CN113060758A - Method for preparing stannic oxide and stannate by using tin-copper slag - Google Patents
Method for preparing stannic oxide and stannate by using tin-copper slag Download PDFInfo
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Abstract
A method for preparing stannic oxide and stannate by using tin-copper slag comprises the steps of grinding tin-copper slag containing metallic tin, screening, and screening by using a 40-mesh screen or a 60-mesh screen to obtain flaky tin flowers serving as raw materials for preparing potassium stannate; filtering the undersize material which is sieved by a 100-mesh sieve to obtain a powdery tin material which is used as a raw material for preparing tin dioxide; synthesizing stannic acid salt solution from the stannic flower and alkali liquor at high temperature and high pressure in an oxidizing atmosphere, and concentrating and crystallizing the solution to obtain stannate products; the method comprises the steps of synthesizing a tin dioxide intermediate product from a powdery tin material and sulfuric acid at high temperature and high pressure in an oxidizing atmosphere in a closed container, adding water for washing, neutralizing with ammonium bicarbonate, drying and calcining a solid obtained after liquid-solid separation to obtain a tin dioxide product, returning residual liquid to prepare a sulfuric acid solution until the copper content reaches 48-52 g/l, and concentrating and crystallizing to obtain a copper sulfate product. The invention realizes tin-copper slag classification by a physical method, and adopts different process methods to produce stannate and stannic oxide, thereby greatly reducing the production cost.
Description
Technical Field
The invention belongs to the technical field of wet metallurgy and chemical industry, and particularly relates to a method for directly synthesizing stannic oxide and stannate by using tin-copper slag.
Background
Tin dioxide (SnO)2) Has wide industrial application, is mainly used for the production of ceramics, enamel, glass, electronic devices, decorative materials and the like, and is also used for the production of chemical reagents such as glaze, pigment, flame retardant, catalyst and the like.
At present, the method for preparing tin dioxide mainly comprises a gasification method and a nitric acid method, wherein the gasification method is mainly characterized in that molten tin is blown into hot air at high temperature to be directly oxidized to generate tin dioxide. The nitric acid method is that tin flower reacts with nitric acid to produce metastannic acid, and then the stannic acid is calcined at high temperature to obtain a stannic oxide product. The industry is mainly a nitric acid method, which has high requirements on equipment corrosion resistance, and generates nitrogen oxides in the reaction process, thereby causing adverse effects on the environment.
Most of the production methods of stannate are mainly pyrogenic methods, and have the problems of poor production environment, high labor intensity of workers, low production efficiency and the like due to a metatitanic acid method and an alkaline hydrolysis method.
Chinese patent No. ZL201810135124.9 discloses a method for producing metastannic acid and tin dioxide by a sulfuric acid process, which comprises reacting sulfuric acid with tin under sealed conditions of adding oxygen, pressurizing and heating to obtain metastannic acid, and calcining at high temperature to obtain tin dioxide. The sulfuric acid is only used as a carrier, so that the consumption is low, but the equipment investment is large.
Chinese patent No. ZL200410100843.5 discloses a method for preparing metastannic acid (tin dioxide) powder, which comprises heating tin under sealed oxygen-adding and pressure conditions to react with nitric acid to obtain metastannic acid, and calcining at high temperature to obtain tin dioxide. The method does not generate nitrogen oxides after the reaction is finished, but the cost of the nitric acid reagent is high.
The chinese patent application No. 200810058872.8 also discloses a method for producing alkali metal stannate, which comprises heating metal tin powder to react with potassium (sodium) hydroxide under sealed oxygen-adding and pressure conditions to produce alkali metal stannate.
The raw materials adopted by the method in the prior art are refined tin, so that the cost of the raw materials is high, and the production cost of the tin dioxide and stannate is also high.
In the welding process, a large amount of tin-copper slag can be generated, the impurity content is high, a certain amount of tin and copper still remain, if the tin-copper slag is discarded, the waste is large, and certain pollution can be caused to the environment, so that research and development of a low-cost effective utilization way of the tin-copper slag are significant.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a method which can replace refined tin with tin-copper slag to prepare tin dioxide and stannate, and has the advantages of low production cost, safety, reliability, cleanness and environmental protection.
