A method for extracting tin and antimony from a tin polymetallic tailings

Abstract

The application discloses a method for extracting tin and antimony from tin polymetallic tailings, which comprises the following steps: grinding and mixing the tin polymetallic tailings, adding a collector and an inhibitor, and then adding pine oil to float to obtain a flotation concentrate A and a flotation tailing A; the collector is obtained by mixing sodium dodecyl sulfonate and N-dodecyl ethanol amine, and the inhibitor is obtained by mixing and reacting starch dissolved in water and acrylamide; the flotation tailing A is floated to obtain a flotation concentrate B and a flotation tailing B; the flotation concentrate B is ground, mixed with a hydrochloric acid solution, stirred, filtered, and then mixed with sodium carbonate to adjust the pH value, and then stirred, filtered and placed to obtain an antimony-containing precipitate; the flotation tailing B is pressure-filtered to obtain a slag, which is then crushed, mixed with a hydrochloric acid solution, stirred, mixed with zinc powder, reacted, filtered and used to produce tin ingots. The application can separate and extract tin and antimony from the tin polymetallic tailings, improve the recovery efficiency of the tin and the antimony, and realize the recycling of the tin polymetallic tailings.

Description

Technical Field

[0001] This invention belongs to the field of tin tailings recycling technology, specifically relating to a method for extracting tin and antimony from tin polymetallic tailings. Background Technology

[0002] Tin polymetallic ores are mostly associated mineral resources, often containing one or more metallic minerals. Cassiterite and these minerals often exhibit complex intergrowth relationships. Due to cassiterite's poor floatability and its density being close to that of associated metallic minerals, traditional flotation or gravity separation of cassiterite is inefficient. Although numerous studies and improvements have been made, achieving a tin recovery rate of around 70%, a considerable portion of cassiterite remains in the tailings after beneficiation. Furthermore, the tailings contain various metals such as antimony, lead, and zinc, and this complex composition increases the difficulty of tailings resource recovery. With the continuous expansion of mining operations, the large amount of tailings generated not only causes loss and waste of ore resources but also serious environmental pollution. Therefore, how to recover metal resources from tailings and reduce environmental pollution is currently one of the key research focuses. Summary of the Invention

[0003] To address the aforementioned shortcomings, this invention discloses a method for extracting tin and antimony from tin polymetallic tailings. This method can separate and extract tin and antimony from tin polymetallic tailings, improve the recovery efficiency of tin and antimony, and realize the recycling of tin polymetallic tailings resources.

[0004] This invention is achieved using the following technical solution:

[0005] A method for extracting tin and antimony from tin polymetallic tailings, comprising the following steps:

[0006] (1) Take tin polymetallic tailings and grind them to obtain slurry A with a particle size of less than 0.074 mm. Add water to slurry A to make the mass ratio of solid to liquid in slurry A 1: (3-5). Then add sodium carbonate to slurry A to adjust the pH value of slurry A to 9-10. Then add collector, inhibitor and pine oil to slurry A for flotation to obtain flotation concentrate A and flotation tailings A. The weight ratio of slurry A, collector, inhibitor and pine oil is 1000: (0. 2~0.3):(0.3~0.4):(0.05~0.08), the collector is obtained by mixing sodium dodecyl sulfonate and N-dodecyl ethanolamine, the inhibitor is obtained by dissolving starch in water, then continuously purging nitrogen and stirring at a constant temperature of 90℃ for 30 min, then cooling to 25℃, then adding ammonium persulfate and stirring, then adding acrylamide and continuing to stir and react for 2 h, then aging for 24 h, then washing, filtering and drying to obtain the inhibitor;

[0007] (2) Take the flotation tailings A mentioned in step (1) and add zinc sulfate, sodium humate, ethyl thiocyanate and pine oil for flotation to obtain flotation concentrate B and flotation tailings B. The weight ratio of flotation tailings A, zinc sulfate, sodium humate, ethyl thiocyanate and pine oil is 1000:(0.3~0.4):(0.03~0.05):(0.1~0.2):(0.05~0.08).

