fig.14 yes Fig.13 Sectional view at the middle BB;

[0049] Fig.15 yes Fig.12 Left view of .

[0050] In the figure: 1. Screen, 2. Aeration separation device, 3. Water inlet pipe, 4. Sedimentation tank, 5. Two-stage gasification equipment, 6. Ball mill, 7. Repair furnace, 8. Dehydration equipment, 9. Crushing equipment, 10. Oxidation furnace, 11. Cooling equipment, 12. Graphite collection tank, 13. Copper oxide collection tank; 2-1. Aeration tank, 2-2. Baffle, 2-3. Aeration area, 2-4. Sedimentation area, 2-5. Connecting hole, 2-6. Feed pipe, 2-8. Air compressor, 2-9. Inlet pipe, 2-10. Central guide tube, 2-11. Vent, 2-12. Stirring motor, 2-13. Stirring motor mounting seat, 2-14. Bearing, 2-15. Stirring shaft, 2-16. Stirring impeller, 2-17. The first extraction pump, 2-18. The first discharge pipe, 2-19. The graphite collection pool, 2-20. The second extraction pump, 2-21. The second discharge pipe, 2-22. The inclined guide plate, 2-23. The separation pool support base, 2-24. The hopper; 5-1. The first gasification furnace, 5-2. The furnace tube, 5-3. The first heater, 5-4. The second gasification furnace, 5-5. The heating chamber, 5-6. The furnace door, 5-7. The second heater, 5-8. The first mounting base, 5-9. The first feed hopper, 5-10. The passive wheel, 5-11. The driving wheel, 5-12. The driving motor, 5-13. The motor mounting seat, 5-14. The handle, 5-15. The intermediate buffer tank, 5-16. The conveyor, 5-17. The support seat, 5-18. conveying bin, 5-19. second feed hopper, 5-20. ventilation pipe, 5-21. conveying structure, 5-22. feeding trolley, 5-23. material transport track, 5-24. gasification chamber; 10-1. crusher assembly, 10-2. oxidation furnace assembly, 10-4. furnace body, 10-6. oxidation air inlet pipe, 10-7. stirring blade, 10-8. valve, 10-9. crushing bin, 10-10. rotor, 10-11. impact component, 10-12. crushing chamber, 10-13. collision plate, 10-14. first drive motor, 10-15. first driving wheel, 10-16. first passive wheel, 10-17. first connecting shaft, 10-18. first belt, 10-19. Support base, 10-20. First bearing seat, 10-21. Feed inlet, 10-22. Discharge port, 10-23. Second drive motor, 10-24. Second driving wheel, 10-25. Second passive wheel, 10-26. Second connecting shaft, 10-27. Second belt, 10-28. Second bearing seat, 10-29. Bracket, 10-30. Dropping bin, 10-31. Screening drum, 10-32. Guide plate, 10-33. Conveyor belt, 10-34. Feed inlet, 10-35. Dropping port, 10-36. Third drive motor, 10-37. Third bearing seat, 10-38. Support frame, 10-39. Conveyor roller, 10-40. Conveyor belt. DETAILED DESCRIPTION

[0051] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0052] like Figure 2 A recovery device using a regeneration and recovery method of copper-containing battery negative electrode materials is shown, and a screen 1 and an aeration separation device 2 are sequentially arranged along the direction of material travel, and the aeration separation device 2 is respectively connected to a liquid recovery component and a sediment recovery component; the liquid recovery component includes a sedimentation tank 4, a two-stage gasification device 5, a ball mill 6, a repair furnace 7 and a graphite collection tank 12 arranged in sequence; the sediment recovery component includes a dehydration device 8, a crushing device 9, an oxidation furnace 10, a cooling device 11 and a copper oxide collection tank 13 arranged in sequence; a water inlet pipe 3 is provided at the top of the aeration separation device 2 for facilitating the entry of pure water, and a reflux pipe connected to the aeration separation device 2 is provided at the top of the sedimentation tank 4.

[0053] like Figures 3 to 6 The aeration separation device 2 shown includes an aeration tank 2-1, a partition 2-2 is provided in the aeration tank 2-1 to divide the aeration tank 2-1 into an aeration zone 2-3 and a sedimentation zone 2-4, a connecting hole 2-5 connecting the aeration zone 2-3 and the sedimentation zone 2-4 is provided at the upper end of the partition 2-2, a feed pipe 2-6 is provided at the upper end of the aeration tank 2-1, a water inlet pipe 3 is provided at the lower end of the aeration tank 2-1, the feed pipe 2-6 and the water inlet pipe 3 are both connected to the aeration zone 2-3, an aeration assembly is provided in the aeration zone 2-3, and the aeration assembly is used to ventilate the aeration zone 2-3;

[0054] A stirring assembly is provided on the aeration tank 2-1, and the stirring end of the stirring assembly extends into the aeration zone 2-3. A second extraction assembly for extracting separated graphite floating objects is provided at the upper end of the sedimentation zone 2-4, and a first extraction assembly for extracting separated copper sheets is provided at the lower end of the sedimentation zone 2-4.

[0055] The aeration tank 2-1 is divided into an aeration zone 2-3 and a sedimentation zone 2-4 by setting a partition 2-2, and the stirring component and the aeration component are used to separate the copper sheet from the graphite powder of the copper-containing negative electrode plate raw material. After the aeration is completed, the liquid containing the graphite floating matter and the copper sheet enters the sedimentation zone 2-4 through the connecting hole 2-5 and precipitates in the sedimentation zone 2-4. After precipitation, the graphite floating matter floats on the liquid surface, while the heavier copper sheet sinks to the bottom of the sedimentation zone 2-4, so that the copper sheet and the graphite powder can be fully separated.

[0056] The aeration assembly includes an air compressor 2-8, an air inlet pipe 2-9 and a central guide tube 2-10. The central guide tube 2-10 is arranged in the aeration zone 2-3. The lower end of the central guide tube 2-10 is connected to the air compressor 2-8 through the air inlet pipe 2-9. The air compressor 2-8 is arranged outside the lower end of the aeration tank 2-1. A plurality of vents 2-11 are provided on the side wall of the central guide tube 2-10. The vents 2-11 connect the inside of the central guide tube 2-10 with the aeration zone 2-3.

[0057] The copper-containing negative electrode raw material and pure water are mixed and placed in the aeration zone 2-3, and air is continuously injected into the aeration zone 2-3 through the air compressor 2-8. Due to the different movement characteristics of materials of different densities in the gas-liquid two-phase flow, the lighter material will be brought to the liquid surface by the air flow, while the heavier material will settle to the bottom of the pool.

[0058] The stirring assembly includes a stirring motor 2-12, a stirring motor mounting seat 2-13, a bearing 2-14, a stirring shaft 2-15 and a stirring impeller 2-16. The stirring motor 2-12 is arranged on the stirring motor mounting seat 2-13. The stirring motor mounting seat 2-13 is arranged at the upper end of the aeration tank 2-1 and is located above the aeration zone 2-3. The upper end of the stirring shaft 2-15 is connected to the motor shaft of the stirring motor 2-12, the lower end of the stirring shaft 2-15 extends into the aeration zone 2-3, and the stirring impeller 2-16 is arranged at the lower end of the stirring shaft 2-15.

[0059] The stirring motor 2-12 drives the stirring impeller 2-16 to rotate to achieve the stirring effect. The stirring can strengthen the contact and mixing between the solid in the liquid and the airflow, improve the uniformity of the gas-liquid two-phase flow, and is beneficial to the improvement of the separation effect. It can also change the flow characteristics of the liquid, such as flow rate, etc., thereby affecting the generation, rise and breakage process of bubbles, and then adjust the separation effect.

[0060] The first extraction assembly includes a first extraction pump 2-17 and a first discharge pipe 2-18, one end of the first discharge pipe 2-18 is connected to the first extraction pump 2-17, and the other end of the first discharge pipe 2-18 extends into the lower end of the sedimentation area 2-4, for extracting the separated copper flakes. The copper flakes that sink to the bottom of the pool after separation are extracted by the first extraction pump 2-17 and the first discharge pipe 2-18 and subsequently crushed.

[0061] The second extraction assembly includes a graphite collection tank 2-19, a second extraction pump 2-20 and a second discharge pipe 2-21, one end of the second discharge pipe 2-21 is connected to the graphite collection tank 2-19, and the other end of the second discharge pipe 2-21 extends into the upper end of the sedimentation zone 2-4, and is used to extract the separated graphite floating matter, and the second extraction pump 2-20 is installed on the second discharge pipe 2-21. The graphite floating matter floating on the liquid surface is extracted into the graphite collection tank 2-19 by the second extraction pump 2-20 and the second discharge pipe 2-21 for subsequent treatment.