The technical scheme adopted by the invention is as follows:
a method for preparing stannic oxide and stannate by using tin-copper slag comprises the steps of grinding tin-copper slag containing metallic tin, classifying the tin-copper slag by sieves with different meshes, and screening materials on the sieve which are screened by a 40-mesh sieve or a 60-mesh sieve into flaky tin flowers with low copper content to serve as raw materials for preparing potassium stannate; filtering the undersize material which is sieved by a 100-mesh sieve to obtain a powdery tin material which is high in copper content and is used as a raw material for preparing tin dioxide; synthesizing the stannum flower and a potassium hydroxide solution or a sodium hydroxide solution into a potassium stannate solution or a sodium stannate solution at high temperature and high pressure in an oxidizing atmosphere, filtering the solution, concentrating and crystallizing to obtain a potassium stannate product or a sodium stannate product; and (2) synthesizing a tin dioxide product from the powdery tin material and sulfuric acid at high temperature and high pressure in an oxidizing atmosphere in a closed container, adding water into the tin dioxide for washing, adding ammonium carbonate for neutralization, carrying out liquid-solid separation, drying and calcining the solid to obtain the tin dioxide product, returning residual liquid to prepare a sulfuric acid solution until the copper content reaches 48-52 g/l, and concentrating and crystallizing to obtain the copper sulfate product.
Furthermore, the tin-copper slag is produced in the wave soldering process, the tin in the tin-copper slag exists in the form of simple substance tin and tin dioxide, and the tin-copper slag contains more than or equal to 55 wt% of Sn, 0.1-2 wt% of Fe, less than or equal to 30 wt% of Cu and less than or equal to 0.1 wt% of Pb.
Further, after the tin-copper slag after ore grinding is graded by sieves with different meshes, the materials between 40 meshes and 100 meshes or between 60 meshes and 100 meshes are returned to the ore grinding.
Further, the ore grinding is performed by a rod mill and a wet type ore grinding, the mass concentration of ore pulp is 40-70%, and the ore grinding time is 15-60 minutes.
Further, synthesizing the stannum flower and a potassium hydroxide solution or a sodium hydroxide solution into a potassium stannate solution or a sodium stannate solution at high temperature and high pressure in an oxidizing atmosphere, wherein the liquid-solid mass ratio of the potassium hydroxide solution or the sodium hydroxide solution to the stannum flower is 7-10: 1, the initial alkalinity of the potassium hydroxide solution or the sodium hydroxide solution is 80-150 g/l, the reaction pressure is not less than 0.6MPa, the reaction temperature is 130-200 ℃, the reaction time is 2-6 hours, reacting and synthesizing to obtain a potassium stannate slurry or a sodium stannate slurry, carrying out liquid-solid separation on the slurry, concentrating and crystallizing the filtrate to obtain a potassium stannate product or a sodium stannate product, returning the concentrated mother liquor to prepare an alkali solution, and returning the filter residue to copper smelting for the iron-containing.
Further, the tin dioxide product is synthesized by the powdery tin material and sulfuric acid at high temperature and high pressure in an oxygen atmosphere in a closed container, the mass ratio of liquid to solid of the sulfuric acid to the powdery tin material is 4-10: 1, the initial acidity of the sulfuric acid is not more than 150g/l, the reaction pressure is not less than 0.5MPa, the reaction temperature is 130-200 ℃, the reaction time is 4-8 hours, tin dioxide intermediate product slurry is obtained through reaction synthesis, the slurry is subjected to liquid-solid separation, residual liquid is returned to prepare a sulfuric acid solution until the copper content reaches 48-52 g/l, copper sulfate products are produced through concentration crystallization, the separated tin dioxide intermediate product is washed by adding water and is neutralized by ammonium carbonate until the pH is 7-8, then liquid-solid separation is carried out, the separated solid is dried in vacuum at 100-400 ℃ for 5-12 hours, and is roasted at 600-1000 ℃ for 4-8 hours, and the tin dioxide product is obtained.