[0008] (3) Take the flotation concentrate B obtained in step (2), grind it through a 200-mesh sieve, then add hydrochloric acid solution and mix and stir for 1h to 2h, then filter to obtain filtrate A, add sodium carbonate to filtrate A to adjust the pH value to 2.0 to 3.0 and continue stirring for 1h to 2h, then let it stand for 30min and filter to obtain antimony-containing precipitate and filtrate B. The antimony-containing precipitate is decomposed with ammonia water to produce antimony trioxide product, and ammonium sulfate is added to filtrate B to obtain lead sulfate precipitate;

[0009] (4) Take the flotation tailings B obtained in step (2) and filter it to obtain slag. Then crush the slag through a 200-mesh sieve and add hydrochloric acid solution to mix and stir for 1h to 2h. Then filter to obtain filtrate C. Add calcium carbonate to filtrate C to adjust the pH value to 4.0 to 4.5 and stir for 20min to 30min. Then filter to obtain filtrate D. Then add zinc powder to filtrate D and stir to react for 30min to 60min. Filter to obtain tin slag and filtrate E. The filtrate E is used to recover zinc sulfate. The tin slag is dried and then smelted by fire to cast tin ingots.

[0010] Furthermore, the weight ratio of sodium dodecyl sulfonate and N-dodecyl ethanolamine in the collector described in step (1) is 1:(0.5-1.2).

[0011] Furthermore, in the preparation process of the inhibitor in step (1), the mass ratio of starch, water, ammonium persulfate and acrylamide is (3-5):100:(0.02-0.03):(8-10).

[0012] Furthermore, in step (1), a collector, an inhibitor, and pine oil are added to slurry A and flotation is carried out under the condition of stirring speed of 800 r / min to 1000 r / min.

[0013] Furthermore, in step (2), the flotation tailings A described in step (1) are taken and zinc sulfate, sodium humate, ethyl thiocyanate and pine oil are added and flotation is carried out under the condition of stirring speed of 300 r / min to 500 r / min.

[0014] Furthermore, the hydrochloric acid solution has a mass fraction of 10% to 20%.

[0015] Furthermore, in step (3), the mass ratio of flotation concentrate B to hydrochloric acid solution is 1:(0.2-0.4). After crushing the slag through a 200-mesh sieve, the hydrochloric acid solution is added and mixed and stirred at 70℃-80℃ for 1-2 hours. Controlling the appropriate temperature promotes the leaching of metallic antimony and lead in flotation concentrate B.

[0016] Furthermore, in step (4), the weight ratio of slag to hydrochloric acid solution is 1:(0.1 to 0.2). After crushing the slag through a 200-mesh sieve, the hydrochloric acid solution is added and mixed and stirred at 40℃ to 50℃ for 1 to 2 hours.

[0017] Furthermore, in step (4), zinc powder is added to the filtrate D and the mixture is stirred at a speed of 80 r / min to 100 r / min for 30 min to 60 min.

[0018] The flotation concentrate A can be used to recover quartz.

[0019] Compared with existing technologies, this technical solution has the following advantages:

[0020] 1. This invention involves grinding tin polymetallic tailings to a suitable particle size, then adding water to adjust the slurry and adding sodium carbonate to adjust to alkaline conditions before flotation to remove non-metallic substances such as quartz from the tailings. A composite collector prepared by mixing sodium dodecyl sulfonate and N-dodecyl ethanolamine is used, which is beneficial for selectively collecting non-metallic substances such as quartz. At the same time, modified starch obtained by cross-linking acrylamide and starch is added as an inhibitor, which can effectively suppress valuable metals in the tailings and prevent them from being lost due to flotation separation with non-metallic substances such as quartz.

[0021] 2. In this invention, zinc sulfate, sodium humate, ethyl thiocyanate, and pine oil are added to the flotation tailings A after the first flotation to perform a second flotation, resulting in flotation concentrate B containing antimony and lead, and flotation tailings B. Then, flotation concentrate B is mixed with hydrochloric acid solution and leached to obtain a leachate containing antimony and lead. The pH value of the leachate is then adjusted to allow the antimony to precipitate and separate, thereby extracting a high-antimony precipitate. The high-antimony precipitate is then decomposed with ammonia water to produce a high-purity, high-quality antimony trioxide product. Simultaneously, the flotation tailings B are filtered and further ground to obtain small-particle slag powder, which is then leached with hydrochloric acid solution. Sodium carbonate is added to the leachate to adjust the pH value to allow the iron in the leachate to precipitate and separate. Zinc powder is then added to replace the tin in the leachate to obtain high-tin slag. The high-tin slag is dried and then pyrolyzed and cast into high-purity tin ingots. The remaining filtrate can also be used to recover and prepare zinc sulfate products.

