Process and device for separating lead, antimony and silver from high-antimony lead alloy

Abstract

The invention belongs to the technical field of high-antimony lead alloy separation, and particularly relates to a process and device for separating lead, antimony and silver from high-antimony lead alloy.The replacement reaction device of the process comprises a discharging box, two sets of fixing frames are arranged around the discharging box, and a Y-shaped discharging pipe and a funnel are fixedly installed on the two sets of fixing frames respectively; a material receiving barrel is arranged under the material discharging box, a screen is arranged in the material receiving barrel, a liquid discharging pipe is connected to the water outlet position of the material receiving barrel, a transmission gear is rotationally installed at the upper end of the material discharging box, and the three sets of containers continuously rotate in the material discharging box by driving the driving gear. According to the device, silver nitrate leachate and iron powder or a hydrochloric acid solution can be added into the corresponding containers, in the rotating process, the containers can be inversely buckled and returned, silver powder and a ferrous nitrate solution in the containers can be automatically poured out, it is ensured that the silver nitrate leachate can be subjected to a continuous replacement reaction in the three sets of containers, and the silver nitrate leaching efficiency is improved. And the efficiency of replacing the silver powder with the silver nitrate leaching solution is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of separation of high-antimony lead alloys, and in particular relates to a process and a device for separating lead, antimony and silver from high-antimony lead alloys. Background Art

[0002] The separation of lead, antimony and silver in high-antimony lead alloys is usually carried out by combining multiple metallurgical processes. The main common separation methods include: pyrometallurgical process and hydrometallurgical process. The pyrometallurgical process mainly consists of electrolytic refining, chemical leaching, solvent extraction and other steps, which makes the pyrometallurgical process have the advantages of large processing capacity, strong raw material adaptability and mature process.

[0003] The patent with publication number CN108914157B discloses a process for separating lead, antimony and silver from high-antimony lead alloy. The solution is to melt high-antimony lead anode mud into high-antimony lead alloy, and use the technical combination of "pulse electrolysis separation of lead by lead methylsulfonate system - nitric acid oxidation of antimony silver powder - iron powder replacement to extract silver powder" to treat the high-antimony lead alloy process. On the basis of solving the problem of lead and antimony separation in high-antimony lead alloy, the invented process obtains electrolead, antimony dioxide, silver powder and other products from the high-antimony lead alloy, and the process flow is not only simple and environmentally friendly, but also has a high recovery rate for the three types of lead, antimony and silver products.

[0004] In the above scheme, when the silver nitrate leachate is subjected to a replacement reaction, iron powder and hydrochloric acid need to be added sequentially into a container containing the silver nitrate leachate for reaction. Since there is only one group of containers and the capacity is limited, only a certain amount of the silver nitrate leachate can be subjected to the replacement reaction each time, and the reaction cannot be carried out continuously, resulting in a relatively low efficiency of replacing silver powder with the silver nitrate leachate. To this end, the present invention provides a process and device for separating lead, antimony and silver from a high-antimony lead alloy. Summary of the invention

[0005] In order to make up for the deficiencies of the prior art, at least one technical problem raised in the background technology is solved.

[0006] The technical solution adopted by the present invention to solve the technical problem is: a process for separating lead, antimony and silver from a high-antimony lead alloy according to the present invention comprises the following steps: Step 1: Using high antimony lead alloy cast from high antimony lead anode mud as the anode, pulse electrolysis is performed in a lead methanesulfonate system. During electrolysis, the anode is placed in an acid-corrosion-resistant canvas anode bag to receive the anode insoluble matter that falls off during anode electrolysis. Lead is first dissolved into the solution in the form of lead methanesulfonate and then precipitated at the cathode in the form of elemental lead. After electrolysis, the electrolytic lead and antimony silver powder in the anode bag are obtained respectively; Step 2: Using concentrated nitric acid as a leaching agent, subjecting the antimony silver powder obtained in step 1 to oxidative acid leaching, and separating the liquid and solid after the leaching is completed to obtain a silver nitrate leaching solution and an antimony dioxide leaching residue respectively; Step 3: Start the displacement reaction device, and put the silver nitrate leaching solution prepared in Step 2 and iron powder into the two ports at both ends of the Y-shaped discharge pipe according to a certain ratio, so that the silver nitrate leaching solution and iron powder flow into the lower container through the Y-shaped discharge pipe together. After the silver nitrate leaching solution and iron powder react for min, drive the transmission gear to rotate, so that the three conversion frames in the displacement reaction device drive the three containers to rotate, and the container containing the silver nitrate leaching solution and iron powder rotates under the funnel. The next container will rotate under the Y-shaped discharge pipe. Pour hydrochloric acid twice the amount of iron powder into the container containing the silver nitrate leaching solution and iron powder through the funnel, so that the mixed solution in the container reacts further. At the same time, add silver nitrate leaching solution and iron powder to the next container. After 150 min, continue to drive the transmission gear to rotate, and the container containing the mixed solution will automatically pour out silver powder and ferrous nitrate solution. The silver powder and ferrous nitrate solution flow into the receiving bucket through the discharge box, and are filtered through the screen in the receiving bucket to separate the silver powder from the ferrous nitrate solution. Repeat the above operations cyclically to completely displace the silver powder in the silver nitrate leaching solution prepared in Step 2; Under high-temperature conditions, hydrogen is used as a reducing agent to react with antimony trioxide in the antimony trioxide leaching residue to reduce the antimony element to a single substance, and antimony powder is obtained after cooling.

