Tungsten infiltrated copper waste recovery and purification system

Abstract

The utility model discloses a tungsten infiltrated copper waste recycling and purifying system which comprises a waste pretreatment device, the waste pretreatment device is connected with a reaction device through a chute, the reaction device is connected with a filtering and separating device through a rubber hose, and the filtering and separating device is connected with a tungsten recycling device and a copper recycling device through pipelines. The reaction device, the filtering and separating device, the tungsten recycling device and the copper recycling device are connected with a waste gas collecting device and a waste liquid collecting device through pipelines. According to the device, the investment cost of equipment is reduced, the energy consumption and the waste gas treatment cost are reduced, and the device has the characteristics of high recovery quality and purity, low cost and low pollution.

Description

Technical Field

[0001] This utility model belongs to the field of metal waste recycling technology, and relates to a system for recycling and purifying tungsten copper-impregnated waste. Background Technology

[0002] Tungsten-copper infiltrated materials, due to their high resistance to high temperatures, thermal shock, and ablation, as well as good electrical and thermal conductivity and machinability, are commonly used in the manufacture of high-temperature and ablation-resistant components for solid rocket engines, such as gas vanes, protective plates, and throat liners. They are also used in high-temperature counterweights and conductors such as vacuum contacts, counterweights, and conductive nozzles. However, the production, processing, and use of tungsten-copper infiltrated products inevitably generate a large amount of tungsten-copper infiltrated waste. If this waste is disposed of indiscriminately, it will not only result in a significant waste of valuable metal resources but may also pose a threat to the environment.

[0003] Currently, the recycling technologies for tungsten-copper-leached waste mainly cover chemical and physical methods. Chemical methods typically utilize strong inorganic acids such as nitric acid, sulfuric acid, and hydrochloric acid to react with the waste, achieving the separation and recovery of metallic tungsten and copper. In the nitric acid method, copper reacts with nitric acid to form copper nitrate, which enters the solution, while tungsten remains as a precipitate. Subsequent processing steps yield pure metallic tungsten powder and copper nitrate. The sulfuric acid method follows a similar principle. Tungsten is a very inert metal, insoluble in strong acids such as nitric acid and sulfuric acid, and only soluble in aqua regia or a mixture of HF and HNO3. Copper, however, can be oxidized by nitric acid or hot concentrated sulfuric acid to produce copper nitrate or copper sulfate. The reaction equations are as follows:

[0004] Cu+4HNO3(concentrated)=Cu(NO3)2+2NO2↑+2H2O

[0005] 3Cu+8HNO3(dilute)=3Cu(NO3)2+2NO↑+4H2O

[0006] Cu + 2H₂SO₄ (conc.) CuSO4+SO2↑+2H2O.

[0007] Physical methods mainly include smelting and mechanical crushing and screening. Smelting requires high temperatures and consumes a lot of energy. Although mechanical crushing and screening is simple to operate and has a lower cost, it can only achieve preliminary separation of tungsten and copper, and the purity of the product is not good, making it difficult to meet the production requirements of high-quality materials. Utility Model Content

[0008] The purpose of this invention is to provide a system for recycling and purifying tungsten copper-infiltrated waste, which features high recycling quality and purity, low cost, and low pollution.

[0009] The technical solution adopted in this utility model is a tungsten copper infiltration waste recycling and purification system, including a waste pretreatment device, a reaction device connected to the waste pretreatment device via a chute, a filtration and separation device connected to the reaction device via a rubber hose, a tungsten recovery device and a copper recovery device connected to the filtration and separation device via pipelines, and a waste gas collection device and a waste liquid collection device connected to the reaction device, the filtration and separation device, the tungsten recovery device and the copper recovery device via pipelines.

[0010] The features of this utility model also include:

[0011] The waste pretreatment device includes a vibrating feeder, the discharge port of which is connected to the inlet of a crusher and grinder, and the discharge port of the crusher and grinder is connected to the inlet of a magnetic separator.

[0012] The reaction apparatus includes a continuously variable speed stirrer and a temperature-controlled heater. The outlets of the continuously variable speed stirrer and the temperature-controlled heater are connected to the inlet of the reactor. The inlet of the reactor is also connected to the outlet of the magnetic separator via a stainless steel inclined chute.

[0013] The filtration and separation device includes a vacuum filter. The inlet of the vacuum filter is connected to the outlet of the reaction vessel via an acid and alkali resistant rubber hose. The filtrate outlet of the vacuum filter is connected to the feed of a horizontal centrifuge via a polyvinyl chloride pipe.

[0014] A diaphragm metering pump is installed on the PVC pipeline between the vacuum filter and the horizontal centrifuge.

[0015] The tungsten recovery device includes a washing tank, the inlet of which is connected to the outlet of a vacuum filter via a stainless steel conveyor belt, and the outlet of the washing tank is connected to the inlet of a dryer.