[0022] 3. This invention employs a combined flotation and solvent leaching method to effectively separate and extract valuable metals from tin polymetallic tailings, particularly high-purity antimony and tin products. This solves the problems of poor recovery efficiency and stability of tin and antimony in existing technologies, enabling the recycling of tin polymetallic tailings resources. Furthermore, this invention features a simple process, convenient operation, and is suitable for automated and large-scale production. Detailed Implementation

[0023] The present invention is further illustrated by the following examples, but these are not intended to limit the invention. Specific experimental conditions and methods not specified in the following examples are generally conventional methods well known to those skilled in the art.

[0024] Example 1: A method for extracting tin and antimony from tin polymetallic tailings, comprising the following steps:

[0025] (1) Tin polymetallic tailings were ground to obtain slurry A with a particle size of less than 0.074 mm. Water was added to slurry A to make the mass ratio of solid to liquid in slurry A 1:4. Then, sodium carbonate was added to slurry A to adjust the pH value of slurry A to 9.5. Then, collector, depressant and pine oil were added to slurry A and flotation was carried out under the condition of stirring speed of 900 r / min to obtain flotation concentrate A and flotation tailings A. The weight ratio of slurry A, collector, depressant and pine oil was 1000:0.23:0.35:0.06. The collector was ten The collector is obtained by mixing sodium dialkyl sulfonate and N-dodecyl ethanolamine, wherein the weight ratio of sodium dodecyl sulfonate to N-dodecyl ethanolamine is 1:1. The inhibitor is prepared by dissolving starch in water, then continuously purging nitrogen and stirring at a constant temperature of 90°C for 30 minutes, then cooling to 25°C, adding ammonium persulfate and stirring, then adding acrylamide and continuing to stir and react for 2 hours, then aging for 24 hours, and then washing, filtering and drying to obtain the inhibitor. The mass ratio of starch, water, ammonium persulfate and acrylamide is 4:100:0.025:9.

[0026] (2) Take the flotation tailings A mentioned in step (1) and add zinc sulfate, sodium humate, ethyl thiocyanate and pine oil. Perform flotation under the condition of stirring speed of 400 r / min to obtain flotation concentrate B and flotation tailings B. The weight ratio of flotation tailings A, zinc sulfate, sodium humate, ethyl thiocyanate and pine oil is 1000:0.32:0.04:0.16:0.06.

[0027] (3) Take the flotation concentrate B obtained in step (2), grind it through a 200-mesh sieve, then add hydrochloric acid solution and mix and stir for 1.5h, then filter to obtain filtrate A, add sodium carbonate to filtrate A to adjust the pH value to 2.5 and continue stirring for 1.5h, then let it stand for 30min and filter to obtain antimony-containing precipitate and filtrate B. The antimony-containing precipitate is decomposed with ammonia water to produce antimony trioxide product. Ammonium sulfate is added to filtrate B to obtain lead sulfate precipitate. The mass fraction of the hydrochloric acid solution is 15%. The mass ratio of flotation concentrate B to hydrochloric acid solution is 1:0.3. After crushing the slag through a 200-mesh sieve, add hydrochloric acid solution and mix and stir at 75℃ for 1.5h.

[0028] (4) Take the flotation tailings B obtained in step (2) and filter it to obtain slag. Then crush the slag through a 200-mesh sieve and add hydrochloric acid solution to mix and stir for 1.5h. Then filter to obtain filtrate C. Add calcium carbonate to filtrate C to adjust the pH value to 4.2 and stir for 25min. Then filter to obtain filtrate D. Then add zinc powder to filtrate D and stir and react for 45min at a speed of 90r / min. Filter to obtain tin slag and filtrate E. The filtrate E is used to recover zinc sulfate. The tin slag is dried and then smelted by fire to cast tin ingots.