[0007] Preferably, a device for separating lead, antimony, and silver from a high-antimony lead alloy is applicable to the process for separating lead, antimony, and silver from a high-antimony lead alloy described above. It includes a discharge box, with two fixed frames arranged around the discharge box. A Y-shaped discharge pipe and a funnel are respectively and fixedly installed on the two fixed frames. A receiving bucket is arranged directly below the discharge box. A screen is arranged in the receiving bucket, and a drain pipe is connected to the water outlet of the receiving bucket. A transmission gear is rotatably installed at the upper end of the discharge box. The transmission gear meshes with a driving gear, and the driving gear is rotatably installed on one side of the discharge box. Three conversion frames for carrying containers are arranged in the discharge box. The conversion frame includes a U-shaped frame. Three connecting blocks are equiangularly installed on the transmission gear, and the connecting blocks are fixedly connected to the U-shaped frame. Two rotating shafts are respectively rotatably installed at both ends of the U-shaped frame, and the two rotating shafts are symmetrically and fixedly installed on both sides of the container. A torsion spring sleeved on the rotating shaft, one end of the torsion spring is connected to the inner wall of the U-shaped frame, and one end of the torsion spring is connected to the end of the rotating shaft. A flipping gear fixedly sleeved on the rotating shaft, a C-shaped frame movably installed in the U-shaped frame, both ends of the C-shaped frame respectively mesh with the two flipping gears, a support rod fixedly connected to the U-shaped frame, a pulley rotatably installed at the end of the support rod, and an arc-shaped strip for pushing the pulley is arranged on the inner ring of the discharge box; The three groups of containers are continuously rotated in the discharge box by driving the active gears. During each stop, silver nitrate leaching solution and iron powder or hydrochloric acid solution can be added to the corresponding containers. In the process of rotation, the containers can be turned upside down and returned to the right position, so that the silver powder and ferrous nitrate solution in the containers can be automatically poured out, ensuring that the silver nitrate leaching solution can perform continuous replacement reaction in the three groups of containers, thereby improving the efficiency of the silver nitrate leaching solution replacing the silver powder.

[0008] Preferably, a cleaning mechanism for cleaning the container is provided on one side of the receiving barrel, the cleaning mechanism comprises a rubber sleeve, the rubber sleeve is embedded and installed on the discharge box, a nozzle movably plugged into the rubber sleeve, an electric push rod for driving the nozzle, a water pipe fixedly connected to the bottom of the nozzle, four groups of spray holes are provided at the upper end of the nozzle, the lower end of the electric push rod is connected to the nozzle, and the upper end of the electric push rod is connected to the discharge box; The water is sprayed onto the inner wall of the container through the spray hole on the spray pipe. At the same time, the electric push rod continues to drive the spray pipe to move upward, so that the attachments on the inner wall of the container are washed away by water, thereby cleaning the inside of the container and ensuring the cleanliness of the container.

[0009] Preferably, the nozzle comprises a main pipe, the main pipe is movably connected to a rubber sleeve, and four groups of spray holes are provided at the upper end of the main pipe, a movable pipe is arranged inside the nozzle, the lower end of the movable pipe is connected to a water pipe, a movable sleeve is movably mounted on the nozzle, the movable sleeve is fixedly connected to an electric push rod, a spring is mounted on the nozzle, and four groups of rectangular grooves are provided on the nozzle, and scraper racks are arranged in the four groups of rectangular grooves, and the scraper rack comprises a first scraper bar, a second scraper bar hinged to the upper end of the first scraper bar, and a driving rod hinged to the middle part of the first scraper bar, a driven gear is fixedly installed at one end of the driving rod, and a rack meshing with the driven gear is fixedly connected to the movable pipe, a water collecting tank is arranged in the main pipe, the spray hole is connected to the water collecting tank, the movable pipe is movably connected to the water collecting tank, the second scraper bar and the driving rod are both hinged in the rectangular groove, two groups of convex shafts are arranged in the inner ring of the movable sleeve, and two groups of spiral grooves are arranged on the outer ring of the main pipe, and the convex shaft is located in the spiral groove; As the scraper frame rotates, the first scraper bar and the second scraper bar on the scraper frame scrape off the attachments on the inner wall and the bottom of the container respectively, and the water sprayed from the spray hole will be sprayed at the junction of the inner wall and the bottom of the container. The water will be blocked and sprayed in all directions, so that the scraped attachments will be washed away by the water, thereby cleaning the inside of the container more cleanly, greatly reducing the impact of the attachments on the subsequent replacement reaction.

[0010] The beneficial effects of the present invention are as follows: 1. The three groups of containers are continuously rotated in the discharge box by driving the active gear. During each stop, silver nitrate leaching solution and iron powder or hydrochloric acid solution can be added to the corresponding container. In the process of rotation, the container can be turned upside down and returned to the right position, so that the silver powder and ferrous nitrate solution in the container can be automatically poured out, ensuring that the silver nitrate leaching solution can perform continuous replacement reaction in the three groups of containers, thereby improving the efficiency of the silver nitrate leaching solution replacing the silver powder.