[0062] An inclined guide plate 2-22 is formed in the sedimentation zone 2-4, and the inclined guide plate 2-22 is arranged downwardly from the upper end to the lower end of the sedimentation zone 2-4. The design of the inclined guide plate 2-22 plays a guiding role, so that the copper sheet sinks to the bottom of the pool better, which is convenient for subsequent extraction.

[0063] The aeration separation device 2 also includes a plurality of support bases 2-23, which are arranged at the lower end of the aeration tank 2-1; the aeration separation device 2 also includes a hopper 2-24 for feeding copper-containing negative electrode plate raw materials, and the lower end of the hopper 2-24 is connected to the feed pipe 2-6.

[0064] The separation steps of the aeration separation device 2 are as follows:

[0065] Step S21, feeding the copper-containing negative electrode plate raw material into the aeration zone 2-3 through the feed pipe 2-6;

[0066] Step S22, adding pure water into the aeration zone 2-3 through the water inlet pipe 3, the ratio of the copper-containing negative electrode plate raw material added in step S21 to the pure water is 1:2 to 1:4;

[0067] Step S23, start the air compressor 2-8, the air enters the central guide tube 2-10 from the air inlet pipe 2-9, and enters the aeration area 2-3 through the plurality of vents 2-11 on the central guide tube 2-10, and the air flow rate is set to 500L / min to 700L / min;

[0068] Step S24, start the stirring motor 2-12, drive the stirring shaft 2-15 to rotate and then drive the stirring impeller 2-16 to rotate, and the stirring speed is set to 150rpm~250rpm;

[0069] Step S25, maintaining the normal temperature at 25°C, and setting the aeration time to two hours, that is, step S23 and step S24 are run for 2h to 5h;

[0070] Step S26, the liquid containing the graphite floating objects and the copper flakes enters the precipitation area 2-4 through the connecting hole 2-5, and is precipitated in the precipitation area 2-4. After precipitation, the graphite floating objects float on the liquid surface, while the heavier copper flakes sink to the bottom of the precipitation area 2-4;

[0071] Step S27, start the second pumping pump 2-20, extract the graphite floating matter through the second discharge pipe 2-21 into the graphite collection pool 2-19, and perform subsequent treatment;

[0072] Step S28, start the first extraction pump 2-17, discharge the copper sheets from the first discharge pipe 2-18, and collect them for the next step of crushing.

[0073] After aeration, graphite will float on the liquid surface due to its lower density, while the heavier copper sheets will sink to the bottom of the pool. The aeration separation process can fully separate the copper sheets from the graphite powder. This method not only improves the separation efficiency, but also reduces the operational complexity and environmental pollution, making it the preferred process for processing copper-containing negative electrode sheets.

[0074] like Figures 7 to 11 The two-stage gasification equipment 5 shown includes a first-stage gasification equipment, a transmission equipment and a second-stage gasification equipment which are connected in sequence. The first-stage gasification equipment includes a first gasification furnace 5-1, in which a furnace tube 5-2 is rotatably arranged, and the graphite mixture to be heated enters from one end of the furnace tube 5-2. A first heater 5-3 is arranged around the inner wall of the first gasification furnace 5-1, and the first heater 5-3 is located outside the furnace tube 5-2; the two-stage gasification equipment includes a second gasification furnace 5-4, in which a heating chamber 5-5 is opened, and a furnace door 5-6 for adding graphite after a stage of gasification is arranged at the upper end of the second gasification furnace 5-4, and a second heater 5-7 is arranged in the heating chamber 5-5; one end of the transmission equipment is connected to the other end of the furnace tube 5-2, and the other end of the transmission equipment is arranged above the furnace door 5-6. The graphite after a stage of gasification is discharged from the other end of the furnace tube 5-2 and transported to the heating chamber 5-5 of the second gasification furnace 5-4 through the transmission equipment.

[0075] The first gasifier 5-1, the first heater 5-3 and the rotatable furnace tube 5-2 are used to dry the water in the graphite obtained by aeration separation and remove organic impurities to keep the graphite dry. By setting up a transmission device for cooling, the graphite after the first stage of gasification needs to be cooled to prevent thermal shock when directly entering the high-temperature second stage of gasification. The second gasifier 5-4 and the second heater 5-7 are used to further remove excess metal impurities in the graphite, and a secondary graphitization treatment is performed to improve the purity and performance of the graphite.

[0076] The first stage gasification equipment also includes a driving assembly, a first mounting base 5-8 and a first feed hopper 5-9. The driving assembly and the first gasification furnace 5-1 are both mounted on the first mounting base 5-8; the upper end of the driving assembly is sleeved on the other end of the furnace tube 5-2, and the driving assembly is used to drive the furnace tube 5-2 to rotate. The first feed hopper 5-9 is arranged on one end of the furnace tube 5-2.

[0077] The driving assembly includes a passive wheel 5-10 and two driving parts, the two driving parts are respectively arranged on both sides of the passive wheel 5-10, each driving part includes a driving wheel 5-11, a driving motor 5-12 and a 5-motor mounting seat 13, the passive wheel 5-10 is sleeved on the other end of the furnace tube 5-2, the driving wheel 5-11 is installed on the moving end of the driving motor 5-12 and meshes with the passive wheel 5-10 for transmission, the driving motor 5-12 is installed on the motor mounting seat 5-13, and the motor mounting seat 5-13 is installed on the first mounting base 5-8. The passive wheel 5-10 and the driving wheel 5-11 have a simple transmission structure, a strong ability to withstand impact and vibration, a long service life, high reliability, lower noise generated by the transmission, and more stable. The passive wheel driving wheel transmission drives the furnace tube 5-2 to rotate 360 ​​degrees, which is suitable for uniform sintering of graphite.

[0078] The axis of the furnace tube 5-2 is tilted downward toward the direction close to the transmission device, the axis of the moving end of the driving motor 5-12 is parallel to the axis of the furnace tube 5-2, the rotation directions of the two driving wheels 5-11 are the same, and the rotation directions of the driving wheel 5-11 and the driven wheel 5-10 are opposite. The tilted furnace tube 5-2 is more conducive to discharging.

[0079] The second gasifier 5-4 is an ultra-high temperature induction heating furnace, the second heater 5-7 includes an electromagnetic induction heating coil and a heating controller, the heating controller is installed on the second gasifier 5-4, the electromagnetic induction heating coil is spiral and only in the heating chamber 5-5. A handle 5-14 is provided on the furnace door 5-6 of the second gasifier 5-4.

[0080] The transmission equipment includes an intermediate buffer tank 5-15 and a conveyor 5-16 connected in sequence, one end of the intermediate buffer tank 5-15 is connected to the other end of the furnace tube 5-2 through a first feed pipe, and the other end of the intermediate buffer tank 5-15 is connected to one end of the conveyor 5-16 through a first discharge pipe, and the other end of the conveyor 5-16 is arranged above the furnace door 5-6. By setting the transmission equipment for cooling, the graphite after the first stage of gasification needs to be cooled to prevent thermal shock when directly entering the high-temperature second stage of gasification, and the intermediate buffer tank 5-15 is used to temporarily store the graphite after the first stage of gasification.

[0081] The conveyor 5-16 includes a support seat 5-17, a conveying bin 5-18, a second feed hopper 5-19, a ventilation pipe 5-20 and a conveying structure 5-21. The conveying bin 5-18 is installed on the support seat 5-17. A transportation channel is opened in the conveying bin 5-18 from the intermediate buffer tank 5-15 to the direction of the furnace door 5-6. The conveying structure 5-21 is arranged in the transportation channel for transporting graphite to the second gasification furnace 5-4. The second feed hopper 5-19 is arranged on one end of the conveying bin 5-18. The second feed hopper 5-19 is connected to the first discharge pipe. A drop pipe is arranged at the lower end of the other end of the conveying bin 5-18. The drop pipe is arranged above the furnace door 5-6. The ventilation pipe 5-20 is connected from the outside of the conveying bin 5-18 to the conveying channel. The conveying structure 5-21 is used to transport the gasified graphite to the second gasification furnace 5-4, and in the conveying process, inert gas is introduced into the conveying bin 5-18 through the vent pipe 5-20, and the graphite is transported in an inert gas environment to prevent oxidation. The conveying structure 5-21 is a conveyor belt or a spiral conveyor shaft, and the conveyor belt can use a high temperature resistant conveyor belt.

[0082] The first stage gasification equipment also includes: a feeding trolley 5-22, a material transport track 5-23 and a gasification chamber 5-24. The first gasification furnace 5-1 is arranged in the gasification chamber 5-24. The material transport track 5-23 is laid from the outside of the gasification chamber 5-24 to the bottom of one end of the first gasification furnace 5-1. The feeding trolley 5-22 is slidably connected to the material transport track 5-23.