The invention has at least the following beneficial effects:
(1) the separation of partial tin and copper is realized after grinding and screening the tin-copper slag by adopting a physical method, the process is simple and easy to implement, no waste gas, waste water and waste slag are generated and discharged in the process, the energy is saved, the environment is protected, and particularly, the material on a 40-mesh or 60-mesh sieve screened by grinding the tin slag by using a rod mill is a thin tin material which can be directly fed into a reaction kettle as a raw material without an additional screening process;
(2) the screened materials directly enter different tin chemical product processes according to different impurity contents, the coarse tin materials are used for replacing refined tin to produce tin dioxide and stannate, tin and copper in tin-copper slag are effectively utilized, and the production cost of the tin dioxide and the stannate is greatly reduced;
(3) the processes for producing the tin dioxide and the stannate selected for the treatment of the materials are all completed in a closed container, nitrate and nitric acid oxidants are not generated in the reaction process, the safety of the reaction process is high, no waste gas is discharged after the reaction is finished, and clean production is realized;
(4) tin flowers with high tin content and low copper and iron content enter a stannate production process, and iron and copper trace enter a solution, so that the purification process is simple and the purification cost is low; the tin material with high copper content enters the process of producing tin dioxide, high-temperature pressure leaching is carried out, copper enters a solution, tin dioxide enters slag, tin-copper separation is realized, tin dioxide can reach the standard of qualified products through washing of tin dioxide, and meanwhile, a leaching solution can be concentrated and crystallized to produce a copper sulfate product;
(5) according to the invention, the tin-copper slag is used for replacing refined tin as a raw material to produce stannate and tin dioxide, copper in the tin-copper slag is associated with copper products, tin and copper are effectively utilized, the production cost is greatly reduced, the benefit space is obviously increased, and the market competitiveness of the products can be improved.
Detailed Description
The present invention will be further illustrated with reference to the following examples.
The invention relates to a method for preparing stannic oxide and stannate by using tin-copper slag, which comprises the step of grading tin materials with low copper and high copper by carrying out ore grinding treatment on the tin-copper slag generated in the wave soldering process through a wet rod mill, wherein the tin materials with low copper and high copper are used as raw materials for producing stannate products, and the tin materials with high copper and high copper are used as raw materials for producing stannic oxide. The tin in the tin-copper slag generated in the wave soldering process mainly comprises simple substance tin and tin dioxide, wherein the tin-copper slag contains more than or equal to 55 wt% of Sn, 0.1-2 wt% of Fe, less than or equal to 30 wt% of Cu and less than or equal to 0.1 wt% of Pb.
Example 1
The method for preparing tin dioxide and stannate by using tin-copper slag comprises the following specific steps:
(1) carrying out wet grinding on 2000g of tin-copper slag containing 14.5 wt% of copper, 70 wt% of tin, 0.08 wt% of lead, 1.2 wt% of iron, 0.8 wt% of arsenic and 9.9 wt% of sulfur by using a rod mill according to 45% of pulp concentration, grinding the ore for 50 minutes, screening the ground ore pulp by using a 60-mesh rotary screen to obtain 301.5g of oversize material (tin flower) containing 87.45 wt% of tin, 1.58 wt% of copper and-60-mesh ore pulp, screening the 60-mesh ore pulp by using a 100-mesh rotary screen to obtain oversize material and-100-mesh ore pulp, returning the oversize material to continue grinding the ore, and filtering the 100-mesh ore pulp to obtain 1680g of powdered tin material containing 66.42 wt% of tin and 18.34 wt% of copper, and returning filtrate to an ore grinding system for recycling.
(2) Dissolving 400g of potassium hydroxide in 2L of deionized water to obtain a potassium hydroxide solution with the alkalinity of 200g/L, adding the potassium hydroxide solution into a 3L pressure kettle, adding 300g of stannum flower, wherein the liquid-solid mass ratio of the potassium hydroxide solution to the stannum flower is 6.7, introducing oxygen to the kettle pressure of 1.2MPa, heating to 150 ℃, reacting at a constant temperature for 3 hours, cooling, discharging, filtering, concentrating, crystallizing and centrifuging a leaching solution to obtain 668g of a potassium stannate product, wherein the tin content is 38.4 wt%, and the direct tin yield is 97.8 wt%, so that the standard requirement of the product is met. The concentrated mother liquor can be returned to prepare potassium hydroxide. And the filter residue is sold as copper slag.