[0011] 2. Start the electric push rod, which drives the nozzle to move upward along the rubber sleeve until the upper end of the nozzle enters the inverted container. Start the water pump connected to the water pipe to allow water to flow into the nozzle through the water pipe and spray onto the inner wall of the container through the spray hole on the nozzle. At the same time, the electric push rod continues to drive the nozzle to move upward so that the attachments on the inner wall of the container are washed away by water, thereby cleaning the inside of the container and ensuring the cleanliness of the container.

[0012] 3. Due to the limited space inside the water collection tank, a large amount of water will gather in the water collection tank in a short time, and the water will be ejected through the spray hole to release part of the water pressure. At the same time, the water pressure in the water collection tank will push the movable tube together with the four sets of racks to move downward, and the racks will drive the driven gear together with the driving rod to rotate upward. The driving rod will make the second scraper bar rotate synchronously through the first scraper bar, so that the scraper frame extends from the rectangular groove until the first scraper bar and the second scraper bar are perpendicular to each other, and the first scraper bar and the second scraper bar are close to the inner wall and the bottom of the container respectively. At this time, the electric push rod continues to drive the movable sleeve to move upward , so that the two groups of cams also move upward with the movable sleeve, and the cams squeeze the inner wall of the spiral groove, causing the main pipe to rotate. The rotating main pipe will drive the four groups of scraper racks to rotate. As the scraper racks rotate, the first scraper bar and the second scraper bar on the scraper racks will scrape off the attachments on the inner wall and the bottom of the container respectively, and the water sprayed from the spray hole will be sprayed at the junction of the inner wall and the bottom of the container. The water will be blocked and will spray around, so that the scraped attachments will be washed away by water, so that the inside of the container is cleaned more cleanly, greatly reducing the impact of the attachments on the subsequent replacement reaction. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] The present invention will be further described below in conjunction with the accompanying drawings.

[0014] Figure 1 It is a schematic diagram of the structure of the present invention.

[0015] Figure 2 It is a cross-sectional schematic diagram of the material discharge box, material receiving barrel, transmission gear, container, driving gear, connecting block and conversion frame of the present invention.

[0016] Figure 3 The diagram is a cross-sectional view of the container, the connecting block and the conversion frame assembly of the present invention.

[0017] Figure 4Schematic diagram of the combined discharging box, container and cleaning mechanism in cross-section of the present invention.

[0018] Figure 5 Schematic diagram of the combined container and cleaning mechanism of the present invention.

[0019] Figure 6 Schematic diagram of the combined cross-section of the main pipe, movable pipe, movable sleeve, spring and scraping rack of the present invention.

[0020] Figure 7 Front cross-sectional view of the combined scraping rack, movable pipe and main pipe of the present invention.

[0021] Figure 8 Schematic diagram of another state of the combined main pipe, scraping rack and movable sleeve of the present invention.

[0022] In the figure: 1. Discharging box; 101. Arc strip; 2. Fixed frame; 3. Y-shaped discharging pipe; 4. Hopper; 5. Receiving barrel; 501. Sieve mesh; 6. Drain pipe; 7. Transmission gear; 8. Container; 9. Driving gear; 10. Connecting block; 11. Conversion frame; 13. Cleaning mechanism; 111. U-shaped frame; 112. Rotary joint shaft; 113. Torsion spring; 114. C-shaped frame; 115. Support rod; 116. Pulley; 117. Flipping gear; 131. Rubber sleeve; 132. Spray pipe; 133. Spray hole; 134. Electric push rod; 135. Water pipe; 1321. Main pipe; 21. Water collecting tank; 22. Spiral groove; 1322. Movable pipe; 1323. Movable sleeve; 31. Convex shaft; 1324. Spring; 1325. Rectangular groove; 1326. Scraping rack; 61. First scraping strip; 62. Second scraping strip; 63. Driving rod; 64. Driven gear; 65. Rack. Detailed implementation manners

[0023] In order to make the technical means, creative features, achieved purposes and effects of the present invention easy to understand, the present invention will be further described below in conjunction with specific implementation manners. Embodiment

