CN109797288B - Treatment process of tin-smelting sulfur slag - Google Patents
Treatment process of tin-smelting sulfur slag Download PDFInfo
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Abstract
The invention provides a treatment process of tin-smelting sulfur slag, which solves some defects of the existing process. Finally, valuable metal elements Sn and Cu in the tin-smelting sulfur slag are comprehensively recovered, and impurity elements such as S and the like are removed. The adopted process flow is mainly divided into three parts: firstly, carrying out physical separation on tin-smelting sulfur slag, wherein the physical separation adopts a grinding and screening method to obtain materials on a screen and materials under the screen, wherein the materials on the screen are mainly metals, the metals can be directly returned to a smelting system, and the sulfur slag under the screen is subjected to the next step of oxidizing roasting treatment; secondly, oxidizing and roasting the sulfur slag under the sieve, wherein the oxidizing and roasting finally and completely oxidizes metals and metal sulfides in the slag into stable oxides and desulfurizes in the process; then, sulfuric acid leaching is carried out on the calcine obtained by oxidizing roasting, Cu enters leaching liquid in the leaching process, and Sn enters leaching slag, so that the purpose of separating copper and tin is achieved; and finally, respectively recovering and treating the leached leaching solution and the leached residues to obtain copper sulfate and tin oxide products.
Description
Technical Field
The invention belongs to the field of metallurgical solid waste recovery treatment, and particularly relates to a treatment process of tin-smelting sulfur slag.
Background
The metallic tin plays an important role in the fields of life and economy of people and is an indispensable important supporting material for technological development. With the increasingly expanded application range and the corresponding increase of the usage amount of tin, people excavate a great amount of primary tin ore, the primary tin ore resource is exhausted increasingly, and in order to realize the sustainable development of the tin metallurgical industry, it becomes more and more important to effectively recover and utilize a great amount of tin-containing slag produced in the tin smelting process. In the smelting process of tin concentrate, the tin content in the tin-smelting sulfur slag obtained by adding the sulfur powder to remove copper reaches more than 55 percent, the copper content reaches about 20 percent, the recovery value is high, and harmful elements such as sulfur, arsenic and the like contained in the slag can pollute the environment. Comprehensively treating the tin-smelting sulfur slag, recovering tin and copper in the slag to obtain tin oxide and copper sulfate products, recycling the tin-smelting sulfur slag, having great economic benefit and being beneficial to reducing the comprehensive production cost.
(1) Fire smelting: adding a certain proportion of flux into a short kiln for smelting to generate a tin-copper alloy semi-product, and because a large amount of impurities in slag enter the alloy, the alloy product is difficult to further process.
(2) Roasting-leaching method: the roasting of the tin-smelting sulfur slag is carried out, then the sulfuric acid is used for leaching the roasted product, so that the copper is opened from a tin smelting system in the form of a copper sulfate product.
(3) Diaphragm electrolysis: the method is characterized in that firstly, diaphragm electrolysis is carried out on tin-smelting sulfur slag, a certain amount of metal tin is opened in a Sn-Pb alloy mode, and then, oxidation roasting and sulfuric acid leaching are carried out on electrolytic anode mud (diaphragm slag), so that copper is produced as a copper sulfate product, and the purpose of opening the copper circuit is achieved. The method has the defects of low direct recovery rate of tin and low current efficiency during electrolysis due to the existence of powdery copper sulfide, so that the economic benefit is poor.
(4) The full wet process comprises the following steps: some researchers have studied the all-wet treatment process of tin-smelting sulfur slag, in which the tin-smelting sulfur slag is decomposed with hydrochloric acid, all the components in the slag are brought into solution, and then the elements are separated in the solution. The method for treating tin-smelting sulfur slag provided by Chinese patent with publication number CN108359805 adopts a two-stage leaching process of firstly carrying out oxygen pressure alkaline leaching on tin-copper slag and then carrying out normal pressure acid leaching, firstly produces a sodium stannate product, and effectively separates tin and copper from residual residues, so that copper is produced in a copper sulfate product form, and produced tin concentrate returns to a tin smelting system.