(3) Preparing 2L of sulfuric acid solution with acidity of 120g/L, adding the sulfuric acid solution and 400g of powdered tin material (the mass ratio of liquid to solid of the sulfuric acid to the powdered tin material is 5, adding the sulfuric acid solution to a 3L pressure kettle, introducing oxygen to the pressure of the kettle to be 2MPa, heating to 150 ℃, keeping the temperature for 6 hours to obtain intermediate product slurry of tin dioxide after reaction, separating the slurry from liquid and solid, returning residual liquid to the preparation of the sulfuric acid solution, washing the separated intermediate product of tin dioxide with water, neutralizing with ammonium bicarbonate to pH7, then carrying out liquid-solid separation, carrying out vacuum drying on the solid part at 300 ℃ for 10 hours, roasting at 800 ℃ for 6 hours to obtain 310.7g of tin dioxide product, wherein the main content (the content of tin dioxide) of the tin dioxide is 99.27 wt.%, the content of iron is 0.018 wt.%, the content of lead is 0.0024 wt.%, the content of antimony is 0.0016 wt.%, the direct yield of tin is 91.38%, meeting the standard requirement of the product, returning the residual liquid, concentration crystallization yielded a copper sulfate product with a major content of 97.42 wt.%.
Example 2
The method for preparing tin dioxide and stannate by using tin-copper slag comprises the following specific steps:
(1) wet grinding 2000g of tin-copper slag containing 5 wt%, 89.24 wt%, 0.022 wt%, 2 wt%, 1.2 wt% of arsenic and 3.52 wt% of sulfur by using a rod mill according to 70% of pulp concentration, grinding for 15 minutes, screening the ground pulp by using a 60-mesh rotary screen to obtain 364.5g of oversize material (tin flower) containing 93.34 wt% of tin and 0.35 wt% of copper and-60-mesh pulp, screening the 60-mesh pulp by using a 100-mesh rotary screen to obtain oversize material and-100-mesh pulp, returning the oversize material to continue grinding, filtering the 100-mesh pulp to obtain 1623g of powdered tin material containing 88.96 wt% of tin and 5.93 wt% of copper, and returning filtrate to an ore grinding system for recycling.
(2) Dissolving 400g of sodium hydroxide in 2L of deionized water to obtain a sodium hydroxide solution with the alkalinity of 200g/L, adding the sodium hydroxide solution into a 3L pressure kettle, adding 300g of stannum flower, wherein the liquid-solid mass ratio of the sodium hydroxide solution to the stannum flower is 6.7, introducing oxygen to the kettle pressure of 0.8MPa, heating to 200 ℃, reacting at a constant temperature for 2 hours, cooling, discharging, filtering, concentrating, crystallizing and centrifuging a leaching solution to obtain 855.18g of a sodium stannate product, wherein the stannum content is 42.34 wt%, and the stannum direct yield is 96.98 wt%, and the standard requirement of the product is met. The concentrated mother liquor can be returned to prepare sodium hydroxide. And the filter residue is sold as copper slag.
(3) Preparing 2L of sulfuric acid solution with acidity of 60g/L, adding 400g of sulfuric acid solution and powdered tin material (the liquid-solid mass ratio of sulfuric acid to powdered tin material is 5) into a 3L pressure kettle, introducing oxygen until the pressure in the kettle is 1MPa, heating to 200 ℃, keeping the temperature for 4 hours to obtain intermediate product slurry of the reacted tin dioxide, separating the slurry from liquid and solid, returning the residual liquid to prepare sulfuric acid solution, washing the separated intermediate product of the tin dioxide with water, neutralizing the intermediate product with ammonium carbonate to pH8, then carrying out liquid and solid separation, carrying out vacuum drying on the solid part at 400 ℃ for 5 hours, roasting at 1000 ℃ for 4 hours to obtain 439.58g of tin dioxide product, the main content is 99.23 wt.%, the iron content is 0.024 wt.%, the lead content is 0.0018 wt.%, the antimony content is 0.0026 wt.%, the tin yield is 96.42%, the standard requirement of the product is met, the residual liquid is circulated to the copper content of about 49g/l, and the copper sulfate product with the main content of 97.58 wt.% is produced by concentration and crystallization.
