A method for preparing arsenic-antimony-based alloy from arsenic-antimony smelting dust and arsenic-antimony-based alloy

Abstract

The application discloses a method for preparing arsenic-antimony-based alloy from arsenic-antimony smelting fumes and the arsenic-antimony-based alloy. The method comprises the following steps: uniformly mixing arsenic-antimony smelting fumes and carbonaceous reducing agent in proportion to obtain a mixture; loading the mixture into a high-temperature reduction furnace, heating to 800-950 DEG C and keeping the temperature to make reduction reaction occur, the keeping time being 1.0-2.5 h; and after the reduction reaction is completed, removing slag from the melt, keeping the arsenic-antimony-based alloy liquid at the bottom of the furnace body and casting to obtain the arsenic-antimony-based alloy. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method. The arsenic-antimony-based alloy is prepared by the method

Description

Technical Field

[0001] This invention relates to the field of non-ferrous metallurgical technology, specifically to a method for preparing arsenic-antimony-based alloys from arsenic-antimony smelting dust that facilitates comprehensive recovery and reduction of valuable metals from arsenic-antimony smelting dust, and has a simple process flow and low processing cost. Background Technology

[0002] Non-ferrous metal ores (such as copper, lead, and zinc) often contain large amounts of valuable elements such as arsenic and antimony. During the smelting process, to ensure the quality of the main metal product, these associated elements need to be removed. This results in the accumulation of associated elements like arsenic in smelting slag or flue dust, forming hazardous waste. Simultaneously, other valuable elements also accumulate in the smelting slag or flue dust along with arsenic. Due to current limitations in arsenic-containing flue dust treatment technology and environmental protection requirements, arsenic-containing flue dust accumulates and piles up, not only worsening working conditions but also severely polluting the environment and placing enormous environmental pressure on enterprises. Furthermore, the flue dust contains large amounts of valuable metal elements such as antimony, lead, and zinc, which cannot be effectively utilized. Therefore, comprehensive treatment and utilization of high-arsenic flue dust is crucial to solving the arsenic hazard problem and has become a key concern for non-ferrous metal smelting enterprises.

[0003] In lead smelting, the electrolytic production of metallic lead from precious lead generates a large amount of lead anode mud, which contains various valuable elements such as arsenic, antimony, copper, gold, and silver. Currently, lead anode mud is generally treated using pyrometallurgical methods. However, during this process, volatile elements such as arsenic and antimony enter the flue and are collected in large quantities, resulting in a large amount of arsenic and antimony smelting dust. Therefore, how to comprehensively manage and utilize the arsenic and antimony smelting dust generated from lead anode mud is a major challenge currently facing lead smelting enterprises.

[0004] In existing technologies, there are two main methods for separating arsenic and antimony from arsenic-antimony flue dust:

[0005] First, the pyrometallurgical roasting method. The technical concept is to volatilize arsenic in the flue gas as arsenic oxide, while retaining antimony in the material as a less volatile form, such as a high-valence or sulfide. However, this method is difficult to achieve deep separation of arsenic and antimony, resulting in a high antimony content in the volatiles and causing a significant waste of resources.

[0006] Second, wet leaching separation. The technical concept is to use the differences in the oxidizing properties and water solubility of As and Sb compounds to adjust the physicochemical conditions such as pH and oxygen potential of the reaction system to achieve the separation of arsenic and antimony. However, this method not only makes it difficult to achieve the resource recovery of arsenic, but also consumes a lot of reagents and has a complex wastewater treatment process, resulting in high separation costs.

[0007] To address this, existing technologies involve mixing arsenic-antimony dust with reducing agents and metal oxides. Utilizing the differences in reducing and volatility of arsenic and antimony oxides, and the strong binding ability of antimony with low-melting-point metals like tin, bismuth, and cadmium, a reduction-alloying reaction is achieved through reduction roasting. This generates antimony alloy products that remain in the roasting substrate, while the arsenic trioxide phase volatilizes into the gas phase and is recovered through dust collection. This method achieves efficient removal of antimony from arsenic-antimony dust and the preparation of high-purity arsenic trioxide. However, this method requires the addition of metal oxides such as tin oxide, bismuth oxide, and cadmium oxide to bind the low-melting-point tin, bismuth, and cadmium with the antimony, preventing them from volatilizing into the dust with the arsenic trioxide. This results in high processing costs due to the large amount of metal oxides required, increased difficulty in the subsequent treatment of non-volatile mixtures, and high dust collection costs, which inevitably lead to some emissions, increasing the environmental pressure on smelting enterprises. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a method for preparing arsenic-antimony-based alloys from arsenic-antimony smelting dust that facilitates comprehensive recovery and reduced disposal of valuable metals from arsenic-antimony smelting dust, and features a simple process and low processing costs. It also provides an arsenic-antimony-based alloy obtained by the aforementioned method for preparing arsenic-antimony-based alloys from arsenic-antimony smelting dust.