(5) And (3) a fire-wet process: a process for treating the sulfur dregs generated during smelting tin includes such steps as primary leaching with sulfuric acid to obtain stannous sulfate solution, purifying to obtain high-grade stannous sulfate, oxidizing and calcining the leached dregs, secondary leaching with sulfuric acid to obtain copper sulfate solution, concentrating, crystallizing to obtain copper sulfate product or copper electrolyzing system to generate electric copper, and returning the second leached dregs, which is the concentrated tin ore, back to tin smelting system.
Disclosure of Invention
The invention aims to provide a treatment process of tin-smelting sulfur slag, which solves some defects in the existing process. Finally, valuable metal elements Sn and Cu in the tin-smelting sulfur slag are comprehensively recovered, and impurity elements such as S and the like are removed. The process flow adopted by the process is mainly divided into three parts: firstly, carrying out physical separation on tin-smelting sulfur slag, wherein the physical separation adopts a grinding and screening method to obtain materials on a screen and materials under the screen, wherein the materials on the screen are mainly metals, the metals can be directly returned to a smelting system, and the sulfur slag under the screen is subjected to the next step of oxidizing roasting treatment; secondly, oxidizing and roasting the sulfur slag under the sieve, wherein the oxidizing and roasting finally and completely oxidizes metals and metal sulfides in the slag into stable oxides and desulfurizes in the process; then, sulfuric acid leaching is carried out on the calcine obtained by oxidizing roasting, Cu enters leaching liquid in the leaching process, and Sn enters leaching slag, so that the purpose of separating copper and tin is achieved; and finally, respectively recovering and treating the leached leaching solution and the leached residues to obtain copper sulfate and tin oxide products.
The specific technical scheme of the invention is as follows:
a treatment process of tin-smelting sulfur slag comprises the following steps:
(1) and grinding the tin-smelting sulfur slag for 10-30 min by using a sample preparation grinder, and screening by using a 60-mesh screen after grinding to obtain oversize massive metal and undersize powder sulfur slag.
(2) Roasting the screened sulfur slag at 500 ℃ for 60min for the first time, crushing roasted sand obtained by roasting, and roasting for the second time, wherein the second-time roasting temperature is 800 ℃ and the roasting time is 60min to obtain a roasted product;
(3) leaching the obtained roasted product by using sulfuric acid under the condition that the leaching time is 30-90 min,leaching temperature is 60-90 ℃, liquid-solid ratio is 3-9: 1, stirring speed is 100-400 r/min, H2SO4The mass concentration is 10-25%, and leaching solution containing copper sulfate and leaching residue containing tin oxide are obtained under the condition;
(4) removing iron from the leachate by using alkaline copper carbonate, further evaporating, concentrating, cooling and crystallizing to obtain copper sulfate pentahydrate crystals; the obtained leaching residue is washed and dried to obtain SnO2。
Further, the mass of the oversize metal separated by grinding and screening in the step (1) accounts for 23.15-23.66% of the mass of the whole tin-smelting sulfur slag, wherein the mass of the metal tin accounts for 84.34-86.37%, the mass of the copper accounts for 8.67-9.90%, and the part of metal directly returns to the tin smelting process; the mass percentage of Sn which is a main element in the sulfur slag powder under the screen is 63.27-65.50%, the mass percentage of Cu is 18.20-21.09%, and the mass percentage of S is 13.09-13.67%.
The invention has the beneficial effects that:
1. the method for physically separating the sulfur slag ensures that about 25 percent of metal in the sulfur slag is recycled in advance, and the process of oxidizing roasting-sulfuric acid leaching along with sulfide is not needed, so that the subsequent material treatment capacity is reduced, the energy consumption is reduced, and the treatment cost is saved.