[0016] A material distributor is installed on the stainless steel conveyor belt between the vacuum filter and the washing tank.

[0017] The copper recovery device includes an evaporator crystallizer. The inlet of the evaporator crystallizer is connected to the outlet of a horizontal centrifuge via a polytetrafluoroethylene pipe. The outlet of the evaporator crystallizer is connected to an electrolytic cell.

[0018] The waste gas collection device is connected to a reaction device, a filtration and separation device, a tungsten recovery device, and a copper recovery device via stainless steel pipes.

[0019] The waste liquid collection device is connected to the reaction device, filtration and separation device, tungsten recovery device and copper recovery device through engineering plastic pipes.

[0020] The beneficial effects of this utility model are:

[0021] 1. This utility model relates to a tungsten-copper infiltration waste recycling and purification system. Through pretreatment of the waste, optimized control of the reaction process, and efficient separation and purification technology, this utility model significantly improves the recycling efficiency of metallic tungsten and copper. Actual testing has verified that the tungsten recovery rate can reach over 99.2%, and the copper recovery rate can reach over 95.5%, significantly higher than traditional recycling methods. This effectively ensures the efficient recycling of metal resources and improves recycling efficiency.

[0022] 2. This utility model's tungsten-copper waste recycling and purification system incorporates multiple meticulous processes, including washing, drying, reduction, and recrystallization, during the tungsten and copper recycling process. These processes effectively remove impurities and significantly improve the purity of the recycled products. The purity of the recovered tungsten powder can reach over 99%, and the purity of the copper can also reach over 99%, fully meeting the stringent requirements of high-end manufacturing for high-quality metal materials. This provides high-quality raw material support for industrial upgrading and improves product quality.

[0023] 3. This utility model relates to a tungsten-copper infiltration waste recycling and purification system. The system is equipped with a waste gas treatment device that can comprehensively and deeply purify various harmful waste gases generated during the reaction process, ensuring that the waste gases meet emission standards and curbing environmental pollution at its source. Compared with traditional chemical recycling methods, pollutant emissions are significantly reduced, effectively protecting the ecological environment and the health of operators, aligning with the concept of green development, and reducing environmental pollution.

[0024] In summary, this utility model of tungsten-copper infiltration waste recycling and purification system reduces equipment investment costs through optimized design and integrated technology application. Furthermore, its efficient recycling process reduces metal loss and resource waste, while also lowering energy consumption and waste gas treatment costs. This enhances economic benefits, strengthens the company's market competitiveness and sustainable development capabilities, and saves costs. It features high recycling quality and purity, low cost, and low pollution. Attached Figure Description

[0025] Figure 1 This is a schematic diagram of the overall structure of the tungsten copper infiltration waste recycling and purification system of this utility model.

[0026] In the diagram: 1. Waste pretreatment device; 11. Vibrating feeder; 12. Crusher and grinder; 13. Magnetic separator; 2. Reaction device; 21. Reactor; 22. Variable speed stirrer; 23. Temperature-controlled heater; 3. Filtration and separation device; 31. Vacuum filter; 32. Horizontal centrifuge; 4. Tungsten recovery device; 41. Washing tank; 42. Dryer; 5. Copper recovery device; 51. Evaporator crystallizer; 52. Electrolytic cell; 6. Waste gas collection device; 7. Waste liquid collection device. Detailed Implementation

[0027] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments.

[0028] Tungsten-copper infiltration waste recycling and purification system, such as Figure 1 As shown, it includes a waste pretreatment device 1, a reaction device 2 connected to the waste pretreatment device 1 via a chute, a filtration and separation device 3 connected to the reaction device 2 via a rubber hose, a tungsten recovery device 4 and a copper recovery device 5 connected to the filtration and separation device 3 via pipes, and a waste gas collection device 6 and a waste liquid collection device 7 connected to the reaction device 2, the filtration and separation device 3, the tungsten recovery device 4 and the copper recovery device 5 via pipes.

[0029] The waste pretreatment device 1 includes a vibrating feeder 11, the discharge port of which is connected to the inlet of a crusher-grinder 12, and the discharge port of the crusher-grinder 12 is connected to the inlet of a magnetic separator 13. The vibrating feeder 11 precisely controls the feeding speed of the waste to ensure uniform and stable feeding; the crusher-grinder 12 crushes the tungsten copper-infiltrating waste to a suitable particle size, effectively increasing the contact area between the waste and subsequent processing reagents, thus improving reaction efficiency; the magnetic separator 13 removes magnetic impurities from the waste to prevent them from interfering with subsequent recycling processes and to ensure the purity of the recycled products.