Example 3
The method for preparing tin dioxide and stannate by using tin-copper slag comprises the following specific steps:
(1) wet grinding 2000g of tin-copper slag containing 18.21 wt% of copper, 69.56 wt% of tin, 0.058 wt% of lead, 0.1 wt% of iron, 1.1 wt% of arsenic and 6.52 wt% of sulfur by using a rod mill according to 40% of pulp concentration, grinding the ore for 60 minutes, screening the ground ore pulp by using a 40-mesh drum screen to obtain 297.5g of oversize material (tin flower) containing 89.34 wt% of tin and 2.65 wt% of copper and-40-mesh ore pulp, screening the 40-mesh ore pulp by using a 100-mesh drum screen to obtain oversize material and-100-mesh ore pulp, returning the oversize material to continue grinding the ore, and filtering the 100-mesh ore pulp to obtain 1703g of powdered tin material containing 65.35 wt% of tin and 20.89 wt% of copper, and returning filtrate to an ore grinding system for recycling.
(2) Dissolving 400g of sodium hydroxide in 2L of deionized water to obtain a sodium hydroxide solution with the alkalinity of 200g/L, adding the sodium hydroxide solution into a 3L pressure kettle, adding 300g of stannum flower, wherein the liquid-solid mass ratio of the sodium hydroxide solution to the stannum flower is 6.7, introducing oxygen to the kettle pressure of 0.8MPa, heating to 130 ℃, reacting at the constant temperature for 6 hours, cooling, discharging, filtering, concentrating, crystallizing and centrifuging a leaching solution to obtain 823.11g of a sodium stannate product, wherein the stannum content is 42.24 wt%, and the stannum direct yield is 97.78 wt%, so that the standard requirement of the product is met. The concentrated mother liquor can be returned to prepare sodium hydroxide. And the filter residue is sold as copper slag.
(3) Preparing 2L of sulfuric acid solution with acidity of 150g/L, adding 500g of sulfuric acid solution and powdered tin material (the liquid-solid mass ratio of sulfuric acid to powdered tin material is 4) into a 3L pressure kettle, introducing oxygen until the pressure in the kettle is 2MPa, heating to 130 ℃, keeping the temperature for 8 hours to obtain intermediate product slurry of the reacted tin dioxide, separating the slurry liquid from the solid, returning the residual liquid to prepare sulfuric acid solution, washing the separated intermediate product of the tin dioxide with water, neutralizing the intermediate product with ammonium carbonate to pH7.5, then separating the liquid from the solid, vacuum drying the solid part at 100 ℃ for 12 hours, roasting at 600 ℃ for 8 hours to obtain 405.15g of tin dioxide product, the main content of the copper sulfate product is 99.25 wt.%, the iron content is 0.012 wt.%, the lead content is 0.0014 wt.%, the antimony content is 0.0014 wt.%, the tin yield is 96.95%, the standard requirement of the product is met, the residual liquid is recycled to the copper content of 51.18g/l, and the concentration and crystallization yield the copper sulfate product with the main content (copper sulfate content) of 97.32%.
Example 4
The method for preparing tin dioxide and stannate by using tin-copper slag comprises the following specific steps:
(1) wet grinding is carried out on 2000g of tin-copper slag containing 29.14 wt.% copper, 58.21 wt.% tin, 0.022 wt.% lead, 0.46 wt.% iron, 0.25 wt.% arsenic and 2.3 wt.% sulfur by a rod mill according to the pulp concentration of 50%, grinding is carried out for 40 minutes, the ground pulp is sieved by a 60-mesh rotary screen to obtain 212g of oversize material (tin flower) containing 83.64 wt.% tin, 1.78 wt.% copper and-60-mesh pulp, the 60-mesh pulp enters a 100-mesh rotary screen to be sieved to obtain oversize material and-100-mesh pulp, the oversize material returns to be ground, the 100-mesh pulp is filtered to obtain 1723.34g of powdered tin material containing 56.12 wt.% tin and 33.26 wt.% copper, and filtrate returns to an ore grinding system to be recycled.
(2) Dissolving 400g of potassium hydroxide in 2L of deionized water to obtain a potassium hydroxide solution with the alkalinity of 200g/L, adding the potassium hydroxide solution into a 3L pressure kettle, adding 300g of stannum flower, wherein the liquid-solid mass ratio of the potassium hydroxide solution to the stannum flower is 6.7, introducing oxygen to the kettle pressure of 1.2MPa, heating to 150 ℃, reacting at a constant temperature for 3 hours, cooling, discharging, filtering, concentrating, crystallizing and centrifuging a leaching solution to obtain 643g of potassium stannate products, wherein the tin content is 38.24 wt%, and the direct tin yield is 98 wt%, and the standard requirements of the products are met. The concentrated mother liquor can be returned to prepare potassium hydroxide. And the filter residue is sold as copper slag.