[0083] The gasification process of the two-stage gasification device 5 removes graphite and metal impurities, which includes the following steps:

[0084] Step S51, after the graphite mixture to be heated is delivered to one end of the furnace tube 5-2 by the feeding trolley 5-22, the empty feeding trolley 5-22 withdraws from the gasification chamber 5-24, and the door of the gasification chamber 5-24 is closed;

[0085] Step S52, turn on the first heater 5-3, adjust the first heater 5-3 to the heating temperature required for the first stage of gasification through the external temperature control system, set the first stage of gasification temperature to 300°C to 400°C, turn on the drive motor 5-12, drive the furnace tube 5-2 to rotate through the passive wheel 5-10 and the drive wheel 5-11, and set the first stage of gasification time to 1h to 3h;

[0086] Step S53: The graphite obtained in step S52 from which water and organic impurities have been removed is fed into the intermediate buffer tank 5-15 through the first feed pipe for cooling;

[0087] Step S54, the graphite cooled in step S53 passes through the first discharge pipe and the second feed hopper 5-19 into the conveying bin 5-18, and is conveyed from the discharge pipe to the second gasification furnace 5-4 through the conveying structure 5-21. During the conveying, an inert gas is introduced into the conveying bin 5-18 through the ventilation pipe 5-20;

[0088] Step S55, close the furnace door 5-6, turn on the second heater 5-7, adjust the second heater 5-7 to the heating temperature required for the second stage gasification through the external temperature control system, set the second stage gasification temperature to 2800°C to 3000°C, and set the second stage gasification time to 2h to 4h;

[0089] Step S56: After the second-stage gasification in step S55, graphite with metal impurities removed is obtained.

[0090] Removing moisture and organic impurities at a lower temperature avoids energy waste and unnecessary complexity of high-temperature treatment; organic matter is removed at a low temperature to avoid decomposition at high temperature to produce harmful gases such as dioxins, reduce air pollution and protect the environment; by gradually increasing the temperature, excessive sintering of materials or other forms of thermal damage can be avoided, and the quality of the final product can be improved; at high temperatures, metal impurities can be completely removed, and high temperature conditions help to optimize the crystal structure of graphite, improve its purity and performance; by removing most impurities at a lower temperature first, the time and energy required for high-temperature treatment can be reduced, saving energy and reducing costs. The two-stage gasification process saves about 25% of energy compared to single high-temperature treatment; gradually increasing the temperature can reduce the thermal load and stress of equipment, extend the service life of equipment, and reduce maintenance and replacement costs; staged gasification can better control the reaction process and parameters of each treatment stage, ensure the stability and controllability of the treatment process, especially in the high-temperature stage, to ensure the best treatment effect; by gradually increasing the temperature in stages, the risk of sudden thermal reactions and equipment failures can be reduced, and the overall safety of the process can be improved.

[0091] The purpose of setting the first stage gasification temperature to 300℃~400℃ is:

[0092] (1) Remove moisture. In the temperature range of 300℃ to 400℃, the moisture in the material will be effectively evaporated and removed. This step is very important to prevent the risk of rapid gasification and explosion at higher temperatures (such as 2800℃). By removing moisture, damage to equipment and structural changes in materials can be avoided;

[0093] (2) Decomposition of low-temperature volatile organic impurities. In the copper-containing negative electrode material, there may be some residual binders (such as PVDF) and solvents (such as NMP). These substances can be removed by pyrolysis or evaporation in the range of 300°C to 400°C, thereby reducing their interference and the generation of harmful gases during high-temperature treatment;

[0094] (3) Reduce energy consumption. Removing volatile organic impurities and moisture at a lower temperature can reduce the energy consumption of subsequent high-temperature treatment. If directly treated at high temperature, all volatile components will consume more energy to gasify. By pre-treating at low temperature first, the energy consumption of the high-temperature stage can be reduced, making the overall process more energy-efficient (e.g., from 800kWh to 400kWh).

[0095] In addition, PVDF (polyvinylidene fluoride): In the temperature range of 300℃ to 400℃, PVDF will begin to thermally decompose, producing hydrofluoric acid (HF) and some low molecular weight fluorine-containing organic substances (such as fluorinated hydrocarbon compounds). Due to the low temperature, this decomposition reaction is relatively slow, and the by-products produced are relatively small, mainly hydrofluoric acid (HF) and a small amount of tetrafluoroethylene and other gases. Decomposition under this temperature condition can avoid violent reactions at higher temperatures and control the amount of harmful gases generated.

[0096] Removal effect: At 300℃~400℃, the pyrolysis of PVDF is relatively mild and the removal efficiency is high, but it will produce a certain amount of HF gas and other volatile organic compounds. An effective gas treatment system is required to capture these harmful gases.

[0097] If directly treated at 1700℃, PVDF will undergo violent pyrolysis and combustion, generating more fluorides (such as hydrofluoric acid HF) and some more complex fluorocarbons. The decomposition reaction rate at this high temperature is very fast, which may lead to the generation of a large amount of toxic gases (such as HF and carbon tetrafluoride, etc.). In addition, the high temperature of 1700℃ may also cause equipment corrosion and other uncontrollable side reactions.

[0098] Removal effect: Although high temperature can ensure the complete removal of PVDF, it will produce more harmful byproducts, such as hydrofluoric acid and other toxic fluorides. It is very important to control the emission of these harmful substances.

[0099] NMP (N-methylpyrrolidone): In the temperature range of 300℃ to 400℃, NMP will also undergo thermal decomposition to generate some nitrogen oxides (NO x ), carbon monoxide (CO), carbon dioxide (CO2) and other low molecular weight nitrogen-containing organic compounds. The decomposition temperature of NMP is relatively low, so within this temperature range, most of NMP will be evaporated or pyrolyzed and removed.

[0100] Removal effect: In this temperature range, NMP can be removed more effectively and the harmful gases produced are relatively small. Lower temperatures can reduce the generation of toxic byproducts.

[0101] If directly treated at 1700℃, NMP will burn completely or decompose into simple molecules such as carbon dioxide (CO2), water (H2O), nitrogen oxides (NO x ) and carbon monoxide (CO). Due to the extremely high temperature, the decomposition reaction is very thorough, but it may also produce a large amount of nitrogen oxides, which are very harmful to the environment and health.

[0102] Removal effect: NMP can be completely removed at high temperatures, but it will produce a large amount of gases such as nitrogen oxides and carbon monoxide, which requires strict gas treatment and monitoring measures.

[0103] Therefore, in summary, compared with direct treatment at a high temperature of 1700°C, the advantages of setting the first stage gasification temperature to 300°C to 400°C are as follows:

[0104] Removal efficiency: At a high temperature of 1700°C, PVDF and NMP will decompose more thoroughly, but will produce a large amount of harmful gases, such as hydrofluoric acid (HF), nitrogen oxides (NO x ) etc. At 300℃~400℃, although the removal efficiency is slightly lower, it can better control the generation of harmful gases and reduce the impact on the environment;

[0105] Energy consumption: The energy required for the temperature condition of 300℃~400℃ is much lower than that of 1700℃, so the use of lower temperature pretreatment can significantly reduce the overall energy consumption;

[0106] Equipment loss and safety: A high temperature of 1700°C will increase the heat load of the equipment and may cause corrosion or damage to the furnace. In contrast, a processing temperature of 300°C to 400°C is milder, with less loss to the equipment and higher safety.

[0107] The purpose of setting the second stage gasification temperature to 2800℃~3000℃ is:

[0108] (1) Realize secondary graphitization. The temperature requirement for secondary graphitization: Graphitization is usually carried out at a high temperature of 2000℃ to 3000℃. The graphitization process requires a sufficiently high temperature to break the disordered structure in the carbon material and rearrange the carbon atoms into a highly ordered graphite layer structure. The graphitization process will be more thorough at 2800℃ or above, which can significantly improve the crystallinity and purity of graphite and is suitable for high-performance applications;

[0109] (2) Removal of metal impurities: Most metal impurities, such as copper, iron, nickel, etc., have high boiling points. In order to evaporate or oxidize these metals into a form that can be removed, a higher temperature is required. For example, the boiling point of copper is 2562°C, the boiling point of iron is 2862°C, and the boiling point of nickel is 2913°C. Therefore, the temperature must be set at least 2800°C to 3000°C or higher to effectively remove these metal impurities.

[0110] In addition: at a temperature of 2800℃~3000℃ or higher, not only can secondary graphitization be fully achieved, but also all possible metal impurities and other non-metallic impurities (such as sulfur, phosphorus, etc.) can be oxidized or volatilized, and finally high-purity graphite can be obtained.