[0030] The reaction apparatus 2 includes a continuously variable speed stirrer 22 and a temperature-controlled heater 23. The outlets of the continuously variable speed stirrer 22 and the temperature-controlled heater 23 are connected to the inlet of the reaction vessel 21. The inlet of the reaction vessel 21 is also connected to the outlet of the magnetic separator 13 via a stainless steel inclined chute. The chute is inclined at an angle of 30-45° to allow the material to flow smoothly into the reaction vessel 21 under gravity. The inner wall of the chute is polished to reduce material residue and the risk of blockage. A manual gate valve is installed at the connection between the chute and the inlet to control the material feeding speed and start / stop, ensuring the stability and safety of the reaction vessel during the feeding process. The reaction vessel 21 is made of zirconium material resistant to strong acid corrosion. The reaction vessel 21 is equipped with a stirring device and a heating device. The stirring device, through an optimized blade structure and speed adjustment function, achieves thorough and uniform stirring of the reactants, ensuring a complete reaction. The heating device can precisely control the reaction temperature to meet the needs of different reaction conditions. Meanwhile, the reactor 21 is equipped with multiple feed inlets, which can precisely add waste tungsten copper-impregnated material, inorganic acids such as nitric acid or sulfuric acid, and appropriate amounts of oxidants such as hydrogen peroxide, providing ideal material conditions for the reaction.

[0031] The filtration and separation device 3 includes a vacuum filter 31. The inlet of the vacuum filter 31 is connected to the outlet at the bottom of the reaction vessel 21 via an acid and alkali resistant rubber hose. The rubber hose has good flexibility and corrosion resistance, and can adapt to possible relative displacement and vibration between the reaction vessel 21 and the vacuum filter 31, while ensuring the sealing during material transfer. Stainless steel clamps are used to secure the hose to the outlet of the reaction vessel 21 and the inlet of the vacuum filter 31 to prevent material leakage. The filtrate outlet of the vacuum filter 31 is connected to the feed of the horizontal centrifuge 32 via a PVC pipe. The PVC pipe has advantages such as corrosion resistance, smooth inner wall, and low resistance, which is conducive to the rapid and stable transfer of filtrate. A diaphragm metering pump is installed on the PVC pipe between the vacuum filter 31 and the horizontal centrifuge 32 to accurately control the flow rate of filtrate entering the centrifuge, ensuring that the centrifuge operates under optimal conditions and improving the separation effect. Vacuum filter 31 uses filter media with different pore sizes to initially separate solid tungsten and copper-containing solution after reaction based on particle size differences; horizontal centrifuge 32 uses a powerful centrifugal force field to further refine the separation of residual small amount of solid impurities and solution, effectively improving the separation effect and laying a solid foundation for subsequent tungsten and copper recovery.

[0032] The tungsten recovery unit 4 includes a washing tank 41. The inlet of the washing tank 41 is connected to the outlet of a vacuum filter 31 via a stainless steel conveyor belt. The outlet of the washing tank 41 is connected to the inlet of a dryer 42. The surface of the stainless steel conveyor belt is treated with anti-slip material to prevent the filter cake from slipping during transport. The speed of the conveyor belt can be adjusted by a frequency converter to match the feeding requirements of the washing tower. A material distributor is installed on the stainless steel conveyor belt between the vacuum filter 31 and the washing tank 41, specifically at the connection between the conveyor belt and the inlet of the washing tank 41, to ensure that the filter cake enters the washing tower evenly and improves the washing effect. The tungsten product obtained by the tungsten recovery unit 4 undergoes washing, drying, and reduction processes. The washing process uses dilute acids such as dilute nitric acid and dilute sulfuric acid, along with deionized water, to efficiently remove impurities adhering to the tungsten surface through a multi-stage countercurrent washing process. The drying stage employs vacuum drying equipment to ensure the drying quality of the tungsten products in a low-temperature, low-oxygen environment. The reduction treatment is carried out in a high-temperature reduction furnace, where reducing gases such as hydrogen or decomposed ammonia are introduced. The reduction temperature, time, and gas flow rate are precisely controlled to completely reduce the tungsten oxide to metallic tungsten, significantly improving the purity and recovery rate of tungsten.

[0033] The copper recovery device 5 includes an evaporator crystallizer 51. The inlet of the evaporator crystallizer 51 is connected to the outlet of a horizontal centrifuge 32 via a polytetrafluoroethylene (PTFE) pipe, and the outlet of the evaporator crystallizer 51 is connected to an electrolytic cell 52. Specifically, the copper-containing solution first enters the evaporator crystallizer. By precisely controlling key parameters such as temperature and pressure, copper salts such as copper nitrate and copper sulfate are precipitated. Subsequently, a recrystallization process is used to deeply purify the coarse crystals. Utilizing the significant difference in solubility between impurities and copper salts at different temperatures, the purity of the copper salts is further improved. Finally, high-purity metallic copper can be obtained through electrolysis or displacement methods, achieving efficient copper recovery and recycling.