[0024] A process for separating lead, antimony and silver from high-antimony lead alloy includes the following steps: Step 1: Using the high-antimony lead alloy cast from high-antimony lead anode slime as the anode, performing pulsed electrolysis in a lead methanesulfonate system. During electrolysis, the anode is placed in an acid-resistant canvas anode bag to承接 the anode insoluble matter shed during anode electrolysis. Lead first dissolves in the solution in the form of lead methanesulfonate and then precipitates at the cathode in the form of elemental lead. After electrolysis, electrolytic lead and antimony-silver powder in the anode bag are obtained respectively. Step 2: Using concentrated nitric acid as the leaching agent, performing oxidative acid leaching on the antimony-silver powder obtained in Step 1. After the leaching is completed, liquid-solid separation is carried out to obtain silver nitrate leaching solution and antimony dioxide leaching residue respectively. Step 3: Start the replacement reaction device, put the silver nitrate leaching solution and iron powder prepared in step 2 into the two ports of the Y-shaped discharge pipe 3 in a certain proportion, so that the silver nitrate leaching solution and the iron powder flow into the container 8 below through the Y-shaped discharge pipe 3. After the silver nitrate leaching solution and the iron powder react for 150 minutes, the three groups of conversion racks 11 in the replacement reaction device drive the three groups of containers 8 to rotate by driving the transmission gear 7 to rotate, so that the containers 8 containing the silver nitrate leaching solution and the iron powder are rotated to the bottom of the funnel 4. The next group of containers 8 will be rotated to the bottom of the Y-shaped discharge pipe 3, and the hydrochloric acid twice the amount of the iron powder will be poured into the funnel 4. into the container 8 containing the silver nitrate leachate and the iron powder, so that the mixed solution in the container 8 is further reacted, and at the same time, the silver nitrate leachate and the iron powder are added to the next group of containers 8, and after 150 minutes, the transmission gear 7 is continuously driven to rotate, and the container 8 containing the mixed solution will automatically pour out the silver powder and the ferrous nitrate solution, and the silver powder and the ferrous nitrate solution flow into the receiving barrel 5 through the discharge box 1, and are filtered through the screen 501 in the receiving barrel 5 to separate the silver powder from the ferrous nitrate solution. According to the above operation, the cycle is repeated to completely replace the silver powder in the silver nitrate leachate prepared in step 2; Under high temperature conditions, the antimony dioxide leaching residue uses hydrogen as a reducing agent to react with antimony dioxide to reduce the antimony element to a single substance, and then obtains antimony powder after cooling.

[0025] Furthermore, in order to optimize the process of separating lead, antimony and silver from high-antimony lead alloy, the embodiment of the present invention improves the replacement reaction device. By controlling the three groups of containers 8 to rotate continuously at equal angles in the discharge box 1, the containers 8 can pass under the Y-shaped discharge pipe 3 and the funnel 4 in turn, and the containers 8 can automatically flip over to automatically pour out the materials in the containers 8. With the continuous conversion of the three groups of containers 8, a continuous replacement reaction of the silver nitrate leachate is realized, thereby improving the efficiency of replacing the silver powder. Example

[0026] like Figures 1 to 3As shown in the figure, a device for separating lead, antimony, and silver from a high-antimony lead alloy is applicable to the process of separating lead, antimony, and silver from a high-antimony lead alloy as described above. It includes a feeding box 1, around which there are two groups of fixing frames 2. On the two groups of fixing frames 2, a Y-shaped feeding pipe 3 and a funnel 4 are respectively fixedly installed. A receiving bucket 5 is arranged directly below the feeding box 1. A screen 501 is arranged inside the receiving bucket 5, and a drain pipe 6 is connected to the water outlet of the receiving bucket 5. A driving gear 7 is rotatably installed at the upper end of the feeding box 1. The driving gear 7 meshes with a driving gear 9, and the driving gear 9 is rotatably installed on one side of the feeding box 1. Inside the feeding box 1, there are three transfer frames 11 for carrying containers 8. The transfer frame 11 includes a U-shaped frame 111. Three connecting blocks 10 are installed on the driving gear 7 at equal angles, and the connecting blocks 10 are fixedly connected to the U-shaped frame 111. There are two rotating shafts 112, and the two rotating shafts 112 are respectively rotatably installed at both ends of the U-shaped frame 111, and the two rotating shafts 112 are symmetrically fixedly installed on both sides of the container 8. A torsion spring 113 is sleeved on the rotating shaft 112. One end of the torsion spring 113 is connected to the inner wall of the U-shaped frame 111, and one end of the torsion spring 113 is connected to the end of the rotating shaft 112. A flipping gear 117 is fixedly sleeved on the rotating shaft 112. A C-shaped frame 114 is movably installed inside the U-shaped frame 111. Both ends of the C-shaped frame 114 respectively mesh with the two flipping gears 117. A support rod 115 fixedly connected to the U-shaped frame 111, and a pulley 116 is rotatably installed at the end of the support rod 115. An arc-shaped strip 101 for pushing the pulley 116 is arranged on the inner ring of the feeding box 1.