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

[0010] A. Raw material preparation: Mix the arsenic and antimony smelting flue dust and carbonaceous reducing agent thoroughly and evenly according to the proportion to obtain a mixture for later use;

[0011] B. High-Temperature Reduction: The mixture is loaded into a sealed high-temperature reduction furnace, heated to 800–950°C and held at this temperature for 1.0–2.5 hours to induce a reduction reaction. During the high-temperature reduction roasting process, the metal oxides in the arsenic-antimony smelting flue gas react with C in the reducing agent to produce metal, CO, and CO2. CO2 then reacts with C to produce CO, and CO reacts with the metal oxides to produce metal and CO2. Finally, the resulting molten metal mixes to form an arsenic-antimony-based alloy, which sinks to the bottom of the furnace. The main reaction is shown below (Me represents arsenic and antimony):

[0012] ;

[0013] C. Discharge: After the reduction reaction is completed, the slag in the high-temperature reduction furnace is removed so that the arsenic-antimony based alloy liquid remains at the bottom of the furnace body. Then, the arsenic-antimony based alloy liquid is cast to obtain the arsenic-antimony based alloy.

[0014] Furthermore, the arsenic and antimony smelting flue dust in the raw material preparation step is the flue dust collected by the flue dust collection system after the lead electrolysis anode mud is reduced, roasted, and volatilized. The flue dust includes the following components by mass percentage: 45-60% As2O3, 35-50% Sb2O3, 1-2% ZnO, 0.5-2% PbO, 0-1.5% Bi2O3, and unavoidable impurities, with a total amount of 100%.

[0015] Furthermore, the molar ratio of the effective carbon element in the carbonaceous reducing agent to the metal element in the arsenic and antimony smelting flue dust is 1.5 to 2.0.

[0016] Furthermore, the carbonaceous reducing agent includes one or any combination of coke powder, anthracite, pulverized coal, and waste carbonaceous electrode rods / powder.

[0017] Furthermore, the particle size of the carbonaceous reducing agent is 50-300 mesh.

[0018] Furthermore, the high-temperature reduction furnace in the high-temperature reduction step is a resistance furnace with a sealed cover or a medium-frequency induction furnace, and the crucible in the high-temperature reduction furnace is a graphite crucible or a silicon carbide crucible.

[0019] Furthermore, the casting temperature of the arsenic-antimony based alloy liquid in the discharge step is 650–750°C.

[0020] Furthermore, in the discharge 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 slag removal.

[0021] The arsenic-antimony based alloy of the present invention is prepared by the aforementioned method for preparing arsenic-antimony based alloy from arsenic-antimony smelting flue dust.

[0022] Furthermore, the arsenic-antimony-based alloy comprises the following components by mass percentage: 45-60% As, 35-50% Sb, 1-2% ZnO, 0.5-2% PbO, 0-1.5% Bi2O3, and unavoidable impurities, with a total amount of 100%.

[0023] The beneficial effects of this invention are as follows:

[0024] 1. This invention provides a resource-based treatment for arsenic and antimony smelting dust. It fully utilizes the strong oxidizing properties of arsenic and antimony oxides, which readily react with carbon at high temperatures to generate metals, CO, and CO2. Furthermore, the metals generated in the reaction are intersoluble to form arsenic-antimony-based alloys. This facilitates the subsequent technical processing to separate metals such as arsenic, antimony, lead, zinc, and bismuth from the arsenic-antimony-based alloys, achieving comprehensive recovery and reduction of valuable metals from arsenic and antimony smelting dust. Moreover, compared to other treatment processes, this invention is simpler, has lower processing costs, and produces no flue gas emissions.

[0025] 2. This invention employs a sealed high-temperature reduction furnace to perform a high-temperature reduction reaction on arsenic and antimony smelting dust. This effectively prevents the sublimation of metallic arsenic in the arsenic and antimony smelting dust from entering the flue gas and being carried away, thereby reducing the environmental pressure on smelting enterprises. Although some metallic arsenic may adhere to the furnace wall of the high-temperature reduction furnace and leak with the flue gas during slag removal and casting, the direct arsenic recovery rate in arsenic-antimony based alloys using existing non-sealed high-temperature reduction reactions still reaches over 40%. Moreover, the sealed high-temperature reduction reaction can significantly increase the direct recovery rate of metals such as antimony, lead, zinc, and bismuth to over 85%, significantly improving the treatment effect and volume reduction effect of arsenic and antimony smelting dust.