[0034] The waste gas collection device 6 connects to the reaction device 2, filtration and separation device 3, tungsten recovery device 4, and copper recovery device 5 via stainless steel pipelines. The stainless steel pipelines are argon arc welded to ensure their sealing and strength, preventing solution leakage that could cause environmental pollution and material loss. The exhaust port at the top of the reactor 21 in the reaction device 2 is connected to the inlet at the bottom of the waste gas treatment device 6. The stainless steel pipelines are insulated to prevent the temperature of the waste gas from dropping during transmission, which could lead to condensation of acidic gases that could corrode the pipelines or affect subsequent treatment. An induced draft fan is installed on the stainless steel pipelines to generate negative pressure, promptly extracting the waste gas generated during the reaction and transporting it to the waste gas collection device 6. The fan's airflow can be selected and controlled by frequency conversion based on the reactor volume and waste gas generation, ensuring efficient operation of the waste gas treatment system. During the reaction, the waste gas collection device 6 promptly transports the generated nitrogen oxides, sulfur dioxide, and other waste gases to the waste gas treatment tower. The waste gas treatment tower is sequentially filled with an alkaline spray layer, an activated carbon adsorption layer, and a catalytic oxidation layer. The alkaline spray layer uses alkaline solutions such as sodium hydroxide and calcium hydroxide to neutralize acidic waste gas, achieving preliminary purification. The activated carbon adsorption layer, with its huge specific surface area and abundant pore structure, effectively adsorbs residual harmful gases and organic impurities. The catalytic oxidation layer, with the help of specific catalysts such as precious metal catalysts and transition metal oxide catalysts, deeply oxidizes low-valence nitrogen oxides and sulfur dioxide in the waste gas into high-valence harmless substances such as nitrate and sulfate under suitable temperature and oxygen conditions. Finally, the waste gas is discharged in compliance with standards through the tail gas emission system, ensuring the high efficiency and environmental friendliness of waste gas treatment.

[0035] Waste liquid collection device 7 is connected to reaction device 2, filtration and separation device 3, tungsten recovery device 4, and copper recovery device 5 via engineering plastic pipes. The PTFE pipes possess excellent corrosion resistance, resisting the erosion of copper-containing solutions by acid ions and potential trace oxidants. The PTFE pipes are designed with appropriate slopes and directions based on the layout of each device and the location of waste liquid generation, ensuring that the waste liquid flows smoothly into the storage tank under gravity. A drain valve is installed at the lowest point of the pipe to periodically discharge any accumulated sediment. Furthermore, electromagnetic flow meters and regulating valves are installed on the pipes to monitor and control the solution flow rate in real time, ensuring the stable operation of the evaporation and crystallization process. The outlet of waste liquid collection device 7 is connected to the inlet of a precision filter via a corrosion-resistant centrifugal pump. The flow rate and head of the centrifugal pump are selected based on the waste liquid treatment volume and system resistance, ensuring that the waste liquid is stably delivered to the precision filter for preliminary filtration. Check valves and pressure gauges are installed on the pump's inlet and outlet pipes to prevent backflow of waste liquid and monitor the pump's operating pressure, ensuring the safe and stable operation of the system. Waste liquid from waste liquid collection device 7 is collected in a dedicated storage tank. After passing through a precision filter with a pore size of 1-10 μm to remove suspended impurities, it enters an adjustment tank to adjust the pH to 2-5. The ion exchange resin column, specifically a combination of a strong acidic cation exchange resin and a weakly basic anion exchange resin, is pumped in to remove heavy metal ions such as copper and tungsten ions, as well as acid radical ions. The resin can be periodically regenerated and recycled. The treated liquid enters a neutralization reaction tank, where lime slurry or sodium hydroxide solution is added to adjust the pH to 6-9. The resulting precipitate is separated by a plate and frame filter press. The filter cake is properly disposed of, part of the filtrate is reused, and the remainder is discharged after meeting standards.

[0036] Example 1

[0037] Tungsten-copper infiltration waste recycling and purification system, such as Figure 1 As shown, it includes a waste pretreatment device 1, a reaction device 2 connected to the waste pretreatment device 1 via a chute, a filtration and separation device 3 connected to the reaction device 2 via a rubber hose, a tungsten recovery device 4 and a copper recovery device 5 connected to the filtration and separation device 3 via pipes, and a waste gas collection device 6 and a waste liquid collection device 7 connected to the reaction device 2, the filtration and separation device 3, the tungsten recovery device 4 and the copper recovery device 5 via pipes.

[0038] Example 2

[0039] Based on the tungsten copper infiltration waste recycling and purification system provided in Example 1, in this example, the waste pretreatment device 1 includes a vibrating feeder 11, the discharge port of the vibrating feeder 11 is connected to the inlet of the crusher and grinder 12, and the discharge port of the crusher and grinder 12 is connected to the inlet of the magnetic separator 13.

