A method for extracting copper matte from anode slime of lead-antimony ore

Abstract

This invention relates to a method for refining copper matte from anode slag using lead-antimony ore, comprising the following steps: S1, batching: lead-antimony ore, anode slag, soda ash, and reducing coal are batched according to the raw material analysis report and mixed evenly to obtain a mixture; S2, feeding: the mixture is fed into a reverberatory furnace in batches using a specialized feeding device; S3, heating and smelting / reduction; S4, slag removal; S5, adding iron filings and adding copper matte; S6, adding crude lead. This invention features a short process flow, low labor intensity, and high processing capacity. Compared to traditional recovery methods, it increases the overall metal recovery rate by 5%, reduces costs by 25%–35%, and improves furnace operating conditions, essentially eliminating frequent furnace cleaning and heavy slag removal operations.

Description

Technical Field

[0001] This invention belongs to the field of technology for recovering valuable metals from non-ferrous metal smelting waste, specifically relating to a method for extracting copper matte from anode slag using lead-antimony ore. Background Technology

[0002] The anode slag produced during the electrolysis process contains a small amount of metallic sulfides and also melts some precious metals such as silver and gold, possessing significant comprehensive recovery value. For anode slag with low sulfur and high copper content, the traditional soda ash-reducing coal-pyrite smelting process involves adding 20%-40% pyrite to produce matte and crude lead. However, due to the high melting point of pyrite, no valuable metals can be recovered, resulting in a lower overall grade entering the furnace. This is detrimental to reverberatory furnace smelting, easily leading to furnace clogging, poor separation of slag and matte, requiring frequent furnace condition adjustments, resulting in low throughput and high production costs. Therefore, developing a new process that can efficiently treat anode slag, achieve comprehensive recovery of its valuable metals, and is economically efficient and environmentally friendly is of great significance to smelting enterprises. Summary of the Invention

[0003] To address the above problems, this invention provides a method for refining matte from anode slag using lead-antimony ore.

[0004] The specific technical solution is: a method for refining copper matte from anode slag using lead-antimony ore, comprising the following steps:

[0005] S1. Batching: According to the raw material analysis report, lead-antimony ore, anode slag, soda ash, and reducing coal are batched and mixed evenly to obtain a mixture.

[0006] S2. Feeding: The mixture is fed into the reverberatory furnace in batches using a specialized feeding device;

[0007] S3. Heating and melting, reduction: The temperature of the reverberatory furnace is maintained at 1150-1250℃, and melting takes 1-2 hours; after the previous batch of mixture is melted, the next batch of mixture is added until the furnace is full; the reduction temperature is 1250-1350℃, and the reduction time is 4-6 hours.

[0008] S4. Slag Removal: After opening the operating door, observe the molten material inside the furnace. When the mixture has completely melted and there is no bubbling in the molten material, and when a steel rod is inserted into the molten material without any hard lumps, when the steel rod is pulled out of the molten material and the slag is of uniform thickness, smooth and without lumps, then the melting point is reached. The slag and matte and crude lead have completely separated and the slag removal operation can be carried out.

[0009] S5. Adding Iron Scrap and Plating Matte: Calculate the total amount of iron scrap to be added based on the lead content in the matte layer, and add it in several batches, sprinkling it evenly onto the surface of the molten metal in the furnace each time. After adding the second batch of iron, use a dried iron rake to stir and agitate the iron scrap and matte layer in the furnace through each operating door to ensure that the iron scrap and matte are in full contact and react. After stirring, maintain the furnace temperature at 1250-1350℃ to allow the iron scrap and matte to react fully. Let it stand for about 20-30 minutes and observe whether the iron scrap on the surface of the molten metal in the furnace has melted completely. If it has melted completely, it is necessary to check whether the amount of iron scrap added is sufficient. Insert a waste oxygen iron pipe into the matte layer and stir for about 1 minute. If the iron pipe is corroded, it means that the amount of iron scrap added is insufficient, and more iron scrap needs to be added until there are iron scrap residues on the surface of the molten metal and the matte layer becomes sticky. At this point, the displacement reaction is over, and the matte removal operation can begin.