[0027] Specifically, the container 8 is made of transparent glass. When the silver nitrate leachate needs to be replaced, the silver nitrate leachate and the iron powder are put into the two ports of the Y-shaped discharge pipe 3 in a certain proportion. The mixed solution formed by the silver nitrate leachate and the iron powder flows into the container 8 below through the Y-shaped discharge pipe 3. After the silver nitrate leachate and the iron powder in the container 8 react for 150 minutes, the driving gear 9 is driven by the motor to rotate 120 degrees, and the driving gear 9 drives the transmission gear 7 to rotate. The transmission gear 7 drives the three groups of conversion frames 11 and the corresponding containers 8 to rotate together inside the discharge box 1 through the three groups of connecting blocks 10. The container 8 containing the mixed solution will rotate to the bottom of the funnel 4, and the next group of containers 8 will rotate to the Y-shaped discharge pipe 3. Below the material pipe 3, a certain amount of hydrochloric acid solution is then poured into the container 8 containing the mixed solution through the funnel 4 to allow the mixed solution to further react. During this process, the silver nitrate leaching solution and the iron powder can be added to the next group of containers 8 for reaction. After 150 minutes, the container 8 containing the mixed solution will obtain silver powder and ferrous nitrate solution, and the driving gear 9 is driven to rotate 120 degrees again. During the process of the conversion frame 11 driving the container 8 containing the mixed solution to rotate, the pulley 116 on the conversion frame 11 will roll along the inner ring of the discharge box 1 until the pulley 116 rolls to the end of the arc strip 101, and the pulley 116 will be squeezed by the end of the arc strip 101, so that the pulley 116 drives the support rod 115 together with the U-shaped frame 11 1 moves toward the center of the discharge box 1. As the U-shaped frame 111 moves, the U-shaped frame 111 drives the flip gear 117 to rotate, and the flip gear 117 drives the rotating shaft 112 to rotate together with the container 8, and the rotating shaft 112 rotates the torsion spring 113 until the pulley 116 staggers the end of the arc strip 101. At this time, the container 8 will be turned upside down, so that the silver powder and ferrous nitrate solution in the container 8 are poured into the discharge box 1, and the silver powder and the ferrous nitrate solution flow into the receiving barrel 5 along the inner cavity of the discharge box 1. The silver powder and the ferrous nitrate solution are separated by the screen 501 in the receiving barrel 5, so as to obtain silver powder. At the same time, in this process, the hydrochloric acid solution can be added to the next group of containers 8. After the reaction is sufficient, the main drive When the movable gear 9 rotates, the pulley 116 will stagger the entire arc strip 101, and under the action of the torque force of the torsion spring 113, the container 8 will be returned to the center, and the container 8 will return to the bottom of the Y-shaped discharge pipe 3 again, and then the above operation will be repeated in a cycle. Compared with the prior art, the three groups of containers 8 are continuously rotated in the discharge box 1 by driving the active gear 9. During each stop, silver nitrate leachate and iron powder or hydrochloric acid solution can be added to the corresponding container 8, and during the rotation process, the container 8 can be inverted and returned to the center, so that the silver powder and ferrous nitrate solution in the container 8 can be automatically poured out, ensuring that the silver nitrate leachate can perform continuous replacement reaction in the three groups of containers 8, thereby improving the efficiency of the silver nitrate leachate replacing the silver powder.

[0028] like Figure 5As shown, a cleaning mechanism 13 for cleaning the container 8 is provided on one side of the receiving barrel 5, and the cleaning mechanism 13 includes a rubber sleeve 131, the rubber sleeve 131 is embedded and installed on the discharge box 1, a nozzle 132 movably plugged into the rubber sleeve 131, an electric push rod 134 for driving the nozzle 132, a water pipe 135 fixedly connected to the bottom of the nozzle 132, four groups of spray holes 133 are opened at the upper end of the nozzle 132, the lower end of the electric push rod 134 is connected to the nozzle 132, and the upper end of the electric push rod 134 is connected to the discharge box 1.

[0029] Specifically, the water pipe 135 is connected to an external water pump, and the water pipe 135 is made of rubber. When the container 8 is turned upside down, most of the silver powder and ferrous nitrate solution flow into the discharge box 1, but there will be residual attachments on the inner wall of the container 8. The attachments are mainly composed of silver powder, residual reactants, and impurities. If they are not cleaned up, they will affect the subsequent replacement reaction effect. Therefore, after the container 8 is turned upside down, the electric push rod 134 is started, and the electric push rod 134 drives the nozzle 132 to move upward along the rubber sleeve 131 until the upper end of the nozzle 132 enters the inverted container 8, and the water pump connected to the water pipe 135 is started to make water flow into the nozzle 132 through the water pipe 135, and spray onto the inner wall of the container 8 through the spray hole 133 on the nozzle 132. At the same time, the electric push rod 134 continues to drive the nozzle 132 to move upward, so that the attachments on the inner wall of the container 8 are washed away by water, thereby achieving the cleaning of the inside of the container 8 and ensuring the cleanliness of the container 8.

[0030] like Figures 6 to 8 As shown, the nozzle 132 includes a main pipe 1321, the main pipe 1321 is movably connected to the rubber sleeve 131, and four groups of spray holes 133 are opened at the upper end of the main pipe 1321, a movable pipe 1322 is arranged inside the nozzle 132, the lower end of the movable pipe 1322 is connected to the water pipe 135, and the movable sleeve 1323 is installed on the nozzle 132. The movable sleeve 1323 is fixedly connected to the electric push rod 134, the spring 1324 is sleeved on the nozzle 132, and four groups of rectangular grooves 1325 are opened on the nozzle 132. The four groups of rectangular grooves 1325 are all provided with a scraper frame 1326, and the scraper frame 1326 includes a first scraper bar 6 1. A second scraper strip 62 is hinged on the upper end of the first scraper strip 61, and a driving rod 63 is hinged on the middle part of the first scraper strip 61. A driven gear 64 is fixedly installed on one end of the driving rod 63, and a rack 65 meshing with the driven gear 64 is fixedly connected to the movable pipe 1322. A water collecting tank 21 is arranged in the main pipe 1321, and the spray hole 133 is connected to the water collecting tank 21. The movable pipe 1322 is movably connected to the water collecting tank 21. The second scraper strip 62 and the driving rod 63 are both hinged in the rectangular groove 1325. Two groups of convex shafts 31 are arranged in the inner circle of the movable sleeve 1323. Two groups of spiral grooves 22 are arranged on the outer circle of the main pipe 1321, and the convex shafts 31 are located in the spiral grooves 22.