[0040] The reaction apparatus 2 includes a continuously variable speed stirrer 22 and a temperature control heater 23. The outlets of the continuously variable speed stirrer 22 and the temperature control heater 23 are connected to the inlet of the reaction vessel 21. The inlet of the reaction vessel 21 is also connected to the outlet of the magnetic separator 13 through a stainless steel inclined chute.

[0041] Example 3

[0042] Based on the tungsten-copper infiltration waste recovery and purification system provided in Example 2, in this example, the filtration and separation device 3 includes a vacuum filter 31. The inlet of the vacuum filter 31 is connected to the outlet of the reaction vessel 21 via an acid and alkali resistant rubber hose. The filtrate outlet of the vacuum filter 31 is connected to the feed of a horizontal centrifuge 32 via a polyvinyl chloride (PVC) pipe. A diaphragm metering pump is installed on the PVC pipe between the vacuum filter 31 and the horizontal centrifuge 32. The vacuum filter 31 uses filter media with different pore sizes to initially separate the solid tungsten and copper-containing solution after the reaction based on the particle size difference. The horizontal centrifuge 32, with the help of a strong centrifugal force field, further refines the separation of the remaining small amount of solid impurities and solution, effectively improving the separation effect and laying a solid foundation for the subsequent recovery of tungsten and copper.

[0043] Example 4

[0044] Based on the tungsten copper infiltration waste recycling and purification system provided in Example 3, in this example, the tungsten recycling device 4 includes a washing tank 41. The inlet of the washing tank 41 is connected to the outlet of the vacuum filter 31 via a stainless steel conveyor belt. The outlet of the washing tank 41 is connected to the inlet of the dryer 42. A material distributor is provided on the stainless steel conveyor belt between the vacuum filter 31 and the washing tank 41.

[0045] The copper recovery device 5 includes an evaporator crystallizer 51. The inlet of the evaporator crystallizer 51 is connected to the outlet of a horizontal centrifuge 32 via a polytetrafluoroethylene pipe. The outlet of the evaporator crystallizer 51 is connected to an electrolytic cell 52.

[0046] The waste gas collection device 6 is connected to the reaction device 2, the filtration and separation device 3, the tungsten recovery device 4, and the copper recovery device 5 via stainless steel pipes; the waste liquid collection device 7 is connected to the reaction device 2, the filtration and separation device 3, the tungsten recovery device 4, and the copper recovery device 5 via engineering plastic pipes.

[0047] Example 5

[0048] Based on the tungsten copper-infiltrating waste recycling and purification system provided in Example 4, this example describes the recycling of tungsten copper-infiltrating blocks, specifically including the following steps:

[0049] Waste pretreatment: Tungsten copper-infiltrated blocks are placed in a vibrating feeder 11, with a feeding speed of 50 kg / h set according to the block size and hardness, and then fed into a crusher and grinder 12 to be crushed to a particle size of 2-5 mm. A magnetic separator 13 uses a 0.8T magnetic field to remove magnetic impurities, such as iron filings and magnetic oxides, to prevent interference with subsequent reactions.

[0050] Reaction process: Pretreated waste is fed into reactor 21, along with 6 mol / L nitric acid and an appropriate amount of hydrogen peroxide. The liquid-to-solid ratio of nitric acid to hydrogen peroxide is 4:1. The continuously variable speed stirrer 22 is adjusted to 300 r / min for mixing, and the heating jacket is heated to 80℃ for 4 hours. The temperature and pressure sensors inside the reactor work in conjunction with the control system to dynamically adjust the temperature according to the heat of reaction and changes in materials, ensuring a highly efficient and safe reaction.

[0051] Separation operation: After the reaction, the material is fed into a vacuum filter 21 with a vacuum degree of 0.06 MPa. A 0.5 μm polyester filter cloth is used to retain the tungsten skeleton. The filtrate is fed into a horizontal centrifuge 32 with a speed of 4000 r / min and centrifuged for 10 min to remove minor impurities and obtain a clear copper-containing solution.

[0052] Tungsten recovery process: The tungsten filter cake is fed into washing tank 41 and washed for 30 minutes in an ultrasonic environment with a concentration of 2 mol / L dilute nitric acid at a temperature of 40℃, a frequency of 40kHz, and a power of 3kW, using 2 mol / L nitric acid. It is then washed with four stages of countercurrent deionized water until the pH reaches 6.5. After washing, the tungsten is dried for 6 hours in a vacuum rake dryer at a pressure of 0.08MPa and a temperature of 80℃. It is then transferred to a vertical resistance furnace with a flow rate of 2 m³ / h and hydrogen is introduced. The tungsten is reduced in three stages at 400-800-1000℃ to obtain high-purity tungsten powder with a purity of 99.6%, with each stage at 400-800-1000℃ lasting 1.5 hours.