[0010] S6. Coarse lead loading operation: After loading the copper matte, add 6-8 tons of mixed material to reduce the temperature of the reverberatory furnace to below 550℃. Utilize the principle of condensation to reduce the copper content of the crude lead to below 1.5%, and then the coarse lead loading operation can be carried out.

[0011] Furthermore, the composition and content of the anode slag mentioned in step S1 are as follows: Pb 60%~65%, Sb 7%~14%, Cu 5%~10%, Ag 1000g / t~1300g / t, Bi 1%~4%, Sn 0.5%~0.9%, S 0.5%~1.5%.

[0012] Furthermore, the composition and content of the lead-antimony ore mentioned in step S1 are as follows: Pb 22%~28%, Sb 18%~24%, Cu 0.5%~2%, Ag 300g / t~700g / t, Bi 0.1%~0.4%, S 4%~24%.

[0013] Furthermore, in step S1, the ratio of lead-antimony ore, anode slag, soda ash, and reducing coal is 45:100:6:8.

[0014] Furthermore, in step S2, the amount of ingredients added in each batch is controlled to be 4 to 6 tons.

[0015] Furthermore, in step S5, the total amount of iron filings added is 1 / 4 of the amount of lead in the copper matte layer, and when the amount of iron filings added is insufficient, the amount of iron filings added each time is 300-400 kg.

[0016] The technical principle of this invention is as follows: At high temperatures, metallic copper in the anode slag and lead sulfide in the lead-antimony concentrate undergo the following substitution reaction: PbS + Cu = CuS + Pb. This causes the copper metal in the anode slag to form matte, thus separating the copper from the lead. To recover the copper, this method involves mixing fluxes such as soda ash, iron filings, lead-antimony ore, and reducing coal with the anode slag in a reverberatory furnace for smelting. After melting, iron filings are added for stirring and slag formation. The matte and lead liquid are separated into layers due to their different densities and released.

[0017] The beneficial effects of this invention are:

[0018] (1) This invention uses lead-antimony ore instead of pyrite to produce matte, and uses petroleum coke + natural gas as mixed fuel. This can effectively ensure that the smelting reduction temperature reaches 1250-1350℃, the degree of reduction is high, the slag rate is reduced to less than 5%, and the furnace processing capacity reaches 1500-1800 tons / month. The smelting produced matte contains 30%-45% Cu and 7%-9% Pb, and the crude lead contains 72%-83% Pb, 0.15%-1.50% Cu, and 17%-25% Sb. Most of the gold and silver are enriched in the crude lead. The matte contains more than 35% copper and less than 9% lead, and the direct recovery rate of lead and antimony is greater than 98% and 99%, respectively.

[0019] (2) The process is short, the labor intensity is low, and the processing capacity is strong. Compared with the traditional recycling method, the comprehensive metal recovery rate is increased by 5%, the cost is reduced by 25% to 35%, and the furnace operating conditions are improved, basically eliminating the frequent furnace cleaning operation and the heavy slag removal operation. Attached Figure Description

[0020] Figure 1 This is a flowchart of a method for refining copper matte from anode slag using lead-antimony ore, according to the present invention. Implementation

[0021] To make the technical problems and solutions solved by the present invention clearer, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely for explaining the present invention and are not intended to limit the present invention. Example

[0022] The composition and content of the anode slag used in this embodiment are as follows: Pb 65%, Sb 12%, Cu 12%, Ag 1300g / t, Bi 1%, Sn 0.5%, S 0.5%~1.5%, wherein Cu, Pb, Fe, and S exist in the forms of Cu2S, PbS, FeS, Cu, Pb, etc.; the composition and content of the lead-antimony ore used are as follows: Pb 22%, Sb 18%, Cu 0.5%, Ag 300g / t, Bi 0.4%, S 14%; other chemical reagents used are not specifically specified and are obtained through conventional commercial channels.

[0023] This embodiment describes a method for extracting copper matte from anode slag using lead-antimony ore, as described in this invention, including the following steps:

[0024] S1. Batching: According to the raw material analysis report, the raw materials are batched in the ratio of lead-antimony ore: anode slag: soda ash: reducing coal = 45:100:6:8 and mixed evenly. Each batch should contain about 200 tons of raw materials to obtain a mixture.

