A method for producing electrolytic nickel from a nickel-containing solid waste raw material

Abstract

The present application relates to the technical field of nickel-containing waste recovery, and specifically discloses a method for producing electrolytic nickel from nickel-containing solid waste raw materials, which blends and calcines nickel-containing waste, tin-containing waste and a synergist. Tin in the tin-containing waste has a low melting point, can form a Ni3Sn2 metal compound with Ni, and can also form an alloy phase with Co and Cr, and can permeate between nickel-based alloy grains, destroying the original dense structure, effectively reducing the dissolution leaching difficulty of the nickel-based high-temperature alloy waste, and improving the dissolution leaching efficiency of nickel in the waste. Meanwhile, through the action of the synergist, rapid heating and melting can be achieved, and the ferrous iron in the nickel-containing waste can be oxidized to iron oxide, breaking the dense continuity of the original iron-nickel metal phase, reducing the subsequent dissolution leaching difficulty, and by oxidizing Fe 2+ to Fe 3+ , Fe 3+ can form a precipitate at a lower pH, and is easier to separate.

Description

Technical Field

[0001] This invention relates to the field of nickel-containing waste recycling technology, specifically to a method for producing electrolytic nickel from nickel-containing solid waste raw materials. Background Technology

[0002] Nickel, as a scarce strategic metal, holds an irreplaceable position in modern industry. Recovering nickel from nickel-containing waste can alleviate the pressure of primary nickel resource mining and reduce the risk of solid waste pollution, making it a key direction for resource recycling. However, nickel-containing waste has a complex composition, often containing alloying elements such as Co, Cr, and Mo, and has a dense phase structure. For example, the stable intermetallic compounds formed by nickel-based superalloys due to their high-temperature resistance pose a challenge to the efficient recovery of nickel.

[0003] Currently, nickel-containing waste recycling processes are divided into pyrometallurgical processes and hydrometallurgical processes. Pyrometallurgical processes alone are prone to insufficient nickel purity due to impurity accumulation, while hydrometallurgical processes alone face problems such as difficulty in dissolving high-melting-point alloys and poor selectivity in separating valuable metals. This is especially true for nickel-based high-temperature alloy waste, whose high-strength and high-stability microstructure results in low leaching efficiency in conventional hydrometallurgical processes such as acid leaching and alkali leaching. For example, Chinese patent document 201110130345.5 discloses a method for comprehensively treating nickel-containing waste to recover nickel sulfate, including mixing yellow slag with sludge from electroplating wastewater treatment, adding water and mixing evenly, stirring, and leaching; introducing air or oxygen into the leaching solution to oxidize and precipitate iron impurities, filtering, and collecting the filtrate; extracting the filtrate with an extractant to remove impurities, obtaining a nickel sulfate solution, and concentrating and crystallizing to obtain nickel sulfate crystals. The method adopted in the above patent is insufficient to fully destroy the material structure of the nickel-containing waste, making it impossible to fully dissolve the nickel, and the leaching rate still needs further improvement. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a method for producing electrolytic nickel from nickel-containing solid waste raw materials.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] A method for producing electrolytic nickel from nickel-containing solid waste raw materials includes the following steps:

[0007] S1. Preparation of alloy materials

[0008] Nickel-containing waste, tin-containing waste, and synergist are mixed evenly, then heated to melt, and cooled to obtain alloy material.

[0009] In this step, the nickel-containing waste can be selected from waste generated after the scrapping of stainless steel products, positive electrode materials of waste batteries, electroplating sludge, or waste nickel-based catalysts.

[0010] In this step, the tin-containing waste can be selected from waste electronic products, iron-tin alloy slag, glass coating waste, or tin foil waste.