[0031] Specifically, in the initial state, the lower end of the movable tube 1322 is in contact with the ground, the scraper frame 1326 is folded in the rectangular groove 1325, and the movable tube 1322 is coated with a rubber layer, which increases the sealing between the movable tube 1322 and the wall of the water collecting tank 21. Since the direction of the water column at the spraying point of the spray hole 133 is fixed, the force of the water impact on the inner wall of the container 8 is uneven, so that some attachments on the inner wall of the container 8 cannot be completely washed away. Therefore, when cleaning the inside of the container 8, the electric push rod 134 drives the movable sleeve 1323 to move upward, and the movable sleeve 1323 pushes the main pipe 1321 along the rubber sleeve 1324 through the spring 1324. 31 moves upward, the lower end of the movable pipe 1322 will be out of contact with the ground until the upper end surface of the main pipe 1321 is close to the bottom of the container 8, and then the water pump is started, and water flows into the movable pipe 1322 through the water pipe 135, and then is injected into the water collection tank 21 inside the movable pipe 1322 through the movable pipe 1322. Due to the limited space inside the water collection tank 21, a large amount of water will be gathered in the water collection tank 21 in a short time, and the water will be sprayed out through the spray hole 133 to release part of the water pressure. At the same time, the water pressure in the water collection tank 21 will push the movable pipe 1322 and the four sets of racks 65 to move downward, and the racks 65 will drive the driven gear 64 together with the driving rod 63 rotates upward together, the driving rod 63 rotates the second scraper bar 62 synchronously through the first scraper bar 61, so that the scraper frame 1326 extends from the rectangular groove 1325 until the first scraper bar 61 and the second scraper bar 62 are perpendicular to each other, and the first scraper bar 61 and the second scraper bar 62 are close to the inner wall and the bottom of the container 8 respectively. At this time, the electric push rod 134 continues to drive the movable sleeve 1323 to move upward. Since the upper end of the main pipe 1321 is blocked by the bottom of the container 8 and cannot move, the movable sleeve 1323 will slide upward along the main pipe 1321 and compress the spring 1324. At the same time, the two sets of convex shafts 31 also move upward with the movable sleeve 1323. The main pipe 1321 rotates, and the rotating main pipe 1321 drives the four scraper racks 1326 to rotate. As the scraper racks 1326 rotate, the first scraper bar 61 and the second scraper bar 62 on the scraper racks 1326 scrape off the attachments on the inner wall and the bottom of the container 8 respectively, and the water sprayed from the spray hole 133 is sprayed at the junction of the inner wall and the bottom of the container 8. The water is blocked and sprayed around, so that the scraped attachments will be washed away by the water, so that the inside of the container 8 is cleaned more cleanly, which greatly reduces the influence of the attachments on the subsequent replacement reaction.