[0053] Copper recovery steps: Copper-containing liquid is fed into an evaporation and concentration crystallizer, where it is evaporated and concentrated at 70℃ to obtain copper nitrate crystals. The mother liquor is reused. The coarse crystals are fed into a continuous recrystallizer, heated at a rate of 1℃ / min until reaching 85℃ to dissolve the crystals, and then cooled and crystallized at a rate of 0.5℃ / min. After filtration, high-purity copper nitrate is obtained. To produce metallic copper, the copper nitrate is dissolved in a diaphragm electrolytic cell with a current density of 300A / m² and a temperature of 45℃ for electrolysis. The cathode yields metallic copper with a purity of 99.5%.

[0054] Waste gas treatment: The reaction waste gas enters the waste gas collection device 6, where a 3 mol / L NaOH solution is sprayed at a rate of 10 L / min to neutralize the acidic gas. The waste gas collection device 6 contains an activated carbon fiber felt adsorption layer with a specific surface area of ​​2000 m² / g and a thickness of 1 m to capture residual pollutants. The waste gas collection device 6 also contains a 365 nm photocatalytic oxidation layer with a TiO2 loading of 10% and a UV photolysis function with a power of 2 kW to decompose complex pollutants. After treatment, the waste gas meets emission standards, with nitrogen oxide emissions reduced by 90% and SO2 emissions reduced by 95%.

[0055] Wastewater Treatment: The wastewater generated by the system reaction enters a storage tank, passes through a precision filter with a 5μm filter element to remove impurities, and then enters an adjustment tank to adjust the pH to 3. It then enters an ion exchange resin column consisting of a strong acidic cation exchange resin and a weakly basic anion exchange resin in a 2:1 volume ratio connected in series to remove copper, tungsten, and acid radical ions. The treated liquid enters a neutralization reaction tank, where lime slurry is added to adjust the pH to 7.5. The resulting precipitate is separated by a plate and frame filter press. The filter cake is properly disposed of, part of the filtrate is reused, and the remainder is discharged after meeting standards, reducing water waste and pollution.

[0056] Example 6

[0057] Based on the tungsten copper-infiltrating waste recycling and purification system provided in Example 4, this example describes the recycling of tungsten cold isostatic pressing billet powder, specifically including the following steps:

[0058] Waste pretreatment: Tungsten cold isostatic pressing billet recovery powder is fed into crusher and grinder 12 via vibrating feeder 11 at a feeding speed of 30 kg / h, and crushed to a particle size of 0.5-2 mm according to the powder particle size and agglomeration state. Magnetic separator 13 uses a field strength of 0.6T to remove magnetic impurities, ensuring the uniformity and purity of the material.

[0059] Reaction process: The powder is fed into reactor 21, and 5 mol / L sulfuric acid and hydrogen peroxide are added. The liquid-to-solid ratio of sulfuric acid to hydrogen peroxide is 5:1. The speed of the continuously variable stirrer 22 is adjusted to 400 r / min for mixing. The mixture is heated to 75℃ and reacted for 3.5 h. The multi-parameter monitoring and control system inside the reactor optimizes the reaction conditions according to the material characteristics and reaction progress, such as adjusting the amount and timing of hydrogen peroxide addition based on acid concentration, copper dissolution rate, and other factors.

[0060] Separation operation: The reactants are fed into a vacuum filter 21 with a vacuum degree of 0.05 MPa. Tungsten is retained on a 0.2 μm polytetrafluoroethylene filter cloth. The filtrate is fed into a horizontal centrifuge 32 with a speed of 3500 r / min and centrifuged for 8 min. This efficiently separates the solid and liquid, reduces the impurity content, and improves the quality of the solution.

[0061] Tungsten recovery process: Tungsten filter cake is fed into washing tank 41 and washed for 25 minutes in an ultrasonic environment with a concentration of 1.5 mol / L dilute sulfuric acid at a temperature of 45℃, a frequency of 30 kHz, and a power of 2 kW, using 1.5 mol / L sulfuric acid. The mixture is then washed with 5 stages of countercurrent deionized water until the pH reaches 6.8. After washing, the tungsten is dried for 5 hours in a vacuum rake dryer at a pressure of 0.07 MPa and a temperature of 70℃. It is then transferred to a vertical resistance furnace with a flow rate of 1.5 m³ / h and hydrogen is introduced. The tungsten is reduced in three stages at 300-700-900℃ to obtain high-purity tungsten powder with a purity of 99.7%. Each stage at 300-700-900℃ lasts for 1.2 hours. The product exhibits a uniform microstructure and narrow particle size distribution.