[0011] In this step, the mass ratio of the nickel-containing waste, tin-containing waste, and synergist is 100:100-120:10-15. For example, 100:100:10, 100:100:12, 100:100:15, 100:110:10, 100:110:15, 100:120:10, 100:120:12, and 100:120:15 can be selected, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0012] In the technical solution disclosed in this invention, the synergist is composed of calcium peroxide, activated carbon, and fluorite, wherein the mass ratio of calcium peroxide, activated carbon, and fluorite is 10-20:5-10:5-10, for example, 10:5:5, 10:5:10, 10:10:5, 10:10:10, 15:5:5, 15:5:10, 20:5:5, 20:10:5, 20:5:10, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0013] In this step, heating and melting are carried out under a nitrogen atmosphere at a temperature of 1000-1100℃, such as 1000℃, 1010℃, 1020℃, 1030℃, 1040℃, 1050℃, 1060℃, 1070℃, 1080℃, 1090℃, or 1100℃. The heating and melting time is 6-10 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0014] In this invention, nickel-containing waste, tin-containing waste, and an synergist are co-calcined. Tin in the tin-containing waste has a low melting point and can form Ni3Sn2 metal compounds with Ni, as well as alloy phases with Co and Cr. Tin can penetrate into the grains of nickel-based alloys, destroying the original dense structure, effectively reducing the difficulty of dissolving and leaching nickel-based high-temperature alloy waste, and improving the dissolution and leaching efficiency of nickel in the waste. At the same time, by incorporating tin-containing waste, a nickel-tin eutectic alloy is formed, which lowers the heating and melting temperature, allowing alloying to be carried out at a lower temperature and saving energy.

[0015] In the synergist provided by this invention, calcium peroxide decomposes at high temperature to generate calcium oxide and oxygen. The oxygen can oxidize the ferrous iron in nickel-containing waste to ferric oxide, breaking the original dense continuity of the iron-nickel metal phase, reducing the difficulty of subsequent dissolution and leaching, and by... 2+ Oxidized to Fe 3+ Fe 3+It can form precipitates at lower pH levels, making separation easier. In addition, nickel-containing waste often contains acidic impurities such as sulfur and phosphorus. If these impurities are introduced into subsequent wet processes, they will increase the difficulty of impurity removal and even corrode equipment. Calcium oxide, as an alkaline flux, can react with S and P during high-temperature alloying to generate stable slag phases such as calcium sulfide and calcium phosphate, thereby separating sulfur and phosphorus impurities from the alloy material.

[0016] The main component of fluorite is CaF2. CaF2 can lower the melting point of waste and improve its fluidity, making it easier for impurities such as sulfur and phosphorus to accumulate in the slag phase. The carbon element provided by activated carbon can act as a "heterogeneous nucleation core" during alloy solidification, inducing the refinement of alloy grains. At the same time, trace amounts of carbon can form a dispersed carbide phase with nickel, further disrupting the continuity of the original dense structure of nickel-containing waste, which is beneficial for the subsequent dissolution and leaching of nickel.

[0017] S2. Preparation of nickel-rich leachate

[0018] The alloy material obtained in step S1 is crushed and ground into a fine powder and then added to a sulfuric acid solution. Sodium chlorate is then added, and the mixture is heated to leach, resulting in a nickel-rich leachate.

[0019] In this step, the alloy material is crushed and then passed through a 40-mesh sieve.

[0020] In this step, the solid-liquid ratio of the alloy material and the sulfuric acid solution is 1g:10-20mL. In some embodiments of the present invention, for example, 1g:10mL, 1g:12mL, 1g:14mL, 1g:15mL, 1g:16mL, 1g:17mL, 1g:18mL, 1g:19mL, and 1g:20mL can be selected, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0021] Specifically, the concentration of the sulfuric acid solution is 5-10 mol / L. For example, 5 mol / L, 6 mol / L, 7 mol / L, 8 mol / L, 9 mol / L, and 10 mol / L can be selected, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0022] In this step, the mass ratio of the alloy material to sodium chlorate is 1:2-2.5. For example, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, and 1:2.5 can be selected, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0023] In this step, the heating and leaching temperature is 70-80℃, for example, 70℃, 72℃, 74℃, 75℃, 76℃, 77℃, 78℃, 79℃, or 80℃ can be selected; the heating and leaching time is 6-8 hours, for example, 6 hours, 6.5 hours, 7 hours, 7.5 hours, or 8 hours can be selected, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0024] S3. Prepare filtrate

[0025] An alkaline solution is added to the leachate obtained in step S2, and after precipitation and filtration, a filtrate is obtained.

[0026] In this step, the alkaline solution is selected from Na2CO3 solution or NaOH solution, and the concentration of the alkaline solution is 0.5-2 mol / L. For example, 0.5 mol / L, 1 mol / L, 1.5 mol / L, and 2 mol / L can be selected, but it is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0027] In this step, the pH of the leaching solution is first adjusted to 1.5-2 using an alkaline solution, allowing tin to precipitate and separate from the leaching solution. Then, the pH of the leaching solution is adjusted to 4.5-5.5 to remove iron and chromium from the leaching solution.