(3) Preparing 2.4L of sulfuric acid solution with acidity of 120g/L, adding the sulfuric acid solution and 400g of powdered tin material (the mass ratio of liquid to solid of the sulfuric acid to the powdered tin material is 6, adding the sulfuric acid solution to a 3L pressure kettle, introducing oxygen to the pressure of the kettle to be 2MPa, heating to 150 ℃, keeping the temperature for 6 hours to obtain intermediate product slurry of tin dioxide after reaction, separating the slurry from solid, returning residual liquid to the preparation of the sulfuric acid solution, washing the separated intermediate product of tin dioxide with water, neutralizing with ammonium bicarbonate to pH7, then carrying out liquid-solid separation on the solid part, carrying out vacuum drying on the solid part at 300 ℃ for 10 hours, roasting at 800 ℃ for 6 hours to obtain 272.98g of tin dioxide product, wherein the main content of the tin dioxide product is 99.17 wt.%, the iron content is 0.024 wt.%, the lead content is 0.0021 wt.%, the antimony content is 0.0012 wt.%, and the direct yield of tin is 94.98%, and the standard requirement of the product is achieved.
Claims (6)
1. A method for preparing stannic oxide and stannate by using tin-copper slag is characterized in that after tin-copper slag containing metallic tin is ground, the tin-copper slag is classified by sieves with different meshes, and materials on the sieve after passing through a 40-mesh sieve or a 60-mesh sieve are flaky tin flowers with low copper content and are used as raw materials for preparing potassium stannate; filtering the undersize material which is sieved by a 100-mesh sieve to obtain a powdery tin material which is high in copper content and is used as a raw material for preparing tin dioxide; synthesizing the stannum flower and a potassium hydroxide solution or a sodium hydroxide solution into a potassium stannate solution or a sodium stannate solution at high temperature and high pressure in an oxidizing atmosphere, filtering the solution, concentrating and crystallizing to obtain a potassium stannate product or a sodium stannate product; and (2) synthesizing a tin dioxide product from the powdery tin material and sulfuric acid at high temperature and high pressure in an oxidizing atmosphere in a closed container, adding water into the tin dioxide for washing, adding ammonium carbonate for neutralization, carrying out liquid-solid separation, drying and calcining the solid to obtain the tin dioxide product, returning residual liquid to prepare a sulfuric acid solution until the copper content of the solution reaches 48-52 g/l, and concentrating and crystallizing to obtain the copper sulfate product.
2. The method for preparing tin dioxide and stannate by using tin-copper slag as claimed in claim 1, wherein the tin-copper slag is tin-copper slag generated in wave soldering process, the tin in the tin-copper slag exists in the form of simple substance tin and tin dioxide, and the tin-copper slag contains not less than 55 wt.% of Sn, 0.1-2 wt.% of Fe, not more than 30 wt.% of Cu, and not more than 0.1 wt.% of Pb.
3. The method for preparing tin dioxide and stannate by using tin-copper slag according to claim 1, wherein the tin-copper slag after ore grinding is classified by sieves with different meshes, and materials between 60 meshes and 100 meshes are returned to the ore grinding.
4. The method for preparing tin dioxide and stannate from tin-copper slag according to claim 1, wherein the ore grinding is performed by a rod mill and a wet-type ore grinding, the mass concentration of ore pulp is 40-70%, and the ore grinding time is 15-60 minutes.
5. The method for preparing tin dioxide and stannate by using tin-copper slag according to claim 1, wherein tin flower and potassium hydroxide solution or sodium hydroxide solution are synthesized into potassium stannate solution or sodium stannate solution at high temperature and high pressure in an oxidizing atmosphere, the mass ratio of liquid to solid of the potassium hydroxide solution or sodium hydroxide solution to the tin flower is 7-10: 1, the initial alkalinity of the potassium hydroxide solution or sodium hydroxide solution is 80-150 g/l, the reaction pressure is not less than 0.6MPa, the reaction temperature is 130-200 ℃, the reaction time is 2-6 hours, potassium stannate slurry or sodium stannate slurry is obtained through reaction synthesis, the slurry is subjected to liquid-solid separation, filtrate is concentrated and crystallized to produce potassium stannate product or sodium stannate product, concentrated mother liquor returns to prepare alkali solution, and filter residue is iron-containing copper slag and returns to copper smelting.