[0111] like Figures 12 to 15 The oxidation furnace 10 shown includes a crusher assembly 10-1, an oxidation furnace assembly 10-2 and a cooling device 11. The oxidation furnace assembly 10-2 includes a furnace body 10-4, a first driving mechanism and an oxidation air inlet pipe 10-6; the first driving mechanism is used to drive the furnace body 10-4 to rotate, a plurality of stirring blades 10-7 are spirally arranged on the inner wall of the furnace body 10-4, a heater is arranged in the furnace body 10-4, a valve 10-8 for feeding and discharging is arranged on the side wall of the furnace body 10-4, at least a part of the crusher assembly 10-1 is located above the valve 10-8, at least a part of the cooling device 11 is located below the valve 10-8, and one end of the air inlet pipe 10-6 is connected to the furnace body 10-4;

[0112] The crusher assembly 10-1 includes a crushing chamber 10-9, a rotor 10-10 and an impact component 10-11. A crushing chamber 10-12 is formed in the crushing chamber 10-9. The rotor 10-10 is rotatably arranged in the crushing chamber 10-12. The impact component 10-11 is arranged on the rotor 10-10 and is used to collide with the material. A collision plate 10-13 is arranged in the crushing chamber 10-12. The collision plate 10-13 is configured on one side of the rotor 10-10. After colliding with the impact component 10-11, the material collides with the collision plate 10-13.

[0113] The impact component 10-11 is driven to rotate by the rotation of the rotor 10-10, so that the pure copper is hit by the impact component 10-11 and broken, and the broken pure copper is thrown onto the collision plate 10-13 under the action of centrifugal force, and is further broken to a particle size less than or equal to 5 mm, so that the broken pure copper particles are more uniform, which is beneficial to the subsequent oxidation treatment; by setting a rotating furnace body 10-4 and spirally arranging a plurality of stirring blades 10-7 on the inner wall of the furnace body 10-4, it is ensured that the copper particles are evenly distributed, and the particles are heated more evenly, so that they can fully contact with the working gas in the furnace body 10-4 to complete the oxidation reaction.

[0114] The first driving mechanism includes a first driving motor 10-14, a first driving wheel 10-15, a first driven wheel 10-16, a first connecting shaft 10-17 and a first belt 10-18, wherein the first driving wheel 10-15 is arranged on the motor shaft of the first driving motor 10-14, the first driving wheel 10-15 and the first driven wheel 10-16 are driven by the first belt 10-18, and the two ends of the first connecting shaft 10-17 are respectively connected to the first driven wheel 10-16 and the furnace body 10-4. By arranging the first driving motor 10-14 and the belt transmission, the furnace body 10-4 can rotate during the oxidation reaction, so that the pure copper particles in the furnace body 10-4 are heated more evenly.

[0115] The oxidation furnace assembly 10-2 also includes two support bases 10-19 and two first bearing seats 10-20. The two first bearing seats 10-20 are respectively arranged on the support base 10-19 and located at both ends of the furnace body 10-4. The first connecting shaft 10-17 is installed on one of the first bearing seats 10-20 through a bearing, and the oxidation air intake pipe 10-6 is installed on the other first bearing seat 10-20 through a bearing. A feed port 10-21 is provided at the upper end of the crushing bin 10-9, and a discharge port 22 is provided at the lower end of the crushing bin 10-9. The crusher assembly 10-1 also includes two second driving mechanisms and a screening and transporting assembly. The two second driving mechanisms are respectively located on both sides outside the crushing bin 10-9 and connected to both ends of the rotor 10-10. The two driving mechanisms are used to drive the rotor 10-10 to rotate. The screening and transporting assembly is arranged below the drop port 10-35 and is used to receive the crushed material. One end of the screening and transporting assembly extends to the top of the valve 10-8.

[0116] Each second drive mechanism includes a second drive motor 10-23, a second driving wheel 10-24, a second passive wheel 10-25, a second connecting shaft 10-26, a second belt 10-27 and a second bearing seat 10-28. The second driving wheel 10-24 is arranged on the motor shaft of the second drive motor 10-23. The second driving wheel 10-24 and the second passive wheel 10-25 are transmitted by the second belt 10-27. The two ends of the second connecting shaft 10-26 are respectively connected to the second passive wheel 10-25 and the rotor 10-10. The second bearing seat 10-28 is installed on the outer wall of the crushing bin 10-9, and the second connecting shaft 10-26 is installed on the second bearing seat 10-28 through a bearing. By setting up a second drive motor 10-23 and a belt drive, the rotor 10-10 can rotate at high speed, so that a high-speed collision occurs between the impact component 10-11 and the pure copper material to crush the pure copper material. In addition, the pure copper material that is not crushed thoroughly enough is thrown out by the centrifugal force and thrown onto the collision plate 10-13, and is further impacted and crushed.

[0117] The screening and transporting assembly includes a support 10-29, a material drop bin 10-30, a screening drum 10-31, a guide plate 10-32 and a conveyor belt 10-33. The material drop bin 10-30 is arranged above the support 10-29. An inlet 10-34 is provided at the upper end of the material drop bin 10-30. The inlet 10-34 is connected to the discharge port 10-22. A material drop port 10-35 is provided at the lower end of the material drop bin 10-30. The screening drum 10-31 is obliquely installed on the support 10-29. One end of the screening drum 10-31 is connected to the material outlet 10-35, and a plurality of screening holes are provided on the side wall of the screening drum 10-31. A guide plate 10-32 is arranged on the other end of the screening drum 10-31, and the guide plate 10-32 is arranged lower than the material outlet 10-35. A conveyor belt 10-33 is arranged on a bracket 10-29, and one end of the conveyor belt 10-33 is located below the screening holes of the screening drum 10-31, and the other end of the conveyor belt 10-33 extends to the top of 10-8.

[0118] The crushed pure copper particles fall into the drop bin 10-30, and are further screened by the screening cylinder 10-31 to ensure that the diameter of the pure copper particles entering the oxidation furnace is less than or equal to 5 mm, thereby improving the oxidation efficiency. Copper blocks larger than 5 mm continue to roll along the screening cylinder 10-31 to the guide plate 10-32, and are collected for secondary crushing.

[0119] The bracket 10-29 is provided with a third drive motor 10-36 and a third bearing seat 10-37, the motor shaft of the third drive motor 10-36 is connected to the other end of the screening drum 10-31, the third bearing seat 10-37 is installed on the bracket 10-29, and the motor shaft of the third drive motor 10-36 is installed on the third bearing seat 10-37 through a bearing. The third drive motor 10-36 is provided to enable the screening drum 10-31 to rotate, thereby improving screening efficiency.

[0120] The cooling device 11 includes a support frame 10-38, a conveying roller 10-39 and a conveying belt 10-40. The conveying roller 10-39 is rotatably mounted on the upper end of the support frame 10-38. The conveying belt 10-40 is arranged on the outer side of the conveying roller 10-39. The conveying belt 10-40 is located below the valve 10-8. The conveying belt 10-40 is arranged below the valve 10-8, so that the copper oxide after oxidation is completed can be directly dropped on the conveying belt 10-40 for cooling. Through the cooperation of the conveying roller 10-39 and the conveying belt 10-40, the copper oxide cooled to room temperature can be continuously transported to the next process for collection or packaging.

[0121] The oxidation process of the oxidation furnace 10 oxidizes the regenerated copper powder into copper oxide, which includes the following steps:

[0122] Step S101, crushing processing, start the second driving motor 10-23 to drive the second driving wheel 10-24 to rotate, the second driving wheel 10-24 and the second driven wheel 10-25 are driven by the second belt 10-27, so that the rotor 10-10 rotates, and then the impact component 10-11 installed on the rotor 10-10 rotates with the rotor 10-10, and the pure copper obtained from the aeration separation is put into the crushing chamber 10-12 of the crushing bin 10-9 from the feed port 10-21, and the pure copper is hit by the impact component 10-11 and crushed, and The crushed pure copper is thrown onto the collision plate 10-13 under the action of centrifugal force and is further crushed. The crushed copper blocks fall into the drop bin 30 from the discharge port 10-22, and then enter the screening cylinder 10-31 through the drop port 10-35 of the drop bin 10-30. The sieve hole diameter of the screening cylinder 10-31 is 5mm. Copper blocks less than or equal to 5mm pass through the sieve hole and fall onto the conveyor belt 10-33. Copper blocks larger than 5mm continue to roll along the screening cylinder 10-31 to the guide plate 10-32 and are collected for secondary crushing.