[0062] Copper recovery steps: Copper-containing liquid is fed into an MVR evaporator and concentrated crystallizer, where it is concentrated at 65℃ to precipitate copper sulfate crystals. The mother liquor is reused. The coarse crystals are fed into a continuous recrystallizer, heated to 82℃ at a rate of 0.8℃ / min until crystals dissolve, and then cooled and crystallized at a rate of 0.6℃ / min. High-purity copper sulfate is obtained by filtration. To produce metallic copper, copper sulfate is dissolved in a diaphragm electrolytic cell with a current density of 250A / m² and a temperature of 42℃ for electrolysis. The cathode yields metallic copper with a purity of 99.4%, and the product has a smooth surface and excellent conductivity.

[0063] Waste gas treatment: Waste gas enters the waste gas collection device 6, where it is neutralized by spraying with a 2 mol / L NaOH solution at a rate of 8 L / min. The waste gas collection device 6 contains an activated carbon fiber felt adsorption layer with a specific surface area of ​​1500 m² / g and a thickness of 0.8 m for adsorption and purification. The waste gas collection device 6 also contains a 365 nm photocatalytic oxidation layer with a TiO2 loading of 8% and UV light with a power of 1.5 kW for treatment. The concentration of pollutants in the emitted waste gas is far below the national standard, and the emission of volatile organic compounds is reduced by 95%.

[0064] Wastewater Treatment: The wastewater generated by the system reaction enters a storage tank, and after being filtered through a precision filter with a 3μm filter element to remove impurities, it enters an adjustment tank to adjust the pH to 2.5. It then enters an ion exchange resin column consisting of a strong acid cation exchange resin and a weak base anion exchange resin connected in series at a volume ratio of 3:2 for deep impurity removal. The treated liquid enters a neutralization reaction tank, where sodium hydroxide solution is added to adjust the pH to 8. The resulting precipitate is separated by a plate and frame filter press, and the filter cake is properly disposed of. The filtrate reuse rate reaches 70%, effectively saving water resources and reducing production costs.

[0065] Example 7

[0066] Based on the tungsten copper infiltration waste recycling and purification system provided in Example 4, this example describes the recycling of tungsten sintered billet powder, specifically including the following steps:

[0067] Waste pretreatment: Tungsten sintered billet recovery powder is fed into crusher and grinder 12 via vibrating feeder 11 at a feeding speed of 40 kg / h. The crushing chamber structure and impact frequency are optimized according to the powder hardness and agglomeration degree, and the powder is crushed to a particle size of 1-3 mm. Magnetic separator 13 is selected with a field strength of 0.7T to remove magnetic impurities.

[0068] Reaction process: The powder is fed into reactor 21, and 4 mol / L nitric acid and hydrogen peroxide are added. The liquid-solid ratio of sulfuric acid to hydrogen peroxide is 6:1. The speed of the continuously variable stirrer 22 is adjusted to 350 r / min for mixing. The mixture is heated to 70℃ and reacted for 4 hours. During the reaction, the control system precisely regulates reaction parameters such as acid concentration, oxidant dosage, temperature, and reaction time based on feedback from pH and redox potential sensors, thereby improving reaction efficiency and selectivity.

[0069] Separation operation: The reactants are fed into a vacuum filter 21 with a vacuum degree of 0.04 MPa. Tungsten is retained in the 0.3 μm nylon filter cloth. The filtrate is fed into a horizontal centrifuge 32 with a speed of 3000 r / min and centrifuged for 12 min. The solid and liquid are separated efficiently. The filtrate has a stable copper ion concentration and few impurities.

[0070] Tungsten recovery process: Tungsten filter cake is fed into washing tank 41 and washed for 20 minutes in an ultrasonic environment with a concentration of 1 mol / L dilute sulfuric acid at a temperature of 50℃, a frequency of 25kHz, and a power of 1.5kW, followed by four-stage countercurrent deionized water washing to pH 7. After washing, the tungsten is dried for 4 hours in a vacuum rake dryer at a pressure of 0.06MPa and a temperature of 65℃. Then, it is transferred to a vertical resistance furnace with a flow rate of 1m³ / h and hydrogen is introduced. The tungsten is reduced in three stages at 350-750-950℃ to obtain high-purity tungsten powder with a purity of 99.8%. Each stage at 350-750-950℃ lasts for 1 hour. The product has low oxygen content, high activity, and uniform and controllable particle size.

[0071] Copper recovery steps: Copper-containing liquid is fed into an evaporation and concentration crystallizer, where it is concentrated at 68℃ to precipitate copper sulfate crystals, and the mother liquor is recycled. The coarse crystals are fed into a continuous recrystallizer, heated to 80℃ at a rate of 0.6℃ / min until crystals dissolve, and then cooled and crystallized at a rate of 0.4℃ / min. High-purity copper sulfate is obtained by filtration. To produce metallic copper, copper sulfate is dissolved in a diaphragm electrolytic cell with a current density of 200 A / m² and a temperature of 40℃ for electrolysis. The cathode yields metallic copper with a purity of 99.6%, producing a product with a complete crystal structure, few impurities, and high plasticity.