[0029] The weight ratio of the slag to the hydrochloric acid solution is 1:0.15. After the slag is crushed and passed through a 200-mesh sieve, it is added to the hydrochloric acid solution and mixed and stirred at 45°C for 1.5 hours.

[0030] Example 2: A method for extracting tin and antimony from tin polymetallic tailings, comprising the following steps:

[0031] (1) Tin polymetallic tailings were ground to obtain slurry A with a particle size of less than 0.074 mm. Water was added to slurry A to make the mass ratio of solid to liquid in slurry A 1:3. Then, sodium carbonate was added to slurry A to adjust the pH value of slurry A to 9. Then, a collector, a depressant and pine oil were added to slurry A and flotation was carried out under the condition of stirring speed of 800 r / min to obtain flotation concentrate A and flotation tailings A. The weight ratio of slurry A, collector, depressant and pine oil was 1000:0.2:0.3:0.05. The collector was dodecane. The collector is obtained by mixing sodium dodecyl sulfonate and N-dodecyl ethanolamine. The weight ratio of sodium dodecyl sulfonate to N-dodecyl ethanolamine in the collector is 1:0.5. The inhibitor is obtained by dissolving starch in water, then continuously purging nitrogen and stirring at a constant temperature of 90°C for 30 min, then cooling to 25°C, adding ammonium persulfate and stirring, then adding acrylamide and continuing to stir and react for 2 h, then aging for 24 h, and then washing, filtering and drying to obtain the inhibitor. The mass ratio of starch, water, ammonium persulfate and acrylamide is 3:100:0.02:8.

[0032] (2) Take the flotation tailings A mentioned in step (1) and add zinc sulfate, sodium humate, ethyl thiocyanate and pine oil. Perform flotation under the condition of stirring speed of 300 r / min to obtain flotation concentrate B and flotation tailings B. The weight ratio of flotation tailings A, zinc sulfate, sodium humate, ethyl thiocyanate and pine oil is 1000:0.3:0.03:0.1:0.05.

[0033] (3) Take the flotation concentrate B obtained in step (2), grind it through a 200-mesh sieve, then add hydrochloric acid solution and mix and stir for 1 hour, then filter to obtain filtrate A, add sodium carbonate to filtrate A to adjust the pH value to 2.0 and continue stirring for 1 hour, then let it stand for 30 minutes and filter to obtain antimony-containing precipitate and filtrate B. The antimony-containing precipitate is decomposed with ammonia water to produce antimony trioxide product. Ammonium sulfate is added to filtrate B to obtain lead sulfate precipitate. The mass fraction of the hydrochloric acid solution is 10%. The mass ratio of the flotation concentrate B to the hydrochloric acid solution is 1:0.2. After crushing the slag through a 200-mesh sieve, add hydrochloric acid solution and mix and stir at 70°C for 1 hour.

[0034] (4) Take the flotation tailings B obtained in step (2) and filter it to obtain slag. Then crush the slag through a 200-mesh sieve and add hydrochloric acid solution to mix and stir for 1 hour. Then filter to obtain filtrate C. Add calcium carbonate to filtrate C to adjust the pH value to 4.0 and stir for 20 minutes. Then filter to obtain filtrate D. Then add zinc powder to filtrate D and stir and react for 30 minutes at a speed of 80 r / min. Filter to obtain tin slag and filtrate E. The filtrate E is used to recover zinc sulfate. The tin slag is dried and then smelted by fire to cast tin ingots.

[0035] The weight ratio of the slag to the hydrochloric acid solution is 1:0.1. After the slag is crushed and passed through a 200-mesh sieve, it is added to the hydrochloric acid solution and mixed and stirred at 40°C for 1 hour.