2. The oxidizing roasting of the sulfur slag under the screen is divided into two stages, and the sulfur slag is physically separated before roasting, so that compared with the prior art applied in the industry, the temperature of the two-stage roasting is reduced, and the energy consumption is reduced.
3. In the invention, the crystallization mother liquor generated by concentrating and crystallizing the leaching solution and the washing solution generated by washing the leaching residue can be used for sulfuric acid leaching for recycling, thereby avoiding the treatment of wastewater.
4. The method finally recovers the Cu and Sn elements, and under the optimal process condition, the recovery rate of copper is 90.38%, and the recovery rate of tin is 93.13%. The product finally prepared by the process is CuSO4·5H2O and SnO2Obtaining CuSO4·5H2O purity of 97.66%, SnO2The purity of (A) was 98.78%.
5. The invention adopts the process of physical separation, oxidizing roasting and sulfuric acid leaching to treat the sulfur slag, and has the advantages of relatively simple process, relatively low energy consumption and relatively low economic cost.
Drawings
FIG. 1 is a process flow diagram of a treatment process of a tin-smelting sulfur slag of the invention.
Detailed Description
The technical contents of the present invention will be described further below by way of examples.
Example 1
A treatment process of tin-smelting sulfur slag comprises the following steps:
(1) 500g of tin-smelting sulfur slag is ground for 20min by a sample preparation grinder, and then is sieved by a 60-mesh sieve, so that oversize massive metal and undersize powder sulfur slag are obtained. The metal separated by grinding and screening accounts for 23.66 percent of the total mass of the sulfur slag, wherein the metal tin accounts for 85.79 percent, the copper content accounts for 9.90 percent, and the part of metal is directly returned to the tin smelting process; the percentage content of main elements Sn in the sulfur residue under the sieve is 65.50%, the percentage content of Cu is 18.20%, and the percentage content of S is 13.67%;
(2) roasting the undersize sulfur slag obtained in the step (1) at 500 ℃ for 60min, crushing, and roasting at 800 ℃ for 60min to obtain roasted sand;
(3) leaching the calcine obtained in the step (2) by using sulfuric acid under the condition that the leaching time is 50min, the leaching temperature is 70 ℃, the liquid-solid ratio is 3:1, the stirring speed is 400r/min, and H2SO4The mass concentration is 20 percent, and leaching solution containing copper sulfate and leaching residue containing tin oxide are obtained under the condition;
(4) removing iron from the leaching solution obtained in the step (3) by using basic copper carbonate, further evaporating, concentrating, cooling and crystallizing to obtain CuSO4·5H2O crystals; the obtained leaching residue is washed and dried to obtain SnO2. Under the best process conditions, the recovery rate of copper is 90.38%, and the recovery rate of tin is 93.13%. The obtained CuSO4·5H2O purity of 97.66%, SnO2The purity of (A) was 98.78%.
Example 2
A treatment process of tin-smelting sulfur slag comprises the following steps:
(1) 500g of tin-smelting sulfur slag is ground for 30min by a sample preparation grinder, and then sieved by a 60-mesh sieve to obtain oversize massive metal and undersize powder sulfur slag. The metal separated by grinding and screening accounts for 23.56 percent of the total mass of the sulfur slag, wherein the metal tin accounts for 86.37 percent, the copper content accounts for 8.82 percent, and the part of metal is directly returned to the tin smelting process; the percentage content of the main element Sn in the sulfur residue under the sieve reaches 63.58 percent, the content of Cu is 21.09 percent, and the content of S is 13.09 percent;
(2) roasting the undersize sulfur slag obtained in the step (1) at 500 ℃ for 60min, crushing, and roasting at 800 ℃ for 60min to obtain roasted sand;
(3) leaching the calcine obtained in the step (2) by using sulfuric acid under the condition that the leaching time is 70min, the leaching temperature is 80 ℃, the liquid-solid ratio is 5:1, the stirring speed is 300r/min, and H2SO4The mass concentration is 25 percent, and leaching solution containing copper sulfate and leaching residue containing tin oxide are obtained under the condition;
(4) removing iron from the leaching solution obtained in the step (3) by using basic copper carbonate, further evaporating, concentrating, cooling and crystallizing to obtain CuSO4·5H2O crystals; the obtained leaching residue is washed and dried to obtain SnO2. Under the best process conditions, the recovery rate of copper is 91.09%, and the recovery rate of tin is 92.89%. The obtained CuSO4·5H2O purity of 97.83%, SnO2The purity of (2) was 97.68%.