[0026] 3. This invention uses a closed high-temperature reduction furnace and adds a carbonaceous reducing agent to form an arsenic-antimony-based alloy with arsenic-antimony smelting flue gas. This not only avoids the heat from dissipating with the flue gas during the high-temperature reduction reaction, thus reducing heating costs, but also reduces the cost of the reduction reaction by adding only a low-cost carbonaceous reducing agent. Furthermore, the absence of additives such as metal oxides reduces the difficulty of post-processing of non-volatile mixtures.

[0027] In summary, this invention has the advantages of easily realizing the comprehensive recovery and reduction of valuable metals in arsenic and antimony smelting dust, and has a simple process flow and low processing cost. Attached Figure Description

[0028] Figure 1 This is a process flow diagram of the method for preparing arsenic-antimony based alloys according to the present invention. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the 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 merely illustrative and not intended to limit the invention.

[0030] like Figure 1 As shown, the method for preparing arsenic-antimony-based alloys from arsenic-antimony smelting dust of the present invention includes raw material preparation, high-temperature reduction, and discharge steps, the specific contents of which are as follows:

[0031] A. Raw material preparation: Mix the arsenic and antimony smelting flue dust and carbonaceous reducing agent thoroughly and evenly according to the proportion to obtain a mixture for later use;

[0032] B. High-temperature reduction: The mixture is loaded into a sealed high-temperature reduction furnace, heated to 800-950℃ and held at that temperature to allow the reduction reaction to occur. The holding time is 1.0-2.5 hours.

[0033] C. Discharge: After the reduction reaction is completed, the slag in the high-temperature reduction furnace is removed so that the arsenic-antimony based alloy liquid remains at the bottom of the furnace body. Then, the arsenic-antimony based alloy liquid is cast to obtain the arsenic-antimony based alloy.

[0034] The arsenic and antimony smelting flue dust in the raw material preparation step is the flue dust collected by the flue dust collection system after the lead electrolysis anode mud is reduced, roasted, and volatilized. The flue dust includes the following components by mass percentage: 45-60% As2O3, 35-50% Sb2O3, 1-2% ZnO, 0.5-2% PbO, 0-1.5% Bi2O3, and unavoidable impurities, with a total amount of 100%.

[0035] The molar ratio of the effective carbon element in the carbonaceous reducing agent to the metal element in the arsenic and antimony smelting flue dust is 1.5 to 2.0.

[0036] The carbonaceous reducing agent includes one or any combination of coke powder, anthracite, pulverized coal, and waste carbonaceous electrode rods / powder.

[0037] The particle size of the carbonaceous reducing agent is 50-300 mesh.

[0038] 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.

[0039] The casting temperature of the arsenic-antimony based alloy liquid in the discharge step is 650-750℃.

[0040] After the reduction reaction is completed in the discharge step, the melt in the high-temperature reduction furnace is allowed to stand for 0.5 to 2 hours before slag removal.

[0041] The arsenic-antimony based alloy of the present invention is prepared by the aforementioned method for preparing arsenic-antimony based alloy from arsenic-antimony smelting flue dust.

[0042] The arsenic-antimony-based alloy comprises the following components by mass percentage: 45-60% As, 35-50% Sb, 1-2% ZnO, 0.5-2% PbO, 0-1.5% Bi2O3, and unavoidable impurities, totaling 100%.

[0043] Example 1

[0044] S100: Arsenic and 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 with a particle size of 50 mesh, wherein the molar ratio of effective carbon element in coke powder to metal element in arsenic and antimony smelting dust is 1.5, and the mixture is prepared for use.

[0045] S200: The aforementioned mixture is loaded into a medium-frequency induction furnace, the furnace lid is closed, and the mixture is heated to 850°C and held for 1.6 hours to allow a high-temperature reduction reaction to occur.

[0046] S300: After the high-temperature reduction reaction is completed, stop heating and let the melt in the high-temperature reduction furnace stand for 1.5 hours before removing the slag, so that the arsenic-antimony based alloy liquid remains at the bottom of the furnace body. After the arsenic-antimony based alloy liquid cools to 670°C, it is cast to obtain the arsenic-antimony based alloy.

[0047] The chemical composition of the arsenic-antimony based alloy prepared by the above process was analyzed: 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%.

[0048] Example 2

[0049] S100: Arsenic and 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 with a particle size of 150 mesh, wherein the molar ratio of effective carbon element in coke powder to metal element in arsenic and antimony smelting dust is 1.8, and the mixture is prepared for use.

