Method for preparing arsenic-antimony-based alloy from arsenic-antimony smelting smoke dust, and arsenic-antimony-based alloy

Abstract

Disclosed in the present invention are a method for preparing an arsenic-antimony-based alloy from arsenic-antimony smelting smoke dust, and an arsenic-antimony-based alloy. The method for preparing an arsenic-antimony-based alloy comprises: uniformly mixing arsenic-antimony smelting smoke dust and a carbonaceous reducing agent in proportion, so as to obtain a mixture; placing the mixture into a high-temperature reduction furnace, heating same to 800-950ºC, and maintaining the temperature to perform a reduction reaction, wherein the temperature maintaining time is 1.0-2.5 h; and after the reduction reaction is finished, slagging off the melt, such that an arsenic-antimony-based alloy melt is left at the bottom of the furnace body, and casting same to obtain an arsenic-antimony-based alloy. The arsenic-antimony-based alloy is prepared by using the method for preparing an arsenic-antimony-based alloy. In the present invention, the relatively high oxidizing property of an arsenic oxide and an antimony oxide is fully utilized, and the arsenic oxide and the antimony oxide are prone to being subjected to a reduction reaction with carbon under high-temperature conditions to generate metals, and the metals are molten to form the arsenic-antimony-based alloy, thereby facilitating the subsequent technical treatment, so as to separate arsenic, antimony, lead, zinc, bismuth and other metals, and achieving comprehensive recovery and reduction disposal of valuable metals in the arsenic-antimony smelting smoke dust; and compared with other treatment processes, the process flow is simple, and the treatment cost is low.

Description

Method for preparing arsenic-antimony based alloy from arsenic-antimony smelting dust and arsenic-antimony based alloy Technical Field

[0001] The present invention relates to the technical field of nonferrous metallurgy, and in particular to a method for preparing an arsenic-antimony-based alloy from arsenic-antimony smelting smoke, which is easy to realize comprehensive recovery and reduced disposal of valuable metals in arsenic-antimony smelting smoke, has a simple process flow and low treatment cost, and relates to an arsenic-antimony-based alloy. Background Art

[0002] Non-ferrous metal ores (such as copper, lead, and zinc) often contain significant amounts of valuable elements like arsenic and antimony. To ensure the quality of the primary metal products, these associated elements must be removed during the smelting process. This results in the accumulation of arsenic in smelting slag or flue dust, forming hazardous waste. This accumulation also occurs along with the accumulation of other valuable elements. Limited by current arsenic-containing flue dust treatment technologies and environmental regulations, the accumulation of arsenic-containing dust not only worsens working conditions and severely pollutes the environment, placing significant environmental pressure on companies. Furthermore, the large amounts of valuable metals such as antimony, lead, and zinc contained in the dust remain unutilized. Therefore, comprehensive treatment and utilization of high-arsenic flue dust is crucial to addressing arsenic hazards and has become a key concern for non-ferrous metal smelters.

[0003] For example, during the lead smelting process, the electrolysis of precious lead to produce metallic lead generates a large amount of lead anode slime, which contains a variety of valuable elements such as arsenic, antimony, copper, gold, and silver. Currently, lead anode slime is generally treated by pyrometallurgy. However, during this treatment process, large amounts of volatile elements such as arsenic and antimony enter the flue and are collected, generating a large amount of arsenic-antimony smelting dust. Therefore, how to comprehensively manage and utilize the arsenic-antimony smelting dust generated by lead anode slime is a major challenge facing lead smelters.

[0004] In the prior art, there are two main methods for separating arsenic and antimony from arsenic-antimony dust:

[0005] First, pyro-roasting. The technical concept is to volatilize arsenic in the dust as arsenic oxide, while retaining antimony in the material as a high-potency or less volatile sulfide. However, this method struggles to achieve a deep separation of arsenic and antimony, resulting in a high antimony content in the volatiles and a significant waste of resources.