[0036] Example 3: A method for extracting tin and antimony from tin polymetallic tailings, comprising the following steps:

[0037] (1) Tin polymetallic tailings were ground to obtain slurry A with a particle size of less than 0.074 mm. Water was added to slurry A to make the mass ratio of solid to liquid in slurry A 1:4.5. Then, sodium carbonate was added to slurry A to adjust the pH value of slurry A to 9.5. Then, collector, depressant and pine oil were added to slurry A and flotation was carried out under the condition of stirring speed of 850 r / min to obtain flotation concentrate A and flotation tailings A. The weight ratio of slurry A, collector, depressant and pine oil was 1000:0.28:0.32:0.07. The collector was dodecyl sulfate. The collector is obtained by mixing sodium alkyl sulfonate and N-dodecyl ethanolamine, wherein the weight ratio of sodium alkyl sulfonate to N-dodecyl ethanolamine in the collector is 1:0.8. The inhibitor is prepared by dissolving starch in water, then continuously purging nitrogen and stirring at a constant temperature of 90°C for 30 min, then cooling to 25°C, adding ammonium persulfate and stirring, then adding acrylamide and continuing to stir and react for 2 h, then aging for 24 h, and then washing, filtering and drying to obtain the inhibitor. The mass ratio of starch, water, ammonium persulfate and acrylamide is 4:100:0.025:9.5.

[0038] (2) Take the flotation tailings A mentioned in step (1) and add zinc sulfate, sodium humate, ethyl thiocyanate and pine oil. Perform flotation under the condition of stirring speed of 400 r / min to obtain flotation concentrate B and flotation tailings B. The weight ratio of flotation tailings A, zinc sulfate, sodium humate, ethyl thiocyanate and pine oil is 1000:0.36:0.04:0.18:0.07.

[0039] (3) Take the flotation concentrate B obtained in step (2), grind it through a 200-mesh sieve, then add hydrochloric acid solution and mix and stir for 1.5h, then filter to obtain filtrate A, add sodium carbonate to filtrate A to adjust the pH value to 2.8 and continue stirring for 1.5h, then let it stand for 30min and filter to obtain antimony-containing precipitate and filtrate B. The antimony-containing precipitate is decomposed with ammonia water to produce antimony trioxide product. Ammonium sulfate is added to filtrate B to obtain lead sulfate precipitate. The mass fraction of the hydrochloric acid solution is 10% to 20%. The mass ratio of flotation concentrate B to hydrochloric acid solution is 1:0.3. After crushing the slag through a 200-mesh sieve, add hydrochloric acid solution and mix and stir at 75℃ for 1.5h.

[0040] (4) Take the flotation tailings B obtained in step (2) and filter it to obtain slag. Then crush the slag through a 200-mesh sieve and add hydrochloric acid solution to mix and stir for 1.5h. Then filter to obtain filtrate C. Add calcium carbonate to filtrate C to adjust the pH value to 4.3 and stir for 25min. Then filter to obtain filtrate D. Then add zinc powder to filtrate D and stir and react for 50min at a speed of 90r / min. Filter to obtain tin slag and filtrate E. The filtrate E is used to recover zinc sulfate. The tin slag is dried and then smelted by fire to cast tin ingots.

[0041] The weight ratio of the slag to the hydrochloric acid solution is 1:0.18. After the slag is crushed and passed through a 200-mesh sieve, it is added to the hydrochloric acid solution and mixed and stirred at 45°C for 1.5 hours.

[0042] Example 4: A method for extracting tin and antimony from tin polymetallic tailings, comprising the following steps:

[0043] (1) Tin polymetallic tailings were ground to obtain slurry A with a particle size of less than 0.074 mm. Water was added to slurry A to make the mass ratio of solid to liquid in slurry A 1:5. Then, sodium carbonate was added to slurry A to adjust the pH value of slurry A to 10. Then, a collector, a depressant and pine oil were added to slurry A and flotation was carried out under the condition of stirring speed of 1000 r / min to obtain flotation concentrate A and flotation tailings A. The weight ratio of slurry A, collector, depressant and pine oil was 1000:0.3:0.4:0.08. The collector was dodecane. The collector is obtained by mixing sodium dodecyl sulfonate and N-dodecyl ethanolamine. The weight ratio of sodium dodecyl sulfonate to N-dodecyl ethanolamine in the collector is 1:1.2. The inhibitor is obtained by dissolving starch in water, then continuously purging nitrogen and stirring at a constant temperature of 90°C for 30 minutes, then cooling to 25°C, adding ammonium persulfate and stirring, then adding acrylamide and continuing to stir and react for 2 hours, then aging for 24 hours, and then washing, filtering and drying to obtain the inhibitor. The mass ratio of starch, water, ammonium persulfate and acrylamide is 5:100:0.03:10.