6. The method for preparing tin dioxide and stannate by using tin-copper slag according to claim 1, wherein the tin dioxide product is synthesized by using powdered tin material and sulfuric acid at high temperature and high pressure in an oxygen atmosphere in a closed container, the liquid-solid mass ratio of the sulfuric acid to the powdered tin material is 4-10: 1, the initial acidity of the sulfuric acid is not more than 150g/l, the reaction pressure is not less than 0.5MPa, the reaction temperature is 130-200 ℃, the reaction time is 4-8 hours, tin dioxide intermediate product slurry is obtained by reaction synthesis, the slurry is subjected to liquid-solid separation, the residual liquid is returned to prepare sulfuric acid solution until the copper content reaches 48-52 g/l, copper sulfate product is obtained by concentration and crystallization, the separated tin dioxide intermediate product is washed by adding water and neutralized by ammonium carbonate to the pH value of 7-8, the solid is subjected to liquid-solid separation, the separated solid is dried under vacuum at 100-400 ℃ for 5-12 hours, and is roasted at 600-1000 ℃ for 4-8 hours, obtaining the stannic oxide product.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101643238A (en) * | 2009-06-22 | 2010-02-10 | 云南锡业集团（控股）有限责任公司 | Method for producing tin dioxide |
| US20100147684A1 (en) * | 2008-12-12 | 2010-06-17 | Electronics And Telecommunications Research Institute | Ultra-sensitive gas sensor using oxide semiconductor nanofiber and method of fabricating the same |
| US20140127109A1 (en) * | 2011-05-10 | 2014-05-08 | Mitsubishi Materials Corporation | Tin(ii) oxide powder for replenishing tin component of tin-alloy plating solution and method for manufacturing said powder |
| CN104973620A (en) * | 2015-07-23 | 2015-10-14 | 柳州华锡铟锡材料有限公司 | Production method of large-particle sodium stannate crystals |
| CN108285170A (en) * | 2018-02-09 | 2018-07-17 | 云南锡业研究院有限公司 | The method of Production By Sulfuric Acid Process metastannic acid and stannic oxide |
| CN108359805A (en) * | 2018-02-09 | 2018-08-03 | 云南锡业研究院有限公司 | A kind of method of Whote-wet method processing tin copper ashes |
| CN109234537A (en) * | 2018-10-19 | 2019-01-18 | 长沙汇聚环境技术有限公司 | A kind of recovery method as resource of tin-coated copper rice |
-
2021
- 2021-05-07 CN CN202110496415.2A patent/CN113060758B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100147684A1 (en) * | 2008-12-12 | 2010-06-17 | Electronics And Telecommunications Research Institute | Ultra-sensitive gas sensor using oxide semiconductor nanofiber and method of fabricating the same |
| CN101643238A (en) * | 2009-06-22 | 2010-02-10 | 云南锡业集团（控股）有限责任公司 | Method for producing tin dioxide |
| US20140127109A1 (en) * | 2011-05-10 | 2014-05-08 | Mitsubishi Materials Corporation | Tin(ii) oxide powder for replenishing tin component of tin-alloy plating solution and method for manufacturing said powder |
| CN104973620A (en) * | 2015-07-23 | 2015-10-14 | 柳州华锡铟锡材料有限公司 | Production method of large-particle sodium stannate crystals |
| CN108285170A (en) * | 2018-02-09 | 2018-07-17 | 云南锡业研究院有限公司 | The method of Production By Sulfuric Acid Process metastannic acid and stannic oxide |
| CN108359805A (en) * | 2018-02-09 | 2018-08-03 | 云南锡业研究院有限公司 | A kind of method of Whote-wet method processing tin copper ashes |
| CN109234537A (en) * | 2018-10-19 | 2019-01-18 | 长沙汇聚环境技术有限公司 | A kind of recovery method as resource of tin-coated copper rice |
Non-Patent Citations (2)
| Title |
|---|
| SHARMA,ASHUTOSH1: "Pulse plated Sn-Cu solder coatings from stannate bath", 《SOLDERING & SURFACE MOUNT TECHNOLOGY》 * |
| 吴杰等: "某锡铜硫化矿选厂磨矿分级工艺优化研究与实践", 《矿冶》 * |
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