Method for recycling antimony resource in arsenic-removed lead anode slime through fluorination conversion method

Abstract

The invention relates to a method for recovering an antimony resource in arsenic-removed lead anode slime by a fluorination conversion method, which comprises the following steps of: grinding fluoride, a slag former, a reducing agent and the arsenic-removed lead anode slime to a certain particle size, and mixing according to a certain proportion to obtain a mixed material; the mixed material is subjected to high-temperature reduction smelting, the adding amount of fluoride, the adding amount of a slag former, the adding amount of a reducing agent, the smelting temperature and the smelting time are controlled, sodium antimonate in the arsenic-removed lead anode slime reacts with fluoride to generate sodium fluoride and antimony pentoxide, antimony pentoxide is reduced into metal antimony by the reducing agent, and lead-antimony alloy is formed; antimony resources in the arsenic-removed lead anode slime are recycled, and other components become smelting slag; and the addition amount of the fluoride relative to the arsenic-removed lead anode slime is 5-10 wt%. Compared with the prior art, the recovery efficiency of antimony resources in the arsenic-removed lead anode slime is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of comprehensive resource utilization and relates to a method for recovering antimony resources in de-arsenicized lead anode mud by a fluorination conversion method. Background Art

[0002] In recent years, due to the increasing scarcity of antimony resources and the increasing consumption of antimony, the recovery of antimony from secondary resources has received increasing attention. Lead anode slime, a byproduct of the lead electrolytic refining process, is a significant secondary resource due to its rich content of valuable elements such as gold, silver, bismuth, and antimony. Lead anode slime is a byproduct of the lead electrolytic refining process. It typically contains Fe, Co, Ni, Cd, Zn, Te, Se, Sb, Bi, As, Cu, Au, Ag, Sn, and platinum group metals. Antimony recovery methods are primarily divided into wet processes and pyrometallurgical processes. Wet processes primarily include acid leaching and alkaline leaching. Acid leaching primarily uses ferric chloride, antimony pentachloride, or chlorine as a leaching agent to extract antimony in an acidic environment. The leachate can then be subjected to electrolytic or reduction treatment to produce metallic antimony, but most methods directly produce chemical products such as antimony white. The alkaline leaching method usually uses an aqueous solution of alkali metal sulfide, which can easily dissolve antimony sulfide. It can not only selectively dissolve the antimony in the concentrate, but also the sodium sulfide can be regenerated during the electrolytic process and returned for leaching. Although the hydrometallurgical process of antimony has many advantages, it also has many disadvantages. For example, the cost of producing metallic antimony using the wet process is significantly higher than that of the pyrometallurgical process; in terms of environmental protection, although there is no harm from sulfur dioxide (SO2), there are also certain problems in wastewater treatment. The waste liquid from acid leaching contains high concentrations of chloride ions (Cl - ), resulting in high processing costs. Pyrometallurgical processes primarily rely on traditional reduction smelting, recovering antimony metal through high-temperature reduction smelting. Because metals' affinity for oxygen decreases with increasing temperature, while carbon's affinity for oxygen increases, carbon can act as a reducing agent for many metal oxides at high temperatures, with the higher the temperature, the stronger its reducing power. Furthermore, carbon is inexpensive and readily available, and the reduction product, gaseous carbon monoxide (CO), is easily separated from the target metal, making it a good reducing agent for metal oxides. However, when recovering antimony from dearsenicized lead anode slime, the antimony element primarily exists in the form of sodium antimonate. Due to the dense crystal structure of sodium antimonate (NaSbO3), carbon reduction is difficult to decompose, and carbon reduction requires breaking through the oxygen binding energy, resulting in low antimony recovery efficiency, with actual reaction efficiency of only 40-60%.

[0003] At present, it remains to be studied what methods and reagents should be used to improve the recovery efficiency of antimony from dearsenicized lead anode mud. Summary of the Invention

[0004] The purpose of the present invention is to overcome at least one of the defects of the above-mentioned prior art and provide a method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion method. The present invention improves the recovery efficiency of antimony resources from dearsenicized lead anode mud.

[0005] The purpose of the present invention can be achieved by the following technical solutions:

[0006] One of the technical solutions of the present invention is to provide a method for recovering antimony resources from de-arsenicized lead anode mud using the fluorination conversion method, the method comprising the following steps:

[0007] S1. Grinding the fluoride, slagging agent, reducing agent and dearsenicized lead anode mud to a certain particle size, and uniformly mixing them in a certain proportion to obtain a mixed material;

[0008] S2. Reduction smelting the mixed material at high temperature, controlling the amount of fluoride added, the amount of slagging agent added, the amount of reducing agent added, as well as the smelting temperature and smelting time, so that the sodium antimonate in the dearsenicized lead anode slime reacts with the fluoride to generate sodium fluoride and antimony pentoxide, and the antimony pentoxide is reduced to metallic antimony by the reducing agent to form a lead-antimony alloy, thereby recovering the antimony resources in the dearsenicized lead anode slime, and the other components become smelting slag;

[0009] In step S1, the amount of fluoride added relative to the dearsenicized lead anode slime is 5-10 wt%.