[0044] (2) Take the flotation tailings A mentioned in step (1) and add zinc sulfate, sodium humate, ethyl thiocyanate and pine oil. Perform flotation under the condition of stirring speed of 500 r / min to obtain flotation concentrate B and flotation tailings B. The weight ratio of flotation tailings A, zinc sulfate, sodium humate, ethyl thiocyanate and pine oil is 1000:0.4:0.05:0.2:0.08.

[0045] (3) Take the flotation concentrate B obtained in step (2), grind it through a 200-mesh sieve, then add hydrochloric acid solution and mix and stir for 2 hours, then filter to obtain filtrate A, add sodium carbonate to filtrate A to adjust the pH value to 3.0 and continue stirring for 2 hours, then let it stand for 30 minutes and filter to obtain antimony-containing precipitate and filtrate B. The antimony-containing precipitate is decomposed with ammonia water to produce antimony trioxide product. Ammonium sulfate is added to filtrate B to obtain lead sulfate precipitate. The mass fraction of the hydrochloric acid solution is 20%. The mass ratio of the flotation concentrate B to the hydrochloric acid solution is 1:0.4. After crushing the slag through a 200-mesh sieve, add hydrochloric acid solution and mix and stir at 80°C for 2 hours.

[0046] (4) Take the flotation tailings B obtained in step (2) and filter it to obtain slag. Then crush the slag through a 200-mesh sieve and add hydrochloric acid solution to mix and stir for 2 hours. Then filter to obtain filtrate C. Add calcium carbonate to filtrate C to adjust the pH value to 4.5 and stir for 30 minutes. Then filter to obtain filtrate D. Then add zinc powder to filtrate D and stir and react for 60 minutes at a speed of 100 r / min. Filter to obtain tin slag and filtrate E. The filtrate E is used to recover zinc sulfate. The tin slag is dried and then smelted by fire to cast tin ingots.

[0047] The weight ratio of the slag to the hydrochloric acid solution is 1:0.2. After the slag is crushed and passed through a 200-mesh sieve, it is added to the hydrochloric acid solution and mixed and stirred at 50°C for 2 hours.

[0048] Comparative Example 1: The method for extracting tin and antimony from tin polymetallic tailings described in this comparative example differs from the method described in Example 1 only in that: in step (1), the collector is sodium dodecyl sulfonate.

[0049] Comparative Example 2: The method for extracting tin and antimony from tin polymetallic tailings described in this comparative example differs from the method described in Example 1 only in that: in step (1), the inhibitor is unmodified starch.

[0050] Comparative Example 3: The method for extracting tin and antimony from tin polymetallic tailings described in this comparative example differs from the method described in Example 1 only in that: in step (1), the inhibitor is sodium humate in the same amount.

[0051] Experimental example: The composition of tin polymetallic tailings was determined (results are shown in Table 1). Then, tin and antimony were extracted and recovered according to the methods described in Examples 1-4 and Comparative Examples 1-3. The recovery rates of tin and antimony by different methods are shown in Table 2.

[0052] Table 1. Results of component analysis in tin polymetallic tailings.

[0053] Zinc (%) antimony(%) lead(%) sulfur(%) tin(%) Element content 2.16 0.31 0.40 6.65 0.38

[0054] Table 2. Recovery rates of tin and antimony using different methods

[0055] Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Tin recovery rate (%) 82.3 81.3 82.9 81.8 72.6 66.3 70.4 Antimony recovery rate (%) 84.1 82.3 83.5 82.7 75.9 63.4 68.9