[0025] Among them, (1) the purpose of adding lead-antimony concentrate is to increase the sulfur in the mixture, which is beneficial to the production of matte. At the same time, valuable metals such as lead, antimony, silver, bismuth and gold in lead-antimony concentrate can enter crude lead, reducing production costs; (2) the purpose of adding soda ash is to lower the melting point of slag and matte, so that the smelting process can be carried out at a lower temperature, and at the same time, the lead content of slag and matte can be reduced; (3) the role of adding anthracite is to reduce lead oxide to metallic lead and prevent the surface of the melt from oxidizing during the smelting process.

[0026] S2. Feeding: The mixture is fed into the reverberatory furnace in batches through a special feeding device, with each batch controlled at 4 to 6 tons.

[0027] S3. Heating and smelting, reduction: The temperature of the reverberatory furnace is maintained at 1150-1250℃, and smelting takes 1-2 hours; after the previous batch of mixture is smelted, the next batch of mixture is added until the furnace is full. This time, 72.5 tons of mixture (dry weight) are added; the reduction temperature is 1250-1350℃, and the reduction time is 4-6 hours.

[0028] S4. Slag Removal: After opening the operating door, observe the molten material inside the furnace. When all materials have melted and there is no bubbling in the molten material, and when a steel rod is inserted into the molten material without any hard lumps, and when the steel rod is pulled out of the molten material, the slag is of uniform thickness, smooth, and without any lumps, then the melting point is reached. The slag can be removed once the molten slag has completely separated from the matte and crude lead. The amount of slag removed is 4 tons.

[0029] S5. Adding iron filings and releasing matte: Based on 1 / 4 of the lead content in the matte layer, the total amount of iron filings to be added is 2500 kg. Approximately 600-900 kg of iron filings are evenly sprinkled into the molten surface of the furnace each time. After adding the second batch of iron, use a dried iron rake to stir and agitate the iron filings and matte layer in the furnace through each operating door to ensure that the iron filings and lead in the matte are fully in contact and react. After adding iron and stirring, maintain the furnace temperature at 1250-1350℃ to allow the iron filings and matte to react fully. Let it stand for about 20-30 minutes before releasing the matte. A total of 7 tons of matte is produced, with the following composition: lead 6%, copper 35%, antimony 0.5%, iron 22%, and silver 150 g / t.

[0030] The purpose of adding iron filings is to replace lead sulfide (PbS) with metallic lead, thereby reducing the lead content of copper matte.

[0031] S6. Coarse lead loading operation: After loading copper matte, add 7 tons of mixed material to reduce the temperature of the reverberatory furnace to below 550℃. Utilize the principle of condensation to reduce the copper content of the crude lead to below 1.5%, and then the coarse lead loading operation can be carried out.

[0032] The direct lead recovery rate in the crude lead produced in this embodiment is: [(22.5*65%+50*22%)-7*6%] / (22.5*65%+50*22%)=98.36%.

[0033] The direct recovery rate of antimony in the crude lead produced in this embodiment is: [(22.5*12%+50*18%)-7*0.5%] / (22.5*12%+50*18%)=99.70%.

[0034] The treatment of anode slag with lead-antimony ore has the following advantages over traditional treatment methods: (1) Lead sulfide in lead-antimony ore reacts with metallic copper in slag to produce copper sulfide and metallic lead. The added lead-antimony ore is smelted into crude lead. Even if copper is enriched in matte phase, more crude lead is produced, and a large amount of valuable metals such as lead, antimony, silver, and bismuth are recovered. (2) Due to the increased amount of crude lead, the average gold and silver content of crude lead produced by adding lead-antimony ore and adding sulfur concentrate is very close, which can improve the gold and silver recovery rate. (3) Crude lead has a greater solubility for lead sulfide than for iron sulfide. Adding lead-antimony ore is conducive to the reaction of lead sulfide with metallic copper in crude lead to reduce the copper content of crude lead. (4) Lead sulfide reacts with lead oxide in slag to produce metallic lead, which can reduce the lead content of slag. (5) Lead-antimony ore has less impurities such as SiO2, Fe, and CaO than pyrite, and the slag rate is lower. The amount of slag in the next step of treatment is less. The distribution rate of metals in crude lead and the distribution rate of copper in matte change with the amount of sulfur concentrate added. (6) Lead-antimony ore has a lower melting point than pyrite, which can improve the smelting conditions of the furnace.