[0028] S4. Preparation of nickel sulfate solution

[0029] The obtained filtrate was extracted to obtain a nickel sulfate solution.

[0030] In this step, the extractant used in the extraction process consists of P507 and kerosene, with P507 accounting for 10-20% by volume.

[0031] In this step, multi-stage extraction can be used.

[0032] S5. Preparation of electrolytic nickel

[0033] Electrolysis of the obtained nickel sulfate solution yields electrolytic nickel.

[0034] In this step, existing processes are used to electrolyze the nickel sulfate solution. For example, a Pb-Ag-Ca alloy can be selected as the anode and a stainless steel plate as the cathode, with a current density of 1000 A / m. 2 Electrolysis was carried out at an electrolyte temperature of 25℃ and an electrolyte circulation rate of 1L / min.

[0035] Compared with the prior art, the present invention has the following beneficial effects:

[0036] (1) This invention involves co-calcining nickel-containing waste, tin-containing waste, and an enhancer. Tin in the tin-containing waste has a low melting point and can form Ni3Sn2 metal compound with Ni, as well as alloy phase with Co and Cr. It can penetrate into the grains of nickel-based alloys, destroy the original dense structure, effectively reduce the difficulty of dissolving and leaching nickel-based high-temperature alloy waste, and improve the dissolution and leaching efficiency of nickel in the waste. At the same time, by adding tin-containing waste, the heating and melting temperature is reduced, and alloying can be carried out at a lower temperature, saving energy consumption.

[0037] (2) In the synergist provided by this invention, calcium peroxide decomposes at high temperature to generate calcium oxide and oxygen. The weak oxidizing atmosphere can achieve rapid heating and melting, and at the same time, it can oxidize the ferrous iron in nickel-containing waste to ferric oxide, breaking the original dense continuity of the iron-nickel metal phase, reducing the difficulty of subsequent dissolution and leaching, and by... 2+ Oxidized to Fe 3+ Fe 3+ It can form precipitates at lower pH levels, making separation easier. In addition, nickel-containing waste often contains acidic impurities such as sulfur and phosphorus. If these impurities are introduced into subsequent wet processes, they will increase the difficulty of impurity removal and even corrode equipment. Calcium oxide, as an alkaline flux, can react with S and P during high-temperature alloying to generate stable slag phases such as calcium sulfide and calcium phosphate, thereby separating sulfur and phosphorus impurities from the alloy material.

[0038] (3) The main component of fluorite is CaF2. CaF2 can lower the melting point of waste and improve its fluidity, making it easier for impurities such as sulfur and phosphorus to accumulate in the slag phase. The carbon element provided by activated carbon can act as a "heterogeneous nucleation core" during alloy solidification, inducing the refinement of alloy grains. At the same time, trace amounts of carbon can form a dispersed carbide phase with nickel, further disrupting the continuity of the original dense structure of nickel-containing waste, which is beneficial for the subsequent dissolution and leaching of nickel.

[0039] (4) This invention prepares nickel sulfate solution by blending and smelting nickel-containing waste, tin-containing waste and synergist, followed by oxidation leaching, precipitation and extraction to remove impurities, and can also effectively recover tin from tin-containing waste, thus achieving the goal of simultaneous resource recycling and reuse. Detailed Implementation

[0040] The present invention will be further described in detail below through specific preferred embodiments, but the present invention is not limited to the following embodiments.

[0041] It should be noted that, unless otherwise specified, all chemical reagents involved in this invention were purchased through commercial channels.

[0042] The nickel-containing waste used in this embodiment of the invention is nickel-containing waste catalyst, and its main components are: 12.6% Ni, 6.3% Cu, 4.8% Fe, 1.1% S, 2.0% Zn, 3.9% Cr, and 4.3% SiO2.

[0043] Tin-containing waste is tin-containing electronic waste, with a tin content of 10.2% and a nickel content of 0.3%.

[0044] The mesh size of calcium peroxide is 200.

[0045] The activated carbon is coconut shell activated carbon with a mesh size of 325.

[0046] The fluorite has a mesh size of 80.