[0032] Working principle: silver nitrate leaching solution and iron powder are put into the two ports of the Y-type discharge pipe 3 in a certain proportion, and the mixed solution formed by the silver nitrate leaching solution and the iron powder flows into the container 8 below through the Y-type discharge pipe 3. After the silver nitrate leaching solution and the iron powder in the container 8 react for 150 minutes, the motor drives the driving gear 9 to rotate 120 degrees, and the driving gear 9 drives the transmission gear 7 to rotate. The transmission gear 7 drives the three sets of conversion frames 11 and the corresponding containers 8 to rotate inside the discharge box 1 through the three sets of connecting blocks 10, and the container 8 containing the mixed solution will rotate to the funnel 4. At the same time, the next group of containers 8 will rotate to the bottom of the Y-shaped discharge pipe 3, and then a certain amount of hydrochloric acid solution will be poured into the container 8 containing the mixed solution through the funnel 4 to make the mixed solution further react. In this process, the silver nitrate leaching solution and the iron powder can be added to the next group of containers 8 for reaction. After 150 minutes, the container 8 containing the mixed solution will obtain silver powder and ferrous nitrate solution, and the driving gear 9 will be driven to rotate 120 degrees again. In the process of driving the container 8 containing the mixed solution to rotate, the pulley 116 on the conversion frame 11 will rotate along the discharge pipe 3. The inner circle of the box 1 rolls until the pulley 116 rolls to the end of the arc strip 101, and the pulley 116 will be squeezed by the end of the arc strip 101, so that the pulley 116 drives the support rod 115 together with the U-shaped frame 111 to move toward the center of the discharge box 1. As the U-shaped frame 111 moves, the U-shaped frame 111 drives the flip gear 117 to rotate, and the flip gear 117 drives the rotating shaft 112 to rotate together with the container 8, and the rotating shaft 112 rotates the torsion spring 113 until the pulley 116 staggers the end of the arc strip 101. At this time, the container 8 will be turned upside down, so that the silver powder in the container 8 and the nitrate The ferrous acid solution is poured into the discharge box 1, and the silver powder and the ferrous nitrate solution flow into the receiving barrel 5 along the inner cavity of the discharge box 1. The silver powder and the ferrous nitrate solution are separated by the screen 501 in the receiving barrel 5, so as to obtain the silver powder. At the same time, the hydrochloric acid solution can be added to the next group of containers 8 during this process. After the reaction is sufficient, when the driving gear 9 is driven to rotate, the pulley 116 will stagger the entire arc strip 101, and under the torque force of the torsion spring 113, the container 8 is returned to the right position, and the container 8 returns to the bottom of the Y-shaped discharge pipe 3 again, and then the above operation is repeated in a cycle; When cleaning the inside of the container 8, the electric push rod 134 drives the movable sleeve 1323 to move upward, and the movable sleeve 1323 pushes the main pipe 1321 to move upward along the rubber sleeve 131 through the spring 1324, and the lower end of the movable pipe 1322 will be out of contact with the ground until the upper end surface of the main pipe 1321 is close to the bottom of the container 8, and then the water pump is started, and water flows into the movable pipe 1322 through the water pipe 135, and then is injected into the water collection tank 2 inside the movable pipe 1322 through the movable pipe 1322. 1, due to the limited internal space of the water collecting tank 21, a large amount of water will be collected in the water collecting tank 21 in a short time, and the water will be sprayed out through the spray hole 133 to release part of the water pressure. At the same time, the water pressure in the water collecting tank 21 will push the movable pipe 1322 together with the four sets of racks 65 to move downward, and the racks 65 will drive the driven gear 64 together with the driving rod 63 to rotate upward. The driving rod 63 drives the second scraper bar 62 to rotate synchronously through the first scraper bar 61, so that the scraper frame 1326 extends from the rectangular groove 1325. The first scraper strip 61 and the second scraper strip 62 are extended until they are perpendicular to each other and the first scraper strip 61 and the second scraper strip 62 are close to the inner wall and the bottom of the container 8 respectively. At this time, the electric push rod 134 continues to drive the movable sleeve 1323 to move upward. Since the upper end of the main pipe 1321 is blocked by the bottom of the container 8 and cannot move, the movable sleeve 1323 will slide upward along the main pipe 1321 and compress the spring 1324. At the same time, the two sets of convex shafts 31 also move upward with the movable sleeve 1323, and the convex shafts 31 are The shaft 31 squeezes the inner wall of the spiral groove 22 to cause the main pipe 1321 to rotate. The rotating main pipe 1321 will drive the four groups of scraper frames 1326 to rotate. As the scraper frames 1326 rotate, the first scraper bar 61 and the second scraper bar 62 on the scraper frames 1326 will scrape off the attachments on the inner wall and the bottom of the container 8 respectively, and the water sprayed from the spray hole 133 will be sprayed at the intersection of the inner wall and the bottom of the container 8. The water will be blocked and will spray around, so that the scraped attachments will be washed away by the water.

[0033] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. A process for separating lead, antimony and silver from high-antimony lead alloy, characterized in that: The following steps are involved: Step 1: using high antimony lead alloy cast from high antimony lead anode mud as anode, and performing pulse electrolysis in a lead methanesulfonate system; During electrolysis, the anode is placed in an acid-resistant canvas anode bag to receive the anode insoluble matter that falls off during electrolysis. Lead first dissolves into the solution in the form of lead methanesulfonate and then precipitates at the cathode in the form of elemental lead. After electrolysis, lead sheets and antimony silver powder in the anode bag are obtained, thereby separating the lead. Step 2: Using concentrated nitric acid as a leaching agent, subjecting the antimony silver powder obtained in step 1 to oxidative acid leaching, and separating the liquid and solid after the leaching is completed to obtain a silver nitrate leaching solution and an antimony dioxide leaching residue respectively; Step 3: Start the replacement reaction device, and put the silver nitrate leaching solution and iron powder prepared in step 2 into the two ports of the Y-shaped discharge pipe (3) in a certain proportion, so that the silver nitrate leaching solution and the iron powder flow into the container (8) below through the Y-shaped discharge pipe (3). After the silver nitrate leaching solution and the iron powder react for (150) minutes, the three groups of conversion racks (11) in the replacement reaction device are driven to rotate by the driving gear (7), so that the containers (8) containing the silver nitrate leaching solution and the iron powder are rotated to the bottom of the funnel (4), and the next group of containers (8) will be rotated to the bottom of the Y-shaped discharge pipe (3), and the hydrochloric acid twice the amount of the iron powder will be passed through the funnel (4). 4) pouring into a container (8) containing silver nitrate leaching solution and iron powder, so that the mixed solution in the container (8) is further reacted, and at the same time, silver nitrate leaching solution and iron powder are added to the next group of containers (8). After 150 minutes, the transmission gear (7) is continuously driven to rotate, and the container (8) containing the mixed solution will automatically pour out the silver powder and ferrous nitrate solution, and the silver powder and ferrous nitrate solution flow into the receiving barrel (5) through the discharge box (1), and are filtered through the screen (501) in the receiving barrel (5) to separate the silver powder from the ferrous nitrate solution. According to the above operation, the cycle is repeated to completely replace the silver powder in the silver nitrate leaching solution prepared in step 2.