[0010] Furthermore, in step S1, the fluoride is calcium fluoride.

[0011] Furthermore, in step S1, sodium carbonate is used as the slagging agent.

[0012] Furthermore, in step S1, the amount of the slag forming agent added relative to the dearsenicized lead anode slime is 15-25 wt%.

[0013] Furthermore, in step S1, the reducing agent is selected from one or more of carbon monoxide (CO), coke or anthracite.

[0014] Furthermore, in step S1, when carbon monoxide is used as the reducing agent, the concentration of the reducing agent in the gas phase is ≥25 vol%.

[0015] When the reducing agent is selected from coke or anthracite, the amount of the reducing agent added relative to the dearsenicized lead anode slime is 10-20 wt%.

[0016] As a preferred technical solution, in step S1, when the reducing agent is carbon monoxide, the balance gas in the gas phase is nitrogen (N2).

[0017] Furthermore, the content of sodium antimonate in the arsenic-removed lead anode slime in step S1 is 20-35 wt%.

[0018] As a preferred technical solution, in step S1, the antimony content in the dearsenicized lead anode slime is 25-31wt%, the tin content is 1-3wt%, the arsenic content is 16-21wt%, the lead content is 12-15wt%, the sodium content is 4-7wt%, the bismuth content is 4-8wt%, and the sodium antimonate content is 22-25wt%.

[0019] Furthermore, the particle size of the grinding in step S1 is 60-200 mesh.

[0020] Furthermore, the smelting temperature in step S2 is 900-1100°C.

[0021] Furthermore, the smelting time in step S2 is 30 to 150 minutes.

[0022] As a preferred technical solution, the smelting time in step S2 is 90 to 150 minutes.

[0023] As a preferred technical solution, the flue gas generated by smelting in step S2 is discharged into the atmosphere after waste heat recovery and tail gas treatment meet the standards.

[0024] The recovery rate of antimony is ≥90%.

[0025] Compared with the prior art, the present invention has the following beneficial effects:

[0026] (1) The present invention adds fluoride to the reactants, causing the sodium antimonate in the dearsenicized lead anode mud to react with the fluoride to generate sodium fluoride and antimony pentoxide, thereby enabling the antimony resources to be reduced and recovered under high-temperature smelting. The fluoride converts the difficult-to-reduced sodium antimonate into the easily reducible antimony pentoxide, thereby greatly improving the antimony recovery efficiency. The invention has the advantages of low cost, good economy, and low environmental pollution, and has a good prospect for promotion and application.

[0027] (2) In the reduction smelting process of the present invention, by controlling key parameters such as the amount of fluoride added, the amount of sodium carbonate added, the amount of reducing agent added, and the smelting temperature and smelting time, the fluoride reacts with the sodium antimonate phase in the dearsenicized lead anode mud, and the fluoride ions combine with the sodium ions in the sodium antimonate to form sodium fluoride which enters the smelting slag, thereby breaking the structure of the sodium antimonate and converting it into antimony pentoxide. The antimony pentoxide is reduced to metallic antimony by the reducing agent to form a lead-antimony alloy, thereby reducing the loss of metallic antimony and improving the recovery rate of antimony resources. The slag-forming agent further promotes the separation of the alloy phase and the slag phase;

[0028] (3) The present invention can efficiently separate and recover antimony resources in lead anode mud, avoiding the problem of difficult reduction of sodium antimonate in traditional methods and effectively improving the recovery rate of antimony resources. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1This is a flow chart of a method for recovering antimony resources from dearsenicized lead anode mud using a fluorination conversion method according to an embodiment of the present invention. DETAILED DESCRIPTION

[0030] The present invention is described in detail below with reference to specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0031] Unless otherwise specified, the equipment used in the following examples are all conventional equipment in the art; the reagents used are all commercially available products or prepared by conventional methods in the art unless otherwise specified. Anything not described in detail in the following examples can be achieved by conventional experimental means in the art.

[0032] Example 1:

[0033] A method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion, such as Figure 1 The specific steps are as follows:

[0034] S1. The dearsenicized lead anode slime of a smelting company was treated. Its antimony content was 29.88wt%, tin content was 1.39wt%, arsenic content was 16.53wt%, lead content was 13.14wt%, sodium content was 4.32wt%, bismuth content was 4.52wt%, and sodium antimonate content was 22.87wt%.