[0047] Example 1

[0048] A method for producing electrolytic nickel from nickel-containing solid waste raw materials includes the following steps:

[0049] S1. After crushing the nickel-containing waste and tin-containing waste separately, pass them through a 40-mesh sieve. Then, mix 100 parts of nickel-containing waste, 100 parts of tin-containing waste and 10 parts of synergist evenly. The synergist is composed of calcium peroxide, activated carbon and fluorite, with a mass ratio of calcium peroxide, activated carbon and fluorite of 10:5:5. Then, put it into a melting furnace and heat it under a nitrogen atmosphere. The heating and melting temperature is 1000℃ and the heating and melting time is 10h. After the heating and melting is completed, pour it into a crucible to cool and break it to obtain the alloy material.

[0050] S2. After crushing and grinding the alloy material obtained in step S1, pass it through a 40-mesh sieve. Add the alloy material to a 6 mol / L sulfuric acid solution at a solid-liquid ratio of 1:10, and then add sodium chlorate. The mass ratio of the alloy material to sodium chlorate is 1:2. Heat at 70°C for 8 hours to obtain a nickel-rich leachate.

[0051] S3. Add 1 mol / L Na2CO3 solution to the leachate obtained in step S2 to adjust the pH of the leachate to 1.6. Tin precipitates from the leachate first, and is filtered to obtain the first filtrate. Then adjust the pH of the first filtrate to 5.0, and after precipitation and filtration, obtain the second filtrate.

[0052] S4. The second filtrate is subjected to secondary extraction to remove impurities. The extractants used in the extraction process are all composed of P507 and kerosene, with P507 accounting for 10% of the volume, to obtain a nickel sulfate solution.

[0053] S5. Electrolyze the obtained nickel sulfate solution, using a Pb-Ag-Ca alloy as the anode and a stainless steel plate as the cathode, at a current density of 1000 A / m. 2The electrolyte temperature is 25℃, the electrolyte circulation rate is 1L / min, and electrolytic nickel is obtained at the cathode.

[0054] The nickel content in the leaching solution in step S2 was determined. The nickel leaching rate (%) = mass of nickel in the leaching solution / (mass of nickel in nickel-containing waste + mass of nickel in tin-containing waste) × 100%. The nickel leaching rate was 98.9%.

[0055] The tin recovery rate in step S3 was determined. Tin recovery rate (%) = mass of tin in the precipitate / mass of tin in the tin-containing waste × 100%. The tin recovery rate was 97.3%.

[0056] Example 2

[0057] A method for producing electrolytic nickel from nickel-containing solid waste raw materials includes the following steps:

[0058] S1. After crushing the nickel-containing waste and tin-containing waste separately, pass them through a 40-mesh sieve. Then, mix 100 parts of nickel-containing waste, 120 parts of tin-containing waste and 15 parts of synergist evenly. The synergist is composed of calcium peroxide, activated carbon and fluorite, with a mass ratio of calcium peroxide, activated carbon and fluorite of 20:5:10. Then, put it into a melting furnace and heat it under a nitrogen atmosphere. The heating and melting temperature is 1000℃ and the heating and melting time is 10h. After the heating and melting is completed, pour it into a crucible to cool and break it to obtain the alloy material.

[0059] S2. After crushing and grinding the alloy material obtained in step S1, pass it through a 40-mesh sieve. Add the alloy material to a 6 mol / L sulfuric acid solution at a solid-liquid ratio of 1:15, and then add sodium chlorate. The mass ratio of the alloy material to sodium chlorate is 1:2. Heat at 70°C for 8 hours to obtain a nickel-rich leachate.

[0060] S3. Add 1 mol / L Na2CO3 solution to the leachate obtained in step S2 to adjust the pH of the leachate to 1.6. Tin precipitates from the leachate first, and is filtered to obtain the first filtrate. Then adjust the pH of the first filtrate to 5.0, and after precipitation and filtration, obtain the second filtrate.

[0061] S4. The second filtrate is subjected to secondary extraction to remove impurities. The extractants used in the extraction process are all composed of P507 and kerosene, with P507 accounting for 10% of the volume, to obtain a nickel sulfate solution.

[0062] S5. Electrolyze the obtained nickel sulfate solution, using a Pb-Ag-Ca alloy as the anode and a stainless steel plate as the cathode, at a current density of 1000 A / m. 2 The electrolyte temperature is 25℃, the electrolyte circulation rate is 1L / min, and electrolytic nickel is obtained at the cathode.