[0123] Step S102, preheating the oxidation furnace, connecting the heater to an external power source, turning on the heater, raising the temperature of the oxidation zone to a range of 450°C to 550°C, and setting the heating rate to 5°C / min to 15°C / min;

[0124] Step S103, loading, opening the conveyor belt 10-33, transporting the copper blocks with a size of less than or equal to 5 mm obtained in step S101 to the oxidation furnace, opening the valve 10-8, and allowing the broken copper blocks to fall into the furnace body 10-4;

[0125] Step S104, oxidation treatment, the temperature of the oxidation zone is maintained in the range of 450°C to 550°C, oxygen or air is introduced into the furnace body 10-4 through the oxidation air intake pipe 10-6, the air intake flow rate is set to 1L / min to 3L / min, and the first driving motor 10-14 is turned on to drive the first driving wheel 10-15 to rotate, the first driving wheel 10-15 and the first driven wheel 10-16 are driven by the first belt 10-18, so that the furnace body 10-4 rotates, and the copper block in the furnace body 10-4 is stirred by the stirring blade 10-7 as it rotates;

[0126] Step S105, the material is cooled, and after the oxidation reaction is completed, the first drive motor 10-14 is turned off, and the valve 10-8 is opened, and the copper oxide after the oxidation in step S104 falls from the valve 10-8 onto the conveyor belt 10-40;

[0127] Step S106, cooling and collecting, after the copper oxide on the conveyor belt 10-40 cools to room temperature, it is collected and packaged.

[0128] By adopting this oxidation process step, the pure copper obtained from aeration separation is first crushed, and the crushed pure copper particles are more uniform, which increases the contact area between copper and the working gas and is beneficial to the subsequent oxidation treatment. Then the oxidation furnace is preheated to ensure that a stable oxidation environment is reached in the furnace, and the crushed pure copper particles are evenly loaded into the furnace body 10-4. With the cooperation of the stirring blade 10-7, the copper particles are evenly distributed and the particles are heated more evenly to improve the oxidation efficiency. The oxidation treatment is carried out under this parameter to ensure that the pure copper particles are fully in contact with the working gas, so that the oxidation time is reduced from 8h to 4h, and the processing energy consumption is reduced from 800kWh to 400kWh, and the energy consumption is reduced by about 50%; the purity of copper oxide is increased from 95% to 99%, which has the advantages of low energy consumption, high oxidation efficiency and high purity of copper oxide.

[0129] Example 1

[0130] The capacity of aeration tank 2-1 is designed to be 800L, and the raw material of copper-containing negative electrode plate is: 100kg, copper content is 20%, and graphite content is 60%. The raw material of copper-containing negative electrode plate is set to be: 100kg, copper content is 20%, and graphite content is 60%.

[0131] like Figure 1 A method for regenerating and recovering a copper-containing battery negative electrode material is shown, which specifically comprises the following steps:

[0132] Step S1, initial screening of raw materials, where waste negative electrode materials from waste batteries or produced during the production process are screened to remove obvious impurities and non-metallic materials to obtain recycled raw materials;

[0133] Step S2, aeration separation, the recycled raw material obtained in step S1 is put into the aeration separation device, after the aeration separation is completed, the liquid is a graphite-containing liquid, and the precipitate is a copper current collector; specifically: the recycled raw material obtained in step S1 is put into the aeration tank, 400L of pure water is added, the solid-liquid ratio is maintained at 1:3, the aeration equipment is started, and the air flow rate is 600L / min; during the aeration process, the stirring speed is 220rpm, the temperature is room temperature, the aeration time is 3.5h, and the aeration separation is completed;

[0134] Step S3, respectively recovering the liquid and sediment after aeration separation;

[0135] Among them, liquid recovery includes:

[0136] Step S4, sedimentation separation, the graphite-containing liquid obtained in step S2 enters a sedimentation tank, the upper clear liquid of the sedimentation tank flows back to the aeration tank, and the bottom of the sedimentation tank is graphite slurry;

[0137] Step S5, two-stage gasification, adding water to the graphite slurry obtained in step S4 and stirring, with a solid-liquid ratio of 1:1, entering a first-stage gasification device, with a first-stage gasification temperature of 300° C. and a first-stage gasification time of 2 hours, removing moisture and organic impurities to obtain dry graphite; then the dry graphite enters a second-stage gasification device, with a second-stage gasification temperature of 2900° C. and a second-stage gasification time of 3 hours, removing metal impurities to obtain primary graphite;

[0138] Step S6, ball milling, putting the primary graphite obtained in step S5 into a ball mill, the ball milling time is 4 hours, the ball milling medium ratio is 1:3, the rotation speed is controlled at 150 rpm, and the particle size after crushing is required to reach D90<10 μm;

[0139] Step S7, repairing graphite, putting the ball-milled graphite into a repair furnace, introducing a hydrogen atmosphere, the repair temperature is 800°C, the repair time is 2 hours, and the hydrogen flow rate needs to be controlled at 100 ml / min during the repair process. After the repair is completed, the finished graphite is obtained;

[0140] Sediment recovery includes:

[0141] Step S8, dehydration, passing the precipitate obtained in step S2 through a dehydration device to remove excess water to obtain a primary copper current collector;

[0142] Step S9, crushing, the primary copper current collector obtained in step S8 is put into a crushing device, the crusher speed is 500 rpm, the crushing time is 30 minutes, and the particle size of the copper particles after crushing is less than or equal to 5 mm;

[0143] Step S10, oxidation treatment, copper particles are loaded into an oxidation furnace, and copper oxide is obtained through oxidation; specifically, the crushed copper particles are loaded into an oxidation furnace, oxygen is introduced, oxygen concentration: 100% (pure oxygen), oxidation atmosphere: pure oxygen atmosphere, heating rate: 10°C / min, cooling rate: natural cooling, oxygen flow rate: 2L / min, oxidation temperature: 450°C, oxidation time: 4h, and oxidation reaction is completed to obtain copper oxide;

[0144] Step S11, cooling and collecting to obtain finished copper oxide.

[0145] The separation result in step S2: the graphite purity is 97%, and the copper sheet recovery rate is 92%.

[0146] In step S5, the first-stage water and organic impurity removal rate is 98%; the second-stage metal impurity removal rate is 99.9%. Results: graphite purity is 98%, metal impurity content is 0.03%, energy consumption is 400kWh, and dioxin generation is 0.02ng / m 3 .

[0147] Step S10 results: copper oxide purity 95%, energy consumption 375kWh, oxygen consumption 0.12m3 / h.

[0148] Example 2

[0149] The difference from Example 1 is that the amount of pure water added is 480 L, the solid-liquid ratio of the copper-containing negative electrode plate raw material to pure water is 1:3, the air flow rate is set to 600 L / min, the stirring speed is set to 220 rpm, and the aeration time is set to 3.5 h.

[0150] Separation results: graphite purity is 99.2%, and copper sheet recovery rate is 94%.

[0151] Example 3

[0152] The difference from Example 1 is that the amount of pure water added is 600 L, the solid-liquid ratio of the copper-containing negative electrode plate raw material to pure water is 1:3, the air flow rate is set to 600 L / min, the stirring speed is set to 220 rpm, and the aeration time is set to 3.5 h.

[0153] Separation results: graphite purity is 96%, and copper sheet recovery rate is 90%.

[0154] From Examples 1 to 3, it can be seen that when other parameters are the same, when the amount of pure water added is 480 L, the graphite purity and copper sheet recovery rate are the highest.

[0155] Example 4

[0156] The difference from Example 1 is that the amount of pure water added is 480 L, the solid-liquid ratio of the copper-containing negative electrode plate raw material to pure water is 1:2, the air flow rate is set to 600 L / min, the stirring speed is set to 220 rpm, and the aeration time is set to 3.5 h.

[0157] Separation results: graphite purity 95%, copper sheet recovery rate 91%.

[0158] Example 5

[0159] The difference from Example 1 is that the amount of pure water added is 480 L, the solid-liquid ratio of the copper-containing negative electrode plate raw material to pure water is 1:4, the air flow rate is set to 600 L / min, the stirring speed is set to 220 rpm, and the aeration time is set to 3.5 h.

[0160] Separation results: graphite purity 96%, copper sheet recovery rate 92%.

[0161] From Example 2, Example 4 and Example 5, it can be concluded that when other parameters are the same, when the solid-liquid ratio of the copper-containing negative electrode sheet raw material to pure water is 1:3, the graphite purity and copper sheet recovery rate are the highest.

[0162] Example 6

[0163] The difference from Example 1 is that the amount of pure water added is 480 L, the solid-liquid ratio of the copper-containing negative electrode plate raw material to pure water is 1:3, the air flow rate is set to 500 L / min, the stirring speed is set to 220 rpm, and the aeration time is set to 3.5 h.