[0035] 15 g of dearsenicized lead anode mud was ground into 80 mesh, calcium fluoride was ground into 60 mesh, sodium carbonate was ground into 60 mesh, and coke was ground into 60 mesh. The dearsenicized lead anode mud, calcium fluoride, sodium carbonate, and coke were mixed in proportion to obtain a mixed material.

[0036] S2. Using a muffle furnace as a smelting furnace, the mixed material is placed in the smelting furnace and subjected to high-temperature reduction smelting. The amount of calcium fluoride added is controlled to be 5wt%, the amount of sodium carbonate added is 20wt%, the amount of coke added is 15wt%, the smelting temperature is controlled to be 950°C, and the smelting time is controlled to be 120min. The sodium antimonate in the dearsenicized lead anode slime reacts with the calcium fluoride to generate sodium fluoride and antimony pentoxide. The antimony pentoxide is reduced to metallic antimony by the coke. After the reduction smelting is completed, a lead-antimony alloy and smelting slag are generated. The flue gas generated by the smelting is discharged into the atmosphere after waste heat recovery and tail gas treatment to meet the standards.

[0037] After the lead-antimony alloy was taken out, the metals present therein were analyzed and it was found that the recovery rate of antimony reached 93.9%. That is, this embodiment can achieve efficient recovery of antimony resources in dearsenicized lead anode mud.

[0038] Example 2:

[0039] A method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion, such as Figure 1 The specific steps are as follows:

[0040] S1. The dearsenicized lead anode slime of a smelting company was treated. Its antimony content was 30.28wt%, tin content was 1.49wt%, arsenic content was 17.22wt%, lead content was 14.05wt%, sodium content was 4.45wt%, bismuth content was 5.05wt%, and sodium antimonate content was 23.55wt%.

[0041] 15 g of dearsenicized lead anode mud was ground into 100 mesh, calcium fluoride was ground into 80 mesh, sodium carbonate was ground into 80 mesh, and coke was ground into 80 mesh. The dearsenicized lead anode mud, calcium fluoride, sodium carbonate, and coke were mixed in proportion to obtain a mixed material.

[0042] S2. Using a muffle furnace as a smelting furnace, the mixed material is placed in the smelting furnace and subjected to high-temperature reduction smelting. The amount of calcium fluoride added is controlled to be 7.5 wt%, the amount of sodium carbonate added is 20 wt%, the amount of coke added is 15 wt%, the smelting temperature is 1000° C., and the smelting time is 120 min. The sodium antimonate in the dearsenicized lead anode slime reacts with the calcium fluoride to generate sodium fluoride and antimony pentoxide. The antimony pentoxide is reduced to metallic antimony by the coke. After the reduction smelting is completed, a lead-antimony alloy and smelting slag are generated. The flue gas generated by the smelting is discharged into the atmosphere after waste heat recovery and tail gas treatment to meet the standards.

[0043] After the lead-antimony alloy was taken out, the metals present therein were analyzed and tested, and it was found that the recovery rate of antimony reached 95.2%. That is, this embodiment can achieve efficient recovery of antimony resources in dearsenicized lead anode mud.

[0044] Example 3:

[0045] A method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion, such as Figure 1 The specific steps are as follows:

[0046] S1. The dearsenicized lead anode slime of a smelting company was treated. Its antimony content was 25.95wt%, tin content was 2.05wt%, arsenic content was 20.53wt%, lead content was 12.06wt%, sodium content was 6.78wt%, bismuth content was 7.82wt%, and sodium antimonate content was 24.81wt%.

[0047] 15 g of dearsenicized lead anode mud was ground into 200 mesh, calcium fluoride was ground into 100 mesh, sodium carbonate was ground into 100 mesh, and coke was ground into 100 mesh. The dearsenicized lead anode mud, calcium fluoride, sodium carbonate, and coke were mixed uniformly according to a proportion to obtain a mixed material;

[0048] S2. A muffle furnace is used as a smelting furnace, and the mixed material is placed in the smelting furnace for high-temperature reduction smelting. The amount of calcium fluoride added is controlled to be 10wt%, the amount of sodium carbonate added is 20wt%, the amount of coke added is 15wt%, the smelting temperature is 1050°C, and the smelting time is 120min. The sodium antimonate in the dearsenicized lead anode slime reacts with the calcium fluoride to generate sodium fluoride and antimony pentoxide. The antimony pentoxide is reduced to metallic antimony by the coke. After the reduction smelting is completed, a lead-antimony alloy and smelting slag are generated. The flue gas generated by the smelting is discharged into the atmosphere after waste heat recovery and tail gas treatment to meet the standards.