[0063] Calculated according to the method in Example 1, the nickel leaching rate in step S2 is 99.2%, and the tin recovery rate in step S3 is 97.8%.

[0064] Comparative Example 1

[0065] A method for producing electrolytic nickel from nickel-containing solid waste raw materials includes the following steps:

[0066] S1. After crushing the nickel-containing waste, pass it through a 40-mesh sieve. Then, mix 100 parts of the nickel-containing waste with 10 parts of the synergist evenly. The synergist is composed of calcium peroxide, activated carbon, and fluorite, with a mass ratio of 10:5:5. Then, put it into a melting furnace and heat it under a nitrogen atmosphere. The heating and melting temperature is 1000℃ and the heating and melting time is 10h. After the heating and melting is completed, pour it into a crucible to cool and break it to obtain the alloy material.

[0067] S2. After crushing and grinding the alloy material obtained in step S1, pass it through a 40-mesh sieve. Add the alloy material to a 6 mol / L sulfuric acid solution at a solid-liquid ratio of 1:10, and then add sodium chlorate. The mass ratio of the alloy material to sodium chlorate is 1:2. Heat at 70°C for 8 hours to obtain a nickel-rich leachate.

[0068] S3. Add 1 mol / L Na2CO3 solution to the leachate obtained in step S2, adjust the pH of the leachate to 5.0, and obtain the filtrate after precipitation and filtration.

[0069] S4. The obtained filtrate is subjected to secondary extraction to remove impurities. The extractants used in the extraction process are all composed of P507 and kerosene, with P507 accounting for 10% of the volume, to obtain nickel sulfate solution.

[0070] S5. Electrolyze the obtained nickel sulfate solution, using a Pb-Ag-Ca alloy as the anode and a stainless steel plate as the cathode, at a current density of 1000 A / m. 2 The electrolyte temperature is 25℃, the electrolyte circulation rate is 1L / min, and electrolytic nickel is obtained at the cathode.

[0071] Compared with Comparative Example 1 and Example 1, no tin-containing waste was added, and the nickel leaching rate in step S2 was 76.3%.

[0072] Comparative Example 2

[0073] A method for producing electrolytic nickel from nickel-containing solid waste raw materials includes the following steps:

[0074] S1. After crushing the nickel-containing waste and tin-containing waste separately, pass them through a 40-mesh sieve. Then, mix 100 parts of nickel-containing waste, 100 parts of tin-containing waste and 10 parts of synergist evenly. The synergist is composed of calcium oxide, activated carbon and fluorite, with a mass ratio of calcium oxide, activated carbon and fluorite of 10:5:5. Then, put it into a melting furnace and heat it under a nitrogen atmosphere. The heating and melting temperature is 1000℃ and the heating and melting time is 10h. After the heating and melting is completed, pour it into a crucible to cool and break it to obtain the alloy material.

[0075] S2. After crushing and grinding the alloy material obtained in step S1, pass it through a 40-mesh sieve. Add the alloy material to a 6 mol / L sulfuric acid solution at a solid-liquid ratio of 1:10, and then add sodium chlorate. The mass ratio of the alloy material to sodium chlorate is 1:2. Heat at 70°C for 8 hours to obtain a nickel-rich leachate.

[0076] S3. Add 1 mol / L Na2CO3 solution to the leachate obtained in step S2 to adjust the pH of the leachate to 1.6. Tin precipitates from the leachate first, and is filtered to obtain the first filtrate. Then adjust the pH of the first filtrate to 5.0, and after precipitation and filtration, obtain the second filtrate.

[0077] S4. The second filtrate is subjected to secondary extraction to remove impurities. The extractants used in the extraction process are all composed of P507 and kerosene, with P507 accounting for 10% of the volume, to obtain a nickel sulfate solution.

[0078] S5. Electrolyze the obtained nickel sulfate solution, using a Pb-Ag-Ca alloy as the anode and a stainless steel plate as the cathode, at a current density of 1000 A / m. 2 The electrolyte temperature is 25℃, the electrolyte circulation rate is 1L / min, and electrolytic nickel is obtained at the cathode.

[0079] Compared with Comparative Example 2 and Example 1, calcium oxide was used instead of calcium peroxide in the synergist, and the nickel leaching rate in step S2 was 89.4%.