Example 3
A treatment process of tin-smelting sulfur slag comprises the following steps:
(1) 500g of tin-smelting sulfur slag is ground for 10min by a sample preparation grinder, and then the ground tin-smelting sulfur slag is sieved by a 60-mesh sieve to obtain oversize massive metal and undersize powder sulfur slag. The metal separated by grinding and screening accounts for 23.15 percent of the total mass of the sulfur slag, wherein the metal tin accounts for 84.34 percent, the copper content accounts for 8.67 percent, and the part of metal is directly returned to the tin smelting process; the percentage content of main elements Sn in the sulfur residue under the sieve is 63.27%, the percentage content of Cu is 20.55%, and the percentage content of S is 13.34%;
(2) roasting the undersize sulfur slag obtained in the step (1) at 500 ℃ for 60min, crushing, and roasting at 800 ℃ for 60min to obtain roasted sand;
(3) leaching the calcine obtained in the step (2) by using sulfuric acid under the condition that the leaching time is 90min, the leaching temperature is 90 ℃, the liquid-solid ratio is 7:1, the stirring speed is 400r/min, and H2SO4The mass concentration is 15 percent, and leaching solution containing copper sulfate and leaching residue containing tin oxide are obtained under the condition;
(4) removing iron from the leaching solution obtained in the step (3) by using basic copper carbonate, further evaporating, concentrating, cooling and crystallizing to obtain CuSO4·5H2O crystals; the obtained leaching residue is washed and dried to obtain SnO2. Under the best process conditions, the recovery rate of copper is 89.96 percent, and the recovery rate of tin is 92.38 percent. The obtained CuSO4·5H2O purity of 97.26%, SnO2The purity of (2) was 98.05%.
Claims (1)
1. The treatment process of the tin-smelting sulfur slag is characterized by comprising the following steps of:
(1) grinding the tin-smelting sulfur slag for 10-30 min by using a sample preparation grinder, and screening by using a 60-mesh screen after grinding to obtain oversize massive metal and undersize powder sulfur slag; the mass of the oversize blocky metal separated by grinding and screening accounts for 23.15-23.66% of the mass of the whole tin-smelting sulfur slag, wherein the mass of the metal tin accounts for 84.34-86.37%, the mass of the copper accounts for 8.67-9.90%, and the part of metal directly returns to the tin smelting process; the mass percentage of Sn which is a main element in the sulfur slag powder under the screen is 63.27-65.50%, the mass percentage of Cu is 18.20-21.09%, and the mass percentage of S is 13.09-13.67%;
(2) performing primary roasting on the powder sulfur slag screened in the step (1) at 500 ℃ for 60min, crushing roasted sand obtained by roasting, and performing secondary roasting at 800 ℃ for 60min to obtain a roasted product;
(3) leaching the roasted product obtained in the step (2) by using sulfuric acid under the condition that the leaching time is 30-90 min, the leaching temperature is 60-90 ℃, the liquid-solid ratio is 3-9: 1, the stirring speed is 100-400 r/min, and the mass concentration of the sulfuric acid is 10-25%, so that a leaching solution containing copper sulfate and leaching residues containing tin oxide are obtained under the condition;
(4) removing iron from the leachate obtained in the step (3) by using alkaline copper carbonate, further evaporating, concentrating, cooling and crystallizing to obtain copper sulfate pentahydrate crystals; washing and drying the leaching residue obtained in the step (3) to obtain SnO2。
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