[0049] After the lead-antimony alloy was taken out, the metals present therein were analyzed and tested, and it was found that the recovery rate of antimony reached 92.5%. That is, this embodiment can achieve efficient recovery of antimony resources in dearsenicized lead anode mud.

[0050] Example 4:

[0051] A method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion, such as Figure 1 The specific steps are as follows:

[0052] S1. The dearsenicized lead anode slime of a smelting company was treated. Its antimony content was 30.28wt%, tin content was 1.49wt%, arsenic content was 17.22wt%, lead content was 14.05wt%, sodium content was 4.45wt%, bismuth content was 5.05wt%, and sodium antimonate content was 23.55wt%.

[0053] 15 g of dearsenicized lead anode mud was ground into 100 mesh, calcium fluoride was ground into 80 mesh, and sodium carbonate was ground into 80 mesh. The dearsenicized lead anode mud, calcium fluoride, sodium carbonate, and coke were mixed in proportion to obtain a mixed material.

[0054] S2. A muffle furnace is used as a smelting furnace, and the mixed material is placed in the smelting furnace. The mixed material is subjected to high-temperature reduction smelting in a reducing atmosphere of carbon monoxide (CO) and nitrogen (N2). The amount of calcium fluoride added is controlled to be 7.5wt%, the amount of sodium carbonate added is 20wt%, the carbon monoxide concentration is 30vol%, the smelting temperature is 1000°C, and the smelting time is 120min. The sodium antimonate in the dearsenicized lead anode mud reacts with the calcium fluoride to generate sodium fluoride and antimony pentoxide. The antimony pentoxide is reduced to metallic antimony by carbon monoxide. After the reduction smelting is completed, a lead-antimony alloy and smelting slag are generated. The flue gas generated by the smelting is discharged into the atmosphere after waste heat recovery and tail gas treatment to meet the standards.

[0055] After the lead-antimony alloy was taken out, the metals present therein were analyzed and tested, and it was found that the recovery rate of antimony reached 94.8%. That is, this embodiment can achieve efficient recovery of antimony resources in dearsenicized lead anode mud.

[0056] The above description of the embodiments is intended to facilitate understanding and use of the invention by those skilled in the art. It will be apparent that those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without requiring inventive effort. Therefore, the present invention is not limited to the above-described embodiments. Improvements and modifications made by those skilled in the art based on the disclosure of the present invention, without departing from the scope of the present invention, should be within the scope of protection of the present invention.

Claims

1. A method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion, characterized in that: The method comprises the following steps: S1. Grinding the fluoride, slagging agent, reducing agent and dearsenicized lead anode mud to a certain particle size, and mixing them in a certain proportion to obtain a mixed material; S2. Reduction smelting the mixed material at high temperature, controlling the amount of fluoride added, the amount of slagging agent added, the amount of reducing agent added, as well as the smelting temperature and smelting time, so that the sodium antimonate in the dearsenicized lead anode slime reacts with the fluoride to generate sodium fluoride and antimony pentoxide, and the antimony pentoxide is reduced to metallic antimony by the reducing agent to form a lead-antimony alloy, thereby recovering the antimony resources in the dearsenicized lead anode slime, and the other components become smelting slag; In step S1, the amount of fluoride added relative to the dearsenicized lead anode slime is 5-10 wt%.

2. The method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion according to claim 1, characterized in that: In step S1, the fluoride is calcium fluoride.

3. The method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion according to claim 1, characterized in that: In step S1, sodium carbonate is used as the slagging agent.

4. The method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion according to claim 1, characterized in that: In step S1, the amount of the slag forming agent added relative to the dearsenicized lead anode slime is 15-25 wt%.

5. The method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion according to claim 1, characterized in that: In step S1, the reducing agent is selected from one or more of carbon monoxide, coke or anthracite.

6. The method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion according to claim 5, characterized in that: In step S1, when carbon monoxide is used as the reducing agent, the concentration of the reducing agent in the gas phase is ≥ 25 vol%. When the reducing agent is selected from coke or anthracite, the amount of the reducing agent added relative to the dearsenicized lead anode slime is 10-20 wt%.

7. The method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion according to claim 1, characterized in that: The content of sodium antimonate in the dearsenicized lead anode mud in step S1 is 20-35 wt%.

8. The method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion according to claim 1, characterized in that: The particle size of the grinding in step S1 is 60 to 200 meshes.

9. The method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion according to claim 1, characterized in that: The smelting temperature in step S2 is 900-1100°C.

10. The method for recovering antimony resources from dearsenicized lead anode mud by fluorination conversion according to claim 1, characterized in that: The smelting time in step S2 is 30 to 150 minutes.

Images