[0006] Second, wet leaching separation. This technique utilizes differences in the oxidizability and water solubility of As and Sb compounds to adjust the physicochemical conditions of the reaction system, such as pH and oxygen potential, to separate arsenic from antimony. However, this method not only makes it difficult to recycle arsenic, but also requires high reagent consumption and complex wastewater treatment processes, resulting in high separation costs.

[0007] To this end, the prior art also involves mixing arsenic-antimony dust with a reducing agent and a metal oxide, then utilizing the different reducibility and volatility of arsenic and antimony oxides and the strong binding ability of metallic antimony with low-melting-point metals such as tin, bismuth, and cadmium to induce a reduction-alloying reaction between the antimony phase and the metal oxide through reduction roasting, resulting in an antimony alloy product remaining in the roasted substrate, while the arsenic trioxide phase volatilizes into the gas phase and is recovered through dust collection, thereby achieving efficient removal of antimony from arsenic-antimony dust and preparation of high-purity arsenic trioxide. Although this method requires the addition of metal oxides such as tin oxide, bismuth oxide, and cadmium oxide to bind the low-melting-point metals such as tin, bismuth, and cadmium to the metallic antimony to prevent them from volatilizing into the dust with the arsenic trioxide, it achieves efficient removal of antimony from high-arsenic-antimony dust and preparation of high-purity arsenic trioxide. However, the need to add a large amount of metal oxides results in high processing costs, increases the difficulty of subsequent processing of the non-volatile mixture, and increases the cost of dust capture and the inevitable partial emission, which increases the environmental pressure on smelting enterprises. Summary of the Invention

[0008] In response to the deficiencies in the prior art, the present invention provides a method for preparing an arsenic-antimony-based alloy from arsenic-antimony smelting smoke, which is easy to achieve comprehensive recovery and reduction of valuable metals in arsenic-antimony smelting smoke, and has a simple process flow and low treatment cost. Also provided is an arsenic-antimony-based alloy obtained by the aforementioned method for preparing an arsenic-antimony-based alloy from arsenic-antimony smelting smoke.

[0009] The method for preparing arsenic-antimony-based alloy from arsenic-antimony smelting dust of the present invention is implemented as follows: it includes the steps of raw material preparation, high-temperature reduction, and material discharge, and the specific contents are as follows:

[0010] A. Raw material preparation: Mix the arsenic-antimony smelting dust and carbonaceous reducing agent in proportion to obtain a mixed material for later use;

[0011] B. High-temperature reduction: The mixture is placed in a sealed high-temperature reduction furnace, heated to 800-950°C and kept warm to allow a reduction reaction to occur. The holding time is 1.0-2.5 hours. During the high-temperature reduction roasting process, the metal oxides in the arsenic-antimony smelting fume react with the carbon in the reducing agent to produce metal, CO and CO2. The CO2 reacts again with the carbon to produce CO, and the CO reacts with the metal oxides to produce metal and CO2. Finally, the metal melts produced by the reaction are mixed to form an arsenic-antimony-based alloy mainly composed of arsenic and antimony, which sinks to the bottom of the furnace. The main reactions are as follows (Me represents arsenic and antimony):

[0012] MeO+C=Me+CO2MeO+C=2Me+CO2

[0013] CO2+C=2COMeO+CO=Me+CO2

[0014] C. Discharging: After the reduction reaction is completed, the melt in the high-temperature reduction furnace is skimmed to leave the arsenic-antimony based alloy liquid at the bottom of the high-temperature reduction furnace. The arsenic-antimony based alloy liquid is then cast to obtain the arsenic-antimony based alloy.

[0015] Furthermore, the arsenic-antimony smelting dust in the raw material preparation step is the dust collected by the flue dust collection system after the lead electrolysis anode mud is reduced and roasted and volatilized. The dust includes the following components in percentage by mass: 45-60% As2O3, 35-50% Sb2O3, 1-2% ZnO, 0.5-2% PbO, 0-1.5% Bi2O3 and unavoidable impurities, and the total amount is 100%.