2. The device for separating lead, antimony and silver from high antimony lead alloy according to claim 1, characterized in that: The antimony dioxide leaching residue uses hydrogen as a reducing agent to react with antimony dioxide under high temperature conditions to reduce the antimony element to a single substance, and then obtains antimony powder after cooling.

3. A device for separating lead, antimony and silver from a high-antimony lead alloy, which is suitable for the process of separating lead, antimony and silver from a high-antimony lead alloy as claimed in claim 1 or 2, characterized in that: It comprises a discharge box (1), two groups of fixed frames (2) are arranged around the discharge box (1), and Y-shaped discharge pipes (3) and funnels (4) are fixedly installed on the two groups of fixed frames (2), respectively; a receiving bucket (5) is arranged directly below the discharge box (1), a screen (501) is arranged in the receiving bucket (5), and a drainage pipe (6) is connected to the water outlet of the receiving bucket (5); a transmission gear (7) is rotatably installed on the upper end of the discharge box (1), the transmission gear (7) meshes with a driving gear (9), and the driving gear (9) is rotatably installed on one side of the discharge box (1); three groups of conversion frames (11) for carrying containers (8) are arranged in the discharge box (1); The conversion frame (11) comprises: A U-shaped frame (111), three groups of connection blocks (10) are installed at equal angles on the transmission gear (7), and the connection blocks (10) are fixedly connected to the U-shaped frame (111); Two groups of rotary shafts (112), the two groups of rotary shafts (112) are rotatably mounted on both ends of the U-shaped frame (111), and the two groups of rotary shafts (112) are symmetrically fixedly mounted on both sides of the container (8); A torsion spring (113) sleeved on the rotating shaft (112), one end of the torsion spring (113) being connected to the inner wall of the U-shaped frame (111), and one end of the torsion spring (113) being connected to the end of the rotating shaft (112); A flip gear (117) fixedly sleeved on the rotation shaft (112); A U-shaped frame (114) is movably mounted inside the U-shaped frame (111), and two ends of the U-shaped frame (114) are respectively engaged with two groups of flip gears (117); A support rod (115) is fixedly connected to the U-shaped frame (111).

4. The device for separating lead, antimony and silver from high antimony lead alloy according to claim 3, characterized in that: A pulley (116) is rotatably mounted on the end of the support rod (115), and an arc-shaped bar (101) for pushing the pulley (116) is arranged on the inner ring of the discharge box (1).

5. The device for separating lead, antimony and silver from high antimony lead alloy according to claim 4, characterized in that: A cleaning mechanism (13) for cleaning the container (8) is provided on one side of the receiving barrel (5), and the cleaning mechanism (13) comprises: a rubber sleeve (131), and the rubber sleeve (131) is embedded and installed on the discharge box (1); A nozzle (132) movably plugged into the rubber sleeve (131); An electric push rod (134) for driving the nozzle (132); A water pipe (135) is fixedly connected below the spray pipe (132).

6. The device for separating lead, antimony and silver from high antimony lead alloy according to claim 5, characterized in that: The upper end of the nozzle (132) is provided with four groups of nozzle holes (133); the lower end of the electric push rod (134) is connected to the nozzle (132); and the upper end of the electric push rod (134) is connected to the discharge box (1).

7. The device for separating lead, antimony and silver from high antimony lead alloy according to claim 6, characterized in that: The nozzle (132) comprises a main pipe (1321), the main pipe (1321) is movably connected to the rubber sleeve (131), and four groups of spray holes (133) are arranged at the upper end of the main pipe (1321); A movable pipe (1322) is arranged inside the nozzle (132), and the lower end of the movable pipe (1322) is connected to the water pipe (135); A movable sleeve (1323) is mounted on the nozzle (132), and the movable sleeve (1323) is fixedly connected to the electric push rod (134); A spring (1324) sleeved on the nozzle (132); Four groups of rectangular grooves (1325) are provided on the nozzle (132); A scraper frame (1326) is provided in each of the four groups of rectangular grooves (1325).

8. The device for separating lead, antimony and silver from high antimony lead alloy according to claim 7, characterized in that: The scraper frame (1326) comprises a first scraper strip (61); A second scraper strip (62) hingedly connected to the upper end of the first scraper strip (61); A driving rod (63) hingedly connected to the middle portion of the first scraper strip (61); A driven gear (64) is fixedly mounted on one end of the driving rod (63); The rack (65) meshes with the driven gear (64), and the rack (65) is fixedly connected to the movable tube (1322).

9. The device for separating lead, antimony and silver from high antimony lead alloy according to claim 8, characterized in that: A water collecting tank (21) is provided in the main pipe (1321), the spray hole (133) is connected to the water collecting tank (21), and the movable pipe (1322) is movably plugged into the water collecting tank (21).

10. The device for separating lead, antimony and silver from high antimony lead alloy according to claim 9, characterized in that: The second scraper strip (62) and the driving rod (63) are both hinged in the rectangular groove (1325), two groups of convex shafts (31) are arranged in the inner ring of the movable sleeve (1323), two groups of spiral grooves (22) are arranged on the outer ring of the main pipe (1321), and the convex shafts (31) are located in the spiral grooves (22).

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