[0080] Comparative Example 3

[0081] A method for producing electrolytic nickel from nickel-containing solid waste raw materials includes the following steps:

[0082] S1. After crushing the nickel-containing waste and tin-containing waste separately, pass them through a 40-mesh sieve. Then, mix 100 parts of nickel-containing waste, 100 parts of tin-containing waste and 10 parts of synergist evenly. The synergist is composed of calcium peroxide and fluorite, with a mass ratio of calcium peroxide to fluorite of 10:5. Then, put it into a melting furnace and heat it under a nitrogen atmosphere. The heating and melting temperature is 1000℃ and the heating and melting time is 10h. After the heating and melting is completed, pour it into a crucible to cool and break it to obtain the alloy material.

[0083] S2. After crushing and grinding the alloy material obtained in step S1, pass it through a 40-mesh sieve. Add the alloy material to a 6 mol / L sulfuric acid solution at a solid-liquid ratio of 1:10, and then add sodium chlorate. The mass ratio of the alloy material to sodium chlorate is 1:2. Heat at 70°C for 8 hours to obtain a nickel-rich leachate.

[0084] S3. Add 1 mol / L Na2CO3 solution to the leachate obtained in step S2 to adjust the pH of the leachate to 1.6. Tin precipitates from the leachate first, and is filtered to obtain the first filtrate. Then adjust the pH of the first filtrate to 5.0, and after precipitation and filtration, obtain the second filtrate.

[0085] S4. The second filtrate is subjected to secondary extraction to remove impurities. The extractants used in the extraction process are all composed of P507 and kerosene, with P507 accounting for 10% of the volume, to obtain a nickel sulfate solution.

[0086] S5. Electrolyze the obtained nickel sulfate solution, using a Pb-Ag-Ca alloy as the anode and a stainless steel plate as the cathode, at a current density of 1000 A / m. 2 The electrolyte temperature is 25℃, the electrolyte circulation rate is 1L / min, and electrolytic nickel is obtained at the cathode.

[0087] Compared with Comparative Example 3 and Example 1, no activated carbon was added to the synergist, and the nickel leaching rate in step S2 was 91.7%.

[0088] Finally, it should be noted that the above embodiments do not limit the present invention in any way. Those skilled in the art can make modifications and improvements based on the present invention. Therefore, any modifications or improvements made without departing from the spirit of the present invention are within the scope of protection claimed by the present invention.

Claims

1. A method for producing electrolytic nickel from nickel-containing solid waste raw materials, characterized in that, Includes the following steps: S1. Mix nickel-containing waste, tin-containing waste and synergist evenly, then heat to melt, cool, and obtain alloy material; S2. After crushing and grinding the alloy material obtained in step S1, add it to a sulfuric acid solution, then add sodium chlorate, heat and leach to obtain a nickel-rich leachate. S3. Add an alkaline solution to the leachate obtained in step S2, and after precipitation and filtration, obtain the filtrate. S4. Extract the obtained filtrate to obtain a nickel sulfate solution; S5. Electrolyze the obtained nickel sulfate solution to obtain electrolytic nickel; In step S1, the mass ratio of the nickel-containing waste, the tin-containing waste, and the synergist is 100:100-120:10-15. The synergist is composed of calcium peroxide, activated carbon and fluorite, wherein the mass ratio of calcium peroxide, activated carbon and fluorite is 10-20:5-10:5-10.

2. The method according to claim 1, characterized in that, In step S1, the heating and melting temperature is 1000-1100℃, and the heating and melting time is 6-10h.

3. The method according to claim 1, characterized in that, In step S2, the solid-liquid ratio of the alloy material and the sulfuric acid solution is 1g:10-20mL.

4. The method according to claim 1, characterized in that, In step S2, the mass ratio of the alloy material to sodium chlorate is 1:2-2.

5.

5. The method according to claim 1, characterized in that, In step S2, the leaching temperature is 70-80℃, and the leaching time is 6-8 hours.

6. The method according to claim 1, characterized in that, In step S3, the alkaline solution is selected from Na2CO3 solution or NaOH solution.

7. The method according to claim 1, characterized in that, In step S4, the extractant used in the extraction process consists of P507 and kerosene, with P507 accounting for 10-20% of the volume.