[0016] Furthermore, the molar ratio of the effective carbon element in the carbonaceous reducing agent to the metal element in the arsenic-antimony smelting fume is 1.5 to 2.0.

[0017] Furthermore, the carbonaceous reducing agent includes one or any combination of coke powder, anthracite, pulverized coal, and waste carbonaceous electrode rods / powder.

[0018] Furthermore, the particle size of the carbonaceous reducing agent is 50 to 300 meshes.

[0019] Furthermore, the high-temperature reduction furnace in the high-temperature reduction step is a resistance furnace or a medium-frequency induction furnace with a sealed cover, and the crucible in the high-temperature reduction furnace is a graphite crucible or a silicon carbide crucible.

[0020] Furthermore, the casting temperature of the arsenic-antimony based alloy liquid in the discharging step is 650-750°C.

[0021] Furthermore, in the discharging step, after the reduction reaction is completed, the melt in the high-temperature reduction furnace is allowed to stand for 0.5 to 2 hours before slagging.

[0022] The arsenic-antimony based alloy of the present invention is prepared by the above-mentioned method of preparing the arsenic-antimony based alloy from arsenic-antimony smelting dust.

[0023] Furthermore, the arsenic-antimony-based alloy includes the following components in percentage by mass: 45-60% As, 35-50% Sb, 1-2% ZnO, 0.5-2% PbO, 0-1.5% Bi2O3 and unavoidable impurities, and the total amount is 100%.

[0024] The beneficial effects of the present invention are:

[0025] 1. The present invention disposes of arsenic-antimony smelting dust as a resource, making full use of the strong oxidizing properties of arsenic and antimony oxides, which easily undergo reduction reactions with carbon to generate metals, CO and CO2 under high temperature conditions. The metals generated by the reaction dissolve into each other to form an arsenic-antimony-based alloy, which is convenient for subsequent technical treatment to separate arsenic, antimony, lead, zinc, bismuth and other metals in the arsenic-antimony-based alloy, thereby realizing the comprehensive recovery and reduction of valuable metals in arsenic-antimony smelting dust. In addition, compared with other treatment processes, the process is simple, the treatment cost is low, and there is no smoke emission.

[0026] 2. The present invention adopts a sealed high-temperature reduction furnace to carry out a high-temperature reduction reaction on arsenic-antimony smelting dust, which effectively prevents the metallic arsenic in the arsenic-antimony smelting dust from sublimating and entering the flue gas and being carried away, thereby reducing the environmental pressure of the smelting enterprise. Although some metallic arsenic will adhere to the furnace wall of the high-temperature reduction furnace and leak with the flue gas during slag removal and casting, the direct recovery rate of arsenic in arsenic-antimony-based alloys is still more than 40% compared with the existing non-sealed high-temperature reduction reaction. Moreover, the sealed high-temperature reduction reaction can significantly increase the direct recovery rate of metals such as antimony, lead, zinc, and bismuth to more than 85%, which significantly improves the treatment effect and reduction effect of arsenic-antimony smelting dust.

[0027] 3. The present invention adopts a closed high-temperature reduction furnace and forms an arsenic-antimony-based alloy with arsenic-antimony smelting dust by adding a carbonaceous reducing agent. This not only avoids the heat dissipation with the flue gas during the high-temperature reduction reaction, thereby reducing the heating cost, but also reduces the cost of the reduction reaction by only adding a low-cost carbonaceous reducing agent. In addition, the need for adding additives such as metal oxides can reduce the difficulty of subsequent processing of the non-volatile mixture.