[0056] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A method for extracting tin and antimony from tin polymetallic tailings, characterized in that: Includes the following steps: (1) Take tin polymetallic tailings and grind them to obtain slurry A with a particle size of less than 0.074 mm. Add water to slurry A to make the mass ratio of solid to liquid in slurry A 1: (3-5). Then add sodium carbonate to slurry A to adjust the pH value of slurry A to 9-10. Then add collector, inhibitor and pine oil to slurry A for flotation to obtain flotation concentrate A and flotation tailings A. The weight ratio of slurry A, collector, inhibitor and pine oil is 1000: (0. 2~0.3):(0.3~0.4):(0.05~0.08), the collector is obtained by mixing sodium dodecyl sulfonate and N-dodecyl ethanolamine, the inhibitor is obtained by dissolving starch in water, then continuously purging nitrogen and stirring at a constant temperature of 90℃ for 30 min, then cooling to 25℃, then adding ammonium persulfate and stirring, then adding acrylamide and continuing to stir and react for 2 h, then aging for 24 h, then washing, filtering and drying to obtain the inhibitor; (2) Take the flotation tailings A mentioned in step (1) and add zinc sulfate, sodium humate, ethyl thiocyanate and pine oil for flotation to obtain flotation concentrate B and flotation tailings B. The weight ratio of flotation tailings A, zinc sulfate, sodium humate, ethyl thiocyanate and pine oil is 1000:(0.3~0.4):(0.03~0.05):(0.1~0.2):(0.05~0.08). (3) Take the flotation concentrate B obtained in step (2), grind it through a 200-mesh sieve, then add hydrochloric acid solution and mix and stir for 1h to 2h, then filter to obtain filtrate A, add sodium carbonate to filtrate A to adjust the pH value to 2.0 to 3.0 and continue stirring for 1h to 2h, then let it stand for 30min and filter to obtain antimony-containing precipitate and filtrate B. The antimony-containing precipitate is decomposed with ammonia water to produce antimony trioxide product, and ammonium sulfate is added to filtrate B to obtain lead sulfate precipitate; (4) Take the flotation tailings B obtained in step (2) and filter it to obtain slag. Then crush the slag through a 200-mesh sieve and add hydrochloric acid solution to mix and stir for 1h to 2h. Then filter to obtain filtrate C. Add calcium carbonate to filtrate C to adjust the pH value to 4.0 to 4.5 and stir for 20min to 30min. Then filter to obtain filtrate D. Then add zinc powder to filtrate D and stir to react for 30min to 60min. Filter to obtain tin slag and filtrate E. The filtrate E is used to recover zinc sulfate. The tin slag is dried and then smelted by fire to cast tin ingots.

2. The method for extracting tin and antimony from tin polymetallic tailings according to claim 1, characterized in that: The weight ratio of sodium dodecyl sulfonate and N-dodecyl ethanolamine in the collector described in step (1) is 1:(0.5-1.2).

3. The method for extracting tin and antimony from tin polymetallic tailings according to claim 1, characterized in that: In the preparation of the inhibitor in step (1), the mass ratio of starch, water, ammonium persulfate and acrylamide is (3-5):100:(0.02-0.03):(8-10).

4. The method for extracting tin and antimony from tin polymetallic tailings according to claim 1, characterized in that: In step (1), a collector, inhibitor and pine oil are added to slurry A and flotation is carried out at a stirring speed of 800 r / min to 1000 r / min.

5. The method for extracting tin and antimony from tin polymetallic tailings according to claim 1, characterized in that: In step (2), the flotation tailings A described in step (1) are taken and zinc sulfate, sodium humate, ethyl thiocyanate and pine oil are added and flotation is carried out under the condition of stirring speed of 300 r / min to 500 r / min.

6. The method for extracting tin and antimony from tin polymetallic tailings according to claim 1, characterized in that: The hydrochloric acid solution has a mass fraction of 10% to 20%.

7. The method for extracting tin and antimony from tin polymetallic tailings according to claim 1, characterized in that: In step (3), the mass ratio of flotation concentrate B to hydrochloric acid solution is 1: (0.2-0.4). After crushing the slag through a 200-mesh sieve, add hydrochloric acid solution and mix and stir at 70℃-80℃ for 1-2 hours.

8. The method for extracting tin and antimony from tin polymetallic tailings according to claim 1, characterized in that: The weight ratio of slag and hydrochloric acid solution in step (4) is 1:(0.1~0.2). After crushing the slag through a 200-mesh sieve, add the hydrochloric acid solution and mix and stir at 40℃~50℃ for 1h~2h.

9. The method for extracting tin and antimony from tin polymetallic tailings according to claim 1, characterized in that: In step (4), zinc powder is added to filtrate D and the mixture is stirred at a speed of 80 r / min to 100 r / min for 30 min to 60 min.