[0050] S200: The aforementioned mixture is loaded into a medium-frequency induction furnace, the furnace lid is closed, and the mixture is heated to 900°C and kept at that temperature for 1.0 h to allow a high-temperature reduction reaction to occur.

[0051] S300: After the high-temperature reduction reaction is completed, stop heating and let the melt in the high-temperature reduction furnace stand for 1 hour before removing the slag, so that the arsenic-antimony based alloy liquid remains at the bottom of the furnace body. After the arsenic-antimony based alloy liquid cools to 650°C, it is cast to obtain the arsenic-antimony based alloy.

[0052] The chemical composition of the arsenic-antimony based alloy prepared by the above process was analyzed: 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%.

[0053] Example 3

[0054] S100: Arsenic and 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 with a particle size of 300 mesh, wherein the molar ratio of effective carbon element in coke powder to metal element in arsenic and antimony smelting dust is 1.8, and the mixture is prepared for use.

[0055] S200: The aforementioned mixture is loaded into a medium-frequency induction furnace, the furnace lid is closed, and the mixture is heated to 950°C and kept at that temperature for 2.5 hours to allow a high-temperature reduction reaction to occur.

[0056] S300: After the high-temperature reduction reaction is completed, stop heating and let the melt in the high-temperature reduction furnace stand for 0.5 hours before removing the slag, so that the arsenic-antimony based alloy liquid remains at the bottom of the furnace body. After the arsenic-antimony based alloy liquid cools to 710℃, it is cast to obtain the arsenic-antimony based alloy.

[0057] The chemical composition of the arsenic-antimony based alloy prepared by the above process was analyzed: 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%.

[0058] Example 4

[0059] S100: Arsenic and 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 waste carbonaceous electrode powder with a particle size of 200 mesh, wherein the molar ratio of effective carbon element in the waste carbonaceous electrode powder to the metal element in the arsenic and antimony smelting dust is 2.0, and the mixture is prepared for use.

[0060] S200: The aforementioned mixture is loaded into a medium-frequency induction furnace, the furnace lid is closed, and the mixture is heated to 800°C and kept at that temperature for 2.0 hours to induce a high-temperature reduction reaction.

[0061] S300: After the high-temperature reduction reaction is completed, stop heating and let the melt in the high-temperature reduction furnace stand for 2.0 hours before removing the slag, so that the arsenic-antimony based alloy liquid remains at the bottom of the furnace body. After the arsenic-antimony based alloy liquid cools to 750°C, it is cast to obtain the arsenic-antimony based alloy.

[0062] The chemical composition of the arsenic-antimony based alloy prepared by the above process was analyzed: 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%.

[0063] 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 variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing arsenic-antimony-based alloys from arsenic-antimony smelting dust, characterized in that... This includes raw material preparation, high-temperature reduction, and discharge steps, specifically: A. Raw material preparation: The arsenic and antimony smelting flue dust and carbonaceous reducing agent are thoroughly mixed in proportion to obtain a mixture for later use; the arsenic and antimony smelting flue dust is the flue dust collected by the flue dust collection system after the lead electrolysis anode mud is reduced, roasted and volatilized. The flue dust includes the following components by 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%; The molar ratio of effective carbon element in the carbonaceous reducing agent to metal element in arsenic and antimony smelting flue dust is 1.5 to 2.

0. B. High-temperature reduction: The mixture is loaded into a sealed high-temperature reduction furnace, which is a resistance furnace or a medium-frequency induction furnace with a sealed cover. The crucible in the high-temperature reduction furnace is a graphite crucible or a silicon carbide crucible. The mixture is heated to 800-950°C and held at that temperature to allow the reduction reaction to occur. The holding time is 1.0-2.5 hours. C. Discharge: 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 slag removal, so that the arsenic-antimony based alloy liquid remains at the bottom of the furnace body. Then, the arsenic-antimony based alloy liquid is cast at a casting temperature of 650 to 750℃ to obtain the arsenic-antimony based alloy.

2. The method according to claim 1, characterized in that: The carbonaceous reducing agent includes one or any combination of coke powder, anthracite, pulverized coal, and waste carbonaceous electrode rods / powder.

3. The method according to claim 2, characterized in that: The particle size of the carbonaceous reducing agent is 50-300 mesh.

4. An arsenic-antimony-based alloy obtained by a method for preparing arsenic-antimony-based alloys from arsenic-antimony smelting flue dust according to any one of claims 1 to 3.

5. The arsenic-antimony based alloy according to claim 4, characterized in that... It includes the following components by mass percentage: 45-60% As, 35-50% Sb, 1-2% ZnO, 0.5-2% PbO, 0-1.5% Bi2O3, and unavoidable impurities, with a total amount of 100%.

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