[0028] In summary, the present invention has the characteristics of easy realization of comprehensive recovery and reduction of valuable metals in arsenic and antimony smelting dust, simple process flow and low processing cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] FIG1 is a process flow chart of the method for preparing arsenic-antimony based alloys according to the present invention. DETAILED DESCRIPTION

[0030] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0031] As shown in FIG1 , the method for preparing arsenic-antimony-based alloy from arsenic-antimony smelting dust of the present invention includes the steps of raw material preparation, high-temperature reduction, and material discharge, and the specific contents are as follows:

[0032] A. Raw material preparation: Mix the arsenic-antimony smelting dust and carbonaceous reducing agent in proportion to obtain a mixed material for later use;

[0033] B. High-temperature reduction: Place the mixture into a sealed high-temperature reduction furnace, heat the mixture to 800-950°C and keep it warm to allow the reduction reaction to occur. The holding time is 1.0-2.5 hours;

[0034] C. Discharging: After the reduction reaction is completed, the melt in the high-temperature reduction furnace is skimmed to leave the arsenic-antimony based alloy liquid at the bottom of the high-temperature reduction furnace. The arsenic-antimony based alloy liquid is then cast to obtain the arsenic-antimony based alloy.

[0035] The arsenic-antimony smelting dust in the raw material preparation step is the dust collected by the flue dust collection system after the lead electrolysis anode mud is reduced and roasted and volatilized. The dust includes the following components in percentage by mass: 45-60% As2O3, 35-50% Sb2O3, 1-2% ZnO, 0.5-2% PbO, 0-1.5% Bi2O3 and unavoidable impurities, and the total amount is 100%.

[0036] The molar ratio of the effective carbon element in the carbonaceous reducing agent to the metal element in the arsenic-antimony smelting fume is 1.5-2.0.

[0037] The carbonaceous reducing agent includes one or any combination of coke powder, anthracite, pulverized coal, and waste carbonaceous electrode rods / powder.

[0038] The particle size of the carbonaceous reducing agent is 50 to 300 meshes.

[0039] The high-temperature reduction furnace in the high-temperature reduction step is a resistance furnace or a medium-frequency induction furnace with a sealing cover, and the crucible in the high-temperature reduction furnace is a graphite crucible or a silicon carbide crucible.

[0040] The casting temperature of the arsenic-antimony based alloy liquid in the discharging step is 650-750°C.

[0041] In the discharging step, after the reduction reaction is completed, the melt in the high-temperature reduction furnace is allowed to stand for 0.5 to 2 hours before slagging.

[0042] The arsenic-antimony based alloy of the present invention is prepared by the above-mentioned method of preparing the arsenic-antimony based alloy from arsenic-antimony smelting dust.

[0043] The arsenic-antimony based alloy includes the following components in percentage by mass: 45-60% As, 35-50% Sb, 1-2% ZnO, 0.5-2% PbO, 0-1.5% Bi2O3 and unavoidable impurities, and the total amount is 100%.

[0044] Example 1

[0045] S100: Arsenic-antimony smelting dust containing 48.4% As2O3, 46.3% Sb2O3, 1.2% ZnO, 0.5% PbO, 0.3% Bi2O3, and the balance being other impurities, is thoroughly mixed with coke powder having a particle size of 50 mesh, wherein the molar ratio of the effective carbon element of the coke powder to the metal element of the arsenic-antimony smelting dust is 1.5, to obtain a mixed material for use;

[0046] S200: The mixture is placed in a medium frequency induction furnace, the furnace lid is closed, and the mixture is heated to 850° C. and kept at this temperature for 1.6 hours to cause a high temperature reduction reaction;

[0047] S300: After the high-temperature reduction reaction is completed, heating is stopped, and the melt in the high-temperature reduction furnace is allowed to stand for 1.5 hours before slagging, so that the arsenic-antimony-based alloy liquid remains at the bottom of the furnace body of the high-temperature reduction furnace. After the arsenic-antimony-based alloy liquid is cooled to 670° C., casting is performed to obtain an arsenic-antimony-based alloy.

[0048] Analysis of the chemical composition of the arsenic-antimony based alloy prepared by the above process showed that the direct recovery rate of antimony was 94.5%, the direct recovery rate of lead was 96.5%, the direct recovery rate of zinc was 92.5%, the direct recovery rate of bismuth was 91.7%, and the direct recovery rate of arsenic was 55.8%.