[0072] Waste gas treatment: Waste gas enters the waste gas collection device 6, where it is neutralized by spraying a 2.5 mol / L NaOH solution at a rate of 12 L / min. The waste gas collection device 6 contains an activated carbon fiber felt adsorption layer with a specific surface area of ​​2500 m² / g and a thickness of 1.2 m for adsorption and purification. The waste gas collection device 6 also contains a 365 nm photocatalytic oxidation layer with a TiO2 loading of 12% and UV light with a power of 1.5 kW for treatment. The concentration of pollutants in the emitted waste gas is far below the national standard, and the emission of volatile organic compounds is reduced by 92%.

[0073] Wastewater Treatment: The wastewater generated by the system reaction enters a storage tank, and after being filtered through a precision filter with a 3μm filter element to remove impurities, it enters an adjustment tank to adjust the pH to 2.5. It then enters an ion exchange resin column consisting of a strong acid cation exchange resin and a weak base anion exchange resin connected in series at a volume ratio of 3:2 for deep impurity removal. The treated liquid enters a neutralization reaction tank, where sodium hydroxide solution is added to adjust the pH to 8. The resulting precipitate is separated by a plate and frame filter press, and the filter cake is properly disposed of. The filtrate reuse rate reaches 70%, effectively saving water resources and reducing production costs.

Claims

1. A tungsten copper dross recovery and purification system, characterized by, The application relates to a waste material pretreatment device (1) connected with a reaction device (2) through a chute, the reaction device (2) being connected with a filter separation device (3) through a rubber hose, the filter separation device (3) being connected with a tungsten recovery device (4) and a copper recovery device (5) through pipes, and the reaction device (2), the filter separation device (3), the tungsten recovery device (4) and the copper recovery device (5) being connected with a waste gas collecting device (6) and a waste liquid collecting device (7) through pipes.

2. The tungsten copper impregnation waste recovery purification system according to claim 1, characterized in that, The waste material pretreatment device (1) comprises a vibrating feeder (11), the discharging port of the vibrating feeder (11) being communicated with the feeding port of a crushing grinder (12), and the discharging port of the crushing grinder (12) being communicated with the feeding port of a magnetic separator (13).

3. The tungsten copper impregnation waste recovery purification system according to claim 2, characterized in that, The reaction device (2) comprises a stepless speed-variable stirrer (22) and a temperature control heater (23), the discharging ports of the stepless speed-variable stirrer (22) and the temperature control heater (23) being connected with the feeding port of a reaction kettle (21), and the feeding port of the reaction kettle (21) being further communicated with the discharging port of the magnetic separator (13) through a stainless steel inclined chute.

4. The tungsten copper impregnation waste recovery purification system according to claim 3, characterized in that, The filter separation device (3) comprises a vacuum filter (31), the feeding port of the vacuum filter (31) being communicated with the discharging port of the reaction kettle (21) through acid and alkali resistant rubber hoses, and the filtrate outlet of the vacuum filter (31) being communicated with the feeding port of a horizontal centrifuge (32) through a polyvinyl chloride pipe.

5. The tungsten copper impregnation scrap recovery purification system of claim 4, wherein, A diaphragm type metering pump is arranged on the polyvinyl chloride pipe between the vacuum filter (31) and the horizontal centrifuge (32).

6. The tungsten copper impregnation scrap recovery purification system of claim 4, wherein, The tungsten recovery device (4) comprises a washing tank (41), the feeding port of the washing tank (41) being communicated with the discharging port of the vacuum filter (31) through a stainless steel conveying belt, and the discharging port of the washing tank (41) being communicated with the feeding port of a drying machine (42).

7. The tungsten copper impregnation scrap recovery purification system of claim 6, wherein, A material distributor is arranged on the stainless steel conveying belt between the vacuum filter (31) and the washing tank (41).

8. The tungsten copper impregnation scrap recovery purification system of claim 6, wherein, The copper recovery device (5) comprises an evaporation crystallizer (51), the feeding port of the evaporation crystallizer (51) being communicated with the discharging port of the horizontal centrifuge (32) through a polytetrafluoroethylene pipe, and the discharging port of the evaporation crystallizer (51) being communicated with an electrolytic tank (52).

9. The tungsten copper impregnation scrap recovery purification system of claim 1, wherein, The waste gas collecting device (6) is communicated with the reaction device (2), the filter separation device (3), the tungsten recovery device (4) and the copper recovery device (5) through stainless steel pipes.

10. The tungsten copper impregnation scrap recycling purification system according to claim 1, characterized in that, The waste liquid collecting device (7) is communicated with the reaction device (2), the filter separation device (3), the tungsten recovery device (4) and the copper recovery device (5) through engineering plastic pipes.

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