[0164] Separation results: graphite purity 97%, copper sheet recovery rate 92%.

[0165] Example 7

[0166] The difference from Example 1 is that the amount of pure water added is 480 L, the solid-liquid ratio of the copper-containing negative electrode plate raw material to pure water is 1:3, the air flow rate is set to 700 L / min, the stirring speed is set to 220 rpm, and the aeration time is set to 3.5 h.

[0167] Separation results: graphite purity 96%, copper sheet recovery rate 91%.

[0168] From Example 2, Example 6 to Example 7, it can be seen that when other parameters are the same, the air flow rate is set to 600 L / min, and the graphite purity and copper sheet recovery rate are the highest.

[0169] Example 8

[0170] The difference from Example 1 is that the amount of pure water added is 480 L, the solid-liquid ratio of the copper-containing negative electrode plate raw material to pure water is 1:3, the air flow rate is set to 600 L / min, the stirring speed is set to 200 rpm, and the aeration time is set to 3.5 h.

[0171] Separation results: graphite purity 97%, copper sheet recovery rate 92%.

[0172] Example 9

[0173] The difference from Example 1 is that the amount of pure water added is 480 L, the solid-liquid ratio of the copper-containing negative electrode plate raw material to pure water is 1:3, the air flow rate is set to 600 L / min, the stirring speed is set to 250 rpm, and the aeration time is set to 3.5 h.

[0174] Separation results: graphite purity 96%, copper sheet recovery rate 91%.

[0175] It can be seen from Example 2, Example 8 and Example 9 that when other parameters are the same, the stirring speed is set to 220 rpm, and the graphite purity and copper sheet recovery rate are the highest.

[0176] Example 10

[0177] The difference from Example 1 is that the amount of pure water added is 480 L, the solid-liquid ratio of the copper-containing negative electrode plate raw material to pure water is 1:3, the air flow rate is set to 600 L / min, the stirring speed is set to 220 rpm, and the aeration time is set to 2 h.

[0178] Separation results: graphite purity 95%, copper sheet recovery rate 90%.

[0179] Embodiment 11

[0180] The difference from Example 1 is that the amount of pure water added is 480 L, the solid-liquid ratio of the copper-containing negative electrode plate raw material to pure water is 1:3, the air flow rate is set to 600 L / min, the stirring speed is set to 220 rpm, and the aeration time is set to 5 h.

[0181] Separation results: graphite purity 97%, copper sheet recovery rate 92%.

[0182] It can be seen from Example 2, Example 10 and Example 11 that when other parameters are the same, the aeration time is set to 3.5 hours, and the graphite purity and copper sheet recovery rate are the highest.

[0183] It can be seen from Examples 1 to 11 that when the optimal process parameters are the following data, the graphite purity and copper sheet recovery rate are the highest:

[0184] Aeration tank 2-1 capacity: 800L; pure water added: 480L; solid-liquid ratio of copper-containing negative electrode raw material and pure water: 1:3; air flow rate set to: 600L / min; stirring speed set to: 220rpm; temperature: room temperature 25℃; aeration time set to: 3.5h. The separation results obtained with the optimal process parameters are: graphite purity 99.2%, copper sheet recovery rate 94%.

[0185] Example 12

[0186] The difference from Example 1 is: gasification temperature of the first stage: 350℃; gasification time of the first stage: 2h; water and organic impurity removal rate of the first stage: 98%; gasification temperature of the second stage: 2900℃; gasification time of the second stage: 3h; metal impurity removal rate of the second stage: 99.9%. Results: graphite purity 99.2%, metal impurity content 0.01%, energy consumption 375kWh, dioxin generation <0.01ng / m 3 .

[0187] Example 13

[0188] The difference from Example 1 is: gasification temperature of the first stage: 400℃; gasification time of the first stage: 2h; water and organic impurity removal rate of the first stage: 98%; gasification temperature of the second stage: 2900℃; gasification time of the second stage: 3h; metal impurity removal rate of the second stage: 99.9%. Results: graphite purity 97.5%, metal impurity content 0.02%, energy consumption 380kWh, dioxin generation 0.01ng / m 3 .

[0189] From Example 1, Example 12 and Example 13, it can be concluded that when other parameters are the same, when the first-stage gasification temperature is 350° C., the graphite purity is the highest, and the metal impurity content, energy consumption and dioxin generation are the lowest.

[0190] Embodiment 14

[0191] The difference from Example 1 is: gasification temperature of the first stage: 350℃; gasification time of the first stage: 1h; water and organic impurity removal rate of the first stage: 98%; gasification temperature of the second stage: 2900℃; gasification time of the second stage: 3h; metal impurity removal rate of the second stage: 99.9%. Results: graphite purity 98.5%, metal impurity content 0.015%, energy consumption 370kWh, dioxin generation <0.01ng / m 3 .

[0192] Embodiment 15

[0193] The difference from Example 1 is: gasification temperature of the first stage: 350℃; gasification time of the first stage: 3h; water and organic impurity removal rate of the first stage: 98%; gasification temperature of the second stage: 2900℃; gasification time of the second stage: 3h; metal impurity removal rate of the second stage: 99.9%. Results: graphite purity 99%, metal impurity content 0.012%, energy consumption 380kWh, dioxin generation <0.01ng / m 3 .

[0194] From Example 12, Example 14 and Example 15, it can be concluded that when other parameters are the same, when the gasification time is 2 hours, the graphite purity is the highest, and the metal impurity content, energy consumption and dioxin generation are the lowest.

[0195] Example 16

[0196] The difference from Example 1 is: gasification temperature of the first stage: 350℃; gasification time of the first stage: 2h; water and organic impurity removal rate of the first stage: 95%; gasification temperature of the second stage: 2900℃; gasification time of the second stage: 3h; metal impurity removal rate of the second stage: 99.9%. Results: graphite purity 98.8%, metal impurity content 0.015%, energy consumption 385kWh, dioxin generation <0.01ng / m 3 .

[0197] Embodiment 17

[0198] The difference from Example 1 is: gasification temperature of the first stage: 350℃; gasification time of the first stage: 2h; water and organic impurity removal rate of the first stage: 99%; gasification temperature of the second stage: 2900℃; gasification time of the second stage: 3h; metal impurity removal rate of the second stage: 99.9%. Results: graphite purity 99.2%, metal impurity content 0.01%, energy consumption 375kWh, dioxin generation <0.01ng / m3 .

[0199] From Example 12, Example 16 and Example 17, it can be concluded that when other parameters are the same, the best removal rate of water and organic impurities in the first stage is 98%, and the effect is the best at this time.

[0200] Embodiment 18

[0201] The difference from Example 1 is: gasification temperature of the first stage: 350℃; gasification time of the first stage: 2h; water and organic impurity removal rate of the first stage: 98%; gasification temperature of the second stage: 2800℃; gasification time of the second stage: 3h; metal impurity removal rate of the second stage: 99.9%. Results: graphite purity 98.7%, metal impurity content 0.02%, energy consumption 370kWh, dioxin generation <0.01ng / m 3 .

[0202] Embodiment 19

[0203] The difference from Example 1 is: gasification temperature of the first stage: 350℃; gasification time of the first stage: 2h; water and organic impurity removal rate of the first stage: 98%; gasification temperature of the second stage: 3000℃; gasification time of the second stage: 3h; metal impurity removal rate of the second stage: 99.9%. Results: graphite purity 99.2%, metal impurity content 0.01%, energy consumption 375kWh, dioxin generation <0.01ng / m 3 .

[0204] From Example 12, Example 18 and Example 19, it can be concluded that when other parameters are the same, the comprehensive effect is best when the second-stage gasification temperature is 2900°C.

[0205] Embodiment 20

[0206] The difference from Example 1 is: gasification temperature of the first stage: 350℃; gasification time of the first stage: 2h; water and organic impurity removal rate of the first stage: 98%; gasification temperature of the second stage: 2900℃; gasification time of the second stage: 2h; metal impurity removal rate of the second stage: 99.9%. Results: graphite purity 98.9%, metal impurity content 0.02%, energy consumption 370kWh, dioxin generation <0.01ng / m 3 .

[0207] Embodiment 21

[0208] The difference from Example 1 is: gasification temperature of the first stage: 350℃; gasification time of the first stage: 2h; water and organic impurity removal rate of the first stage: 98%; gasification temperature of the second stage: 2900℃; gasification time of the second stage: 4h; metal impurity removal rate of the second stage: 99.9%. Results: graphite purity 99.3%, metal impurity content 0.01%, energy consumption 380kWh, dioxin generation <0.01ng / m 3 .

[0209] From Example 12, Example 20 and Example 21, it can be concluded that when other parameters are the same, the comprehensive effect is best when the second-stage gasification time is 3 hours.