[0049] Example 2

[0050] S100: Arsenic-antimony smelting dust containing 52.4% As2O3, 38.3% Sb2O3, 1.8% ZnO, 1.2% PbO, 0.4% Bi2O3, and the balance being other impurities, is thoroughly mixed with coke powder having a particle size of 150 mesh, wherein the molar ratio of the effective carbon element of the coke powder to the metal element of the arsenic-antimony smelting dust is 1.8, to obtain a mixed material for use;

[0051] S200: The mixture is placed in a medium frequency induction furnace, the furnace lid is closed, and the mixture is heated to 900° C. and kept at this temperature for 1.0 h to cause a high temperature reduction reaction;

[0052] S300: After the high-temperature reduction reaction is completed, heating is stopped, and the melt in the high-temperature reduction furnace is allowed to stand for 1 hour before slagging, so that the arsenic-antimony-based alloy liquid remains at the bottom of the furnace body of the high-temperature reduction furnace. After the arsenic-antimony-based alloy liquid is cooled to 650° C., casting is performed to obtain an arsenic-antimony-based alloy.

[0053] Analysis of the chemical composition of the arsenic-antimony based alloy prepared by the above process showed that the direct recovery rate of antimony was 95.5%, the direct recovery rate of lead was 97.5%, the direct recovery rate of zinc was 91.5%, the direct recovery rate of bismuth was 93.5%, and the direct recovery rate of arsenic was 48.7%.

[0054] Example 3

[0055] S100: Arsenic-antimony smelting dust containing 57.8% As2O3, 36.3% Sb2O3, 1.5% ZnO, 1.1% PbO, 0.8% Bi2O3, and the balance being other impurities, is thoroughly mixed with coke powder having a particle size of 300 mesh, wherein the molar ratio of the effective carbon element of the coke powder to the metal element of the arsenic-antimony smelting dust is 1.8, to obtain a mixed material for use;

[0056] S200: The mixture is placed in a medium frequency induction furnace, the furnace lid is closed, and the mixture is heated to 950° C. and kept at this temperature for 2.5 hours to cause a high temperature reduction reaction;

[0057] S300: After the high-temperature reduction reaction is completed, heating is stopped, and the melt in the high-temperature reduction furnace is allowed to stand for 0.5 hours before slagging, so that the arsenic-antimony-based alloy liquid remains at the bottom of the furnace body of the high-temperature reduction furnace. After the arsenic-antimony-based alloy liquid is cooled to 710° C., casting is performed to obtain an arsenic-antimony-based alloy.

[0058] Analysis of the chemical composition of the arsenic-antimony based alloy prepared by the above process showed that the direct recovery rate of antimony was 95.5%, the direct recovery rate of lead was 93.2%, the direct recovery rate of zinc was 91.1%, the direct recovery rate of bismuth was 92.7%, and the direct recovery rate of arsenic was 43.5%.

[0059] Example 4

[0060] S100: arsenic-antimony smelting dust containing 47.8% As2O3, 46.8% Sb2O3, 1.4% ZnO, 1.5% PbO, 0.7% Bi2O3, and the balance being other impurities, is thoroughly mixed with spent carbonaceous electrode powder having a particle size of 200 mesh, wherein the molar ratio of the effective carbon element of the spent carbonaceous electrode powder to the metal element of the arsenic-antimony smelting dust is 2.0, to obtain a mixed material for use;

[0061] S200: The mixture is placed in a medium frequency induction furnace, the furnace lid is closed, and the mixture is heated to 800° C. and kept at this temperature for 2.0 h to cause a high temperature reduction reaction;

[0062] S300: After the high-temperature reduction reaction is completed, heating is stopped, and the melt in the high-temperature reduction furnace is allowed to stand for 2.0 hours before slagging, so that the arsenic-antimony-based alloy liquid remains at the bottom of the furnace body of the high-temperature reduction furnace. After the arsenic-antimony-based alloy liquid is cooled to 750° C., casting is performed to obtain an arsenic-antimony-based alloy.