[0035] The present invention has been described in detail above through specific and preferred embodiments. However, those skilled in the art should understand that the present invention is not limited to the embodiments described above. Any modifications, equivalent substitutions, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A process for the extraction of copper matte from anode slime of a lead-antimony ore, characterized in that, It comprises the following steps: S1, batching: batching and mixing uniformly the lead-antimony ore, anode residue, soda ash and reducing coal according to the raw material assay sheet to prepare a mixture; S2, feeding: feeding the mixture into the reverberatory furnace in batches through a special feeding device; S3, heating, smelting and reducing: the temperature of the reverberatory furnace is kept at 1150-1250℃, and smelting is carried out for 1-2 hours; after the smelting of the previous batch of mixture is completed, the next batch of mixture is fed in until the furnace is full; the reducing temperature is 1250-1350℃, and the reducing time is 4-6 hours; S4, slagging: after the operation door is opened, the molten material in the furnace is observed; when the mixture is completely melted, the molten material has no bubbling phenomenon, the steel rod inserted into the molten material has no hard block, and when the steel rod is pulled out of the molten material, the adhered slag is uniform, smooth and has no nodule phenomenon, the melting end point is reached, the molten slag is completely separated from the copper matte and crude lead, and the slagging operation can be carried out; S5, adding iron filings and discharging copper matte: the total amount of iron filings is calculated according to the lead content in the copper matte layer, and the iron filings are added in batches, each time being uniformly scattered into the molten material surface in the furnace; after the second iron is added, the iron filings and the copper matte layer in the furnace are stirred and mixed uniformly by using a dried iron rake to ensure that the iron filings and the copper matte are in full contact and reaction; after the iron is added and stirred, the temperature of the furnace is kept at 1250-1350℃ to make the iron filings and the copper matte fully react, and the mixture is kept still for 20-30 minutes to observe whether the iron filings on the surface of the molten material are completely melted; if the iron filings are completely melted, it is necessary to check whether the iron filings are sufficient; if the waste oxygen iron pipe is corroded after being inserted into the copper matte layer and stirred for 1 minute, it indicates that the amount of iron filings is insufficient, and the iron filings need to be added until the surface of the molten material has iron filings remaining and the copper matte layer is sticky, and the displacement reaction is completed, and the operation of discharging the copper matte can be carried out; S6, discharging crude lead operation: after the copper matte is discharged, 6-8 tons of mixture are fed in to reduce the temperature of the reverberatory furnace to below 550℃, and the condensation principle is used to reduce the copper content in the crude lead to below 1.5%, and the operation of discharging the crude lead can be carried out; The composition and content of the anode residue in step S1 are as follows: Pb 60%-65%, Sb 7%-14%, Cu 5%-10%, Ag 1000g / t-1300g / t, Bi 1%-4%, Sn 0.5%-0.9%, and S 0.5%-1.5%. The composition and content of the lead-antimony ore are as follows: Pb 22%-28%, Sb 18%-24%, Cu 0.5%-2%, Ag 300g / t-700g / t, Bi 0.1%-0.4%, and S 4%-24%.

2. A process for the extraction of copper matte from anode slime of lead-antimony ore as claimed in claim 1, wherein, The batching ratio of the lead-antimony ore, anode residue, soda ash and reducing coal in step S1 is 45:100:6:

8.

3. A process for the extraction of copper matte from anode slime of lead-antimony ore as claimed in claim 1, wherein, The feeding amount of each batch of the mixture in step S2 is controlled at 4-6 tons.

4. A process for the extraction of copper matte from anode slime of lead-antimony ore as claimed in claim 1, wherein, The total amount of the iron filings in step S5 is 1 / 4 of the lead content in the copper matte layer, and the amount of the iron filings added at a time is 300-400Kg when the amount of the iron filings is insufficient.

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