[0210] Embodiment 22

[0211] The difference from Example 1 is: gasification temperature of the first stage: 350℃; gasification time of the first stage: 2h; water and organic impurity removal rate of the first stage: 98%; gasification temperature of the second stage: 2900℃; gasification time of the second stage: 3h; metal impurity removal rate of the second stage: 98%. Results: graphite purity 98.5%, metal impurity content 0.02%, energy consumption 375kWh, dioxin generation <0.01ng / m 3 .

[0212] Embodiment 23

[0213] The difference from Example 1 is: gasification temperature of the first stage: 350℃; gasification time of the first stage: 2h; water and organic impurity removal rate of the first stage: 98%; gasification temperature of the second stage: 2900℃; gasification time of the second stage: 3h; metal impurity removal rate of the second stage: 99.99%. Results: graphite purity 99.2%, metal impurity content 0.01%, energy consumption 375kWh, dioxin generation <0.01ng / m 3 .

[0214] From Example 12, Example 22 and Example 23, it can be concluded that when other parameters are the same, the optimal removal rate of the second-stage metal impurities is 99.9%, and the comprehensive effect is the best at this time.

[0215] From Example 1, Example 12 to Example 23, it can be obtained that when the optimal process parameters are the following data, the effect of two-stage gasification of graphite is the best: first-stage gasification temperature: the best effect is at 350°C; first-stage gasification time: the best effect is at 2h; first-stage removal rate: 98% is the best removal rate; second-stage gasification temperature: 2900°C is the best temperature; second-stage gasification time: the best effect is at 3h; second-stage removal rate: 99.9% is the best removal rate. The results obtained with the optimal process parameters are: graphite purity 99.2%, metal impurity content 0.01%, energy consumption 375kWh, dioxin generation <0.01ng / m 3 .

[0216] Embodiment 24

[0217] The difference from Example 1 is: oxidation temperature: 500°C; oxidation time: 4h; oxygen concentration: 100% (pure oxygen); oxidation atmosphere: pure oxygen atmosphere; heating rate: 10°C / min; cooling rate: natural cooling; air flow rate: 2L / min. Result: copper oxide purity 99%, energy consumption 400kWh, oxygen consumption 0.12m 3 / h.

[0218] Embodiment 25

[0219] The difference from Example 1 is: oxidation temperature: 550℃; oxidation time: 4h; oxygen concentration: 100% (pure oxygen); oxidation atmosphere: pure oxygen atmosphere; heating rate: 10℃ / min; cooling rate: natural cooling; air flow rate: 2L / min. Result: copper oxide purity 98%, energy consumption 425kWh, oxygen consumption 0.12m 3 / h.

[0220] Investigating the oxidation temperature, it can be concluded from Example 1, Example 24 and Example 25 that when other parameters are the same, the best effect is achieved when the oxidation temperature is 500°C.

[0221] Embodiment 26

[0222] The difference from Example 1 is: oxidation temperature: 500°C; oxidation time: 2h; oxygen concentration: 100% (pure oxygen); oxidation atmosphere: pure oxygen atmosphere; heating rate: 10°C / min; cooling rate: natural cooling; air flow rate: 2L / min. Result: copper oxide purity 96%, energy consumption 350kWh, oxygen consumption 0.12m 3 / h.

[0223] Embodiment 27

[0224] The difference from Example 1 is: oxidation temperature: 500°C; oxidation time: 6h; oxygen concentration: 100% (pure oxygen); oxidation atmosphere: pure oxygen atmosphere; heating rate: 10°C / min; cooling rate: natural cooling; air flow rate: 2L / min. Result: copper oxide purity 99.5%, energy consumption 450kWh, oxygen consumption 0.12m 3 / h.

[0225] Investigating the oxidation time, it can be concluded from Examples 24, 26 and 27 that when other parameters are the same, the best effect is achieved when the oxidation time is 4 hours.

[0226] Embodiment 28

[0227] The difference from Example 1 is: oxidation temperature: 500℃; oxidation time: 4h; oxygen concentration: 21wt%; oxidation atmosphere: air atmosphere; heating rate: 10℃ / min; cooling rate: natural cooling; air flow rate: 2L / min. Result: copper oxide purity 90%, energy consumption 350kWh, oxygen consumption 0.0252m 3 / h.

[0228] Embodiment 29

[0229] The difference from Example 1 is: oxidation temperature: 500℃; oxidation time: 4h; oxygen concentration: 50wt%; oxidation atmosphere: oxygen / air mixed atmosphere; heating rate: 10℃ / min; cooling rate: natural cooling; air flow rate: 2L / min. Result: copper oxide purity 95%, energy consumption 375kWh, oxygen consumption 0.06m 3 / h.

[0230] In examining the oxygen concentration, it can be seen from Example 24, Example 28 and Example 29 that when other parameters are the same, the best effect is achieved when the oxygen concentration is 100%.

[0231] Embodiment 30

[0232] The difference from Example 1 is: oxidation temperature: 500°C; oxidation time: 4h; oxygen concentration: 80wt%; oxidation atmosphere: 80wt% oxygen + 20wt% inert gas (such as nitrogen or argon); heating rate: 10°C / min; cooling rate: natural cooling; air flow rate: 2L / min. Result: copper oxide purity 97%, energy consumption 400kWh, oxygen consumption 0.096m 3 / h.

[0233] Investigating the oxidizing atmosphere, it can be seen from Example 24 and Example 30 that when other parameters are the same, the oxidizing atmosphere is pure oxygen atmosphere, and the effect is best.

[0234] Embodiment 31

[0235] The difference from Example 1 is: oxidation temperature: 500°C; oxidation time: 4h; oxygen concentration: 100% (pure oxygen); oxidation atmosphere: pure oxygen atmosphere; heating rate: 5°C / min; cooling rate: natural cooling; air flow rate: 2L / min. Result: copper oxide purity 98%, energy consumption 380kWh, oxygen consumption 0.12m 3 / h.

[0236] Embodiment 32

[0237] The difference from Example 1 is: oxidation temperature: 500°C; oxidation time: 4h; oxygen concentration: 100% (pure oxygen); oxidation atmosphere: pure oxygen atmosphere; heating rate: 15°C / min; cooling rate: natural cooling; air flow rate: 2L / min. Result: copper oxide purity 97.5%, energy consumption 420kWh, oxygen consumption 0.12m 3 / h.

[0238] Investigating the heating rate, it can be seen from Examples 24, 31 and 32 that when other parameters are the same, the best effect is achieved when the heating rate is 10°C / min.

[0239] Embodiment 33

[0240] The difference from Example 1 is: oxidation temperature: 500°C; oxidation time: 4 hours; oxygen concentration: 100% (pure oxygen); oxidation atmosphere: pure oxygen atmosphere; heating rate: 10°C / min; cooling rate: controlled cooling; air flow rate: 2L / min. Result: copper oxide purity 98.5%, energy consumption 410kWh, oxygen consumption 0.12m 3 / h.

[0241] Embodiment 34

[0242] The difference from Example 1 is: oxidation temperature: 500°C; oxidation time: 4h; oxygen concentration: 100% (pure oxygen); oxidation atmosphere: pure oxygen atmosphere; heating rate: 10°C / min; cooling rate: rapid cooling; air flow rate: 2L / min. Result: copper oxide purity 96%, energy consumption 420kWh, oxygen consumption 0.12m 3 / h.

[0243] Investigating the cooling rate, it can be seen from Example 24, Example 33 and Example 34 that when other parameters are the same, the cooling rate is best when it is natural cooling.

[0244] Embodiment 35

[0245] The difference from Example 1 is: oxidation temperature: 500°C; oxidation time: 4h; oxygen concentration: 100% (pure oxygen); oxidation atmosphere: pure oxygen atmosphere; heating rate: 10°C / min; cooling rate: natural cooling; air flow rate: 1L / min. Result: copper oxide purity 97%, energy consumption 390kWh, oxygen consumption 0.06m 3 / h.

[0246] Embodiment 36

[0247] The difference from Example 1 is: oxidation temperature: 500°C; oxidation time: 4h; oxygen concentration: 100% (pure oxygen); oxidation atmosphere: pure oxygen atmosphere; heating rate: 10°C / min; cooling rate: natural cooling; air flow rate: 3L / min. Result: copper oxide purity 98.5%, energy consumption 410kWh, oxygen consumption 0.18m 3 / h.

[0248] Investigating the air flow rate, it can be seen from Example 24, Example 35 and Example 36 that when other parameters are the same, the best effect is achieved when the air flow rate is 2 L / min.