[0063] Analysis of the chemical composition of the arsenic-antimony based alloy prepared by the above process showed that the direct recovery rate of antimony was 92.4%, the direct recovery rate of lead was 88.2%, the direct recovery rate of zinc was 85.1%, the direct recovery rate of bismuth was 87.7%, and the direct recovery rate of arsenic was 68.6%.

[0064] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by a person skilled in the art within the technical scope disclosed in the present invention should be included in the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be based on the scope of protection of the claims.

Claims

1. A method for preparing arsenic-antimony based alloy from arsenic-antimony smelting dust, characterized in that It includes raw material preparation, high temperature reduction and discharging steps, and the specific contents are as follows: A. Raw material preparation: fully and evenly mix the arsenic antimony smelting smoke and carbonaceous reducing agent according to the proportion to obtain a mixed material for use; B. High temperature reduction: put the mixture into a sealed high temperature reduction furnace, heat the mixture to 800-950℃ and keep it warm to make the reduction reaction occur. The insulation time is 1.0-2.5h; C. Discharging: After the reduction reaction is completed, the melt in the high-temperature reduction furnace is deslagging, so that the arsenic-antimony-based alloy liquid remains at the bottom of the furnace body of the high-temperature reduction furnace, and then the arsenic-antimony-based alloy liquid is cast to obtain the arsenic-antimony-based alloy.

2. The method for preparing arsenic-antimony based alloy from arsenic-antimony smelting dust according to claim 1, characterized in that The arsenic-antimony smelting dust in the raw material preparation step is the dust collected by the flue dust collection system after the lead electrolysis anode mud is reduced and roasted and volatilized. The dust includes the following components in mass percentage: 45-60% As2O3, 35-50% Sb2O3, 1-2% ZnO, 0.5-2% PbO, 0-1.5% Bi2O3 and unavoidable impurities, and the total amount is 100%.

3. The method for preparing arsenic-antimony based alloy from arsenic-antimony smelting dust according to claim 2, characterized in that The molar ratio of the effective carbon element in the carbonaceous reducing agent to the metal element in the arsenic-antimony smelting fume is 1.5-2.

0.

4. The method for preparing arsenic-antimony based alloy from arsenic-antimony smelting dust according to claim 3, characterized in that The carbonaceous reducing agent includes one or any combination of coke powder, anthracite, pulverized coal, and waste carbonaceous electrode rods / powder.

5. The method for preparing arsenic-antimony based alloy from arsenic-antimony smelting dust according to claim 4, characterized in that The particle size of the carbonaceous reducing agent is 50 to 300 meshes.

6. The method for preparing arsenic-antimony based alloy from arsenic-antimony smelting dust according to any one of claims 1 to 5, characterized in that The high-temperature reduction furnace in the high-temperature reduction step is a resistance furnace or a medium-frequency induction furnace with a sealing cover, and the crucible in the high-temperature reduction furnace is a graphite crucible or a silicon carbide crucible.

7. The method for preparing arsenic-antimony based alloy from arsenic-antimony smelting dust according to any one of claims 1 to 5, characterized in that The casting temperature of the arsenic-antimony based alloy liquid in the discharging step is 650-750°C.

8. The method for preparing arsenic-antimony based alloy from arsenic-antimony smelting dust according to claim 7, characterized in that In the discharging step, after the reduction reaction is completed, the melt in the high-temperature reduction furnace is left to stand for 0.5 to 2 hours before slagging.

9. An arsenic-antimony-based alloy obtained by the method for preparing arsenic-antimony-based alloy from arsenic-antimony smelting dust according to claims 1 to 8.

10. The arsenic-antimony based alloy according to claim 9, characterized in that The invention comprises the following components in percentage by mass: 45-60% As, 35-50% Sb, 1-2% ZnO, 0.5-2% PbO, 0-1.5% Bi2O3 and inevitable impurities, and the total amount is 100%.

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