[0249] In summary, the process parameters of the oxidation furnace shown in Example 1, Example 24 and Example 36 are the best when the following parameters are selected: oxidation temperature: 500°C is the best; oxidation time: 4h is the best time; oxygen concentration: 100% pure oxygen atmosphere is the best; oxidation atmosphere: pure oxygen atmosphere is the best; heating rate: 10°C / min is the best; cooling rate: natural cooling is the best; air flow rate: 2L / min is the best. The results obtained with the optimal process parameters are: copper oxide purity 99%, energy consumption 400kWh, oxygen consumption 0.12m 3 / h.

[0250] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for regenerating and recovering anode materials of copper-containing batteries, characterized in that: The specific steps include: Step S1, initial screening of raw materials, where waste negative electrode materials from waste batteries or produced during the production process are screened to remove obvious impurities and non-metallic materials to obtain recycled raw materials; Step S2, aeration separation, the recycled raw material obtained in step S1 is put into an aeration separation device, and after the aeration separation is completed, the liquid is a graphite-containing liquid, and the precipitate is a copper current collector; Step S3, respectively recovering the liquid and sediment after aeration separation; Wherein, the liquid recovery comprises: Step S4, sedimentation separation, the graphite-containing liquid obtained in step S2 enters a sedimentation tank, the upper clear liquid of the sedimentation tank flows back to the aeration tank, and the bottom of the sedimentation tank is graphite slurry; Step S5, two-stage gasification, adding water to the graphite slurry obtained in step S4 and stirring, with a solid-liquid ratio of 1:1, entering a first-stage gasification device, with a first-stage gasification temperature of 300°C to 400°C, and a first-stage gasification time of 1h to 3h, to remove moisture and organic impurities to obtain dry graphite; then the dry graphite enters a second-stage gasification device, with a second-stage gasification temperature of 2800°C to 3000°C, and a second-stage gasification time of 2h to 4h, to remove metal impurities and obtain primary graphite; Step S6, ball milling, putting the primary graphite obtained in step S5 into a ball mill, the ball milling time is 4 hours, the ball milling medium ratio is 1:3, the rotation speed is controlled at 150 rpm, and the particle size after crushing is required to reach D90<10 μm; Step S7, repairing graphite, putting the ball-milled graphite into a repair furnace, introducing a hydrogen atmosphere, the repair temperature is 800°C, the repair time is 2 hours, and the hydrogen flow rate needs to be controlled at 100 ml / min during the repair process. After the repair is completed, the finished graphite is obtained; The precipitate recovery comprises: Step S8, dehydration, passing the precipitate obtained in step S2 through a dehydration device to remove excess water to obtain a primary copper current collector; Step S9, crushing, the primary copper current collector obtained in step S8 is put into a crushing device, the crusher speed is 500 rpm, the crushing time is 30 minutes, and the particle size of the copper particles after crushing is less than or equal to 5 mm; Step S10, oxidation treatment, copper particles are placed in an oxidation furnace and oxidized to obtain copper oxide; Step S11, cooling and collecting to obtain finished copper oxide.

2. The method for regenerating and recovering the negative electrode material of a copper-containing battery according to claim 1, characterized in that: The aeration separation in step S2 is specifically as follows: the recycled raw material obtained in step S1 is put into an aeration tank, pure water is added, the solid-liquid ratio is maintained at 1:2 to 1:4, the aeration equipment is started, and the air flow rate is 500L / min to 700L / min; during the aeration process, the stirring speed is 150rpm to 250rpm, the temperature is room temperature, the aeration time is 2h to 5h, and the aeration separation is completed.

3. The method for regenerating and recovering the negative electrode material of a copper-containing battery according to claim 1, characterized in that: The oxidation treatment in step S10 is specifically as follows: the crushed copper particles are placed in an oxidation furnace, oxygen or air is introduced, the oxygen flow rate is maintained at 100L / min to 300L / min, the oxidation temperature is 450°C to 550°C, the oxidation time is 2h to 6h, and the oxidation reaction is completed to obtain copper oxide.

4. A recycling device using the method for regenerating and recycling copper-containing battery negative electrode materials according to any one of claims 1 to 3, characterized in that: Along the direction of material travel, a screen and an aeration separation device are sequentially arranged, and the aeration separation device is respectively connected to a liquid recovery component and a sediment recovery component; the liquid recovery component comprises a sedimentation tank, a two-stage gasification device, a ball mill, a repair furnace and a graphite collection tank which are sequentially arranged; the sediment recovery component comprises a dehydration device, a crushing device, an oxidation furnace, a cooling device and a copper oxide collection tank which are sequentially arranged; A water inlet pipe for facilitating the entry of pure water is arranged at the top of the aeration separation device, and a reflux pipe connected with the aeration separation device is arranged at the top of the sedimentation tank.

5. The device for recovering copper-containing battery negative electrode materials according to claim 4, characterized in that: The aeration separation device comprises an aeration tank, a partition is arranged in the aeration tank to separate the aeration tank into an aeration zone and a sedimentation zone, a connecting hole connecting the aeration zone and the sedimentation zone is opened at the upper end of the partition, a feed pipe is arranged at the upper end of the aeration tank, a water inlet pipe is arranged at the lower end of the aeration tank, the feed pipe and the water inlet pipe are both connected to the aeration zone, an aeration assembly is arranged in the aeration zone, and the aeration assembly is used to ventilate the aeration zone; The aeration tank is provided with a stirring assembly, the stirring end of the stirring assembly extends into the aeration zone, the upper end of the sedimentation zone is provided with a second extraction assembly for extracting separated graphite floating objects, and the lower end of the sedimentation zone is provided with a first extraction assembly for extracting separated copper sheets.

6. The device for recovering copper-containing battery negative electrode materials according to claim 5, characterized in that: The aeration assembly comprises an air compressor, an air inlet pipe and a central guide tube. The central guide tube is arranged in the aeration area. The lower end of the central guide tube is connected to the air compressor through the air inlet pipe. The air compressor is arranged outside the lower end of the aeration tank.

7. The device for recovering copper-containing battery negative electrode materials according to claim 4, characterized in that: The two-stage gasification equipment includes a first-stage gasification equipment, a transmission equipment and a second-stage gasification equipment which are sequentially connected and arranged, the first-stage gasification equipment includes a first gasification furnace, a furnace tube is rotatably arranged in the first gasification furnace, the graphite mixture to be heated enters from one end of the furnace tube, a first heater is arranged on the inner wall of the first gasification furnace, and the first heater is located outside the furnace tube; The two-stage gasification equipment includes a second gasification furnace, a heating chamber is provided in the second gasification furnace, a furnace door for adding graphite after a first stage of gasification is provided at the upper end of the second gasification furnace, and a second heater is provided in the heating chamber; One end of the transmission device is connected to the other end of the furnace tube, and the other end of the transmission device is arranged above the furnace door. After a period of gasification, the graphite is discharged from the other end of the furnace tube and transported to the heating chamber of the second gasification furnace through the transmission device.

8. The device for recovering negative electrode materials of copper-containing batteries according to claim 7, characterized in that: The first-stage gasification equipment also includes a driving assembly, a first mounting base and a first feed hopper. The driving assembly and the first gasification furnace are both mounted on the first mounting base. The upper end of the driving assembly is sleeved on the other end of the furnace tube. The driving assembly is used to drive the furnace tube to rotate. The first feed hopper is arranged on one end of the furnace tube.

9. The device for recovering copper-containing battery negative electrode materials according to claim 4, characterized in that: The oxidation furnace comprises a crusher assembly, an oxidation furnace assembly and a cooling device, wherein the oxidation furnace assembly comprises a furnace body, a first driving mechanism and an air inlet pipe; the first driving mechanism is used to drive the furnace body to rotate, a plurality of stirring blades are spirally arranged on the inner wall of the furnace body, a heater is arranged in the furnace body, a valve for feeding and discharging is arranged on the side wall of the furnace body, at least a part of the crusher assembly is located above the valve, at least a part of the cooling device is located below the valve, and one end of the air inlet pipe is connected to the furnace body; The crusher assembly includes a crushing chamber, a rotor and an impact component. A crushing chamber is formed in the crushing chamber. The rotor is rotatably arranged in the crushing chamber. The impact component is arranged on the rotor and is used to collide with the material. A collision plate is arranged in the crushing chamber. The collision plate is configured on one side of the rotor. The material hits the collision plate after colliding with the impact component.

10. The device for recovering copper-containing battery negative electrode materials according to claim 9, characterized in that: The first driving mechanism includes a first driving motor, a first driving wheel, a first driven wheel, a first connecting shaft and a first belt. The first driving wheel is arranged on the motor shaft of the first driving motor. The first driving wheel and the first driven wheel are driven by the first belt. The two ends of the first connecting shaft are respectively connected to the first driven wheel and the furnace body.

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