CN113060758B - 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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- CN113060758B CN113060758B CN202110496415.2A CN202110496415A CN113060758B CN 113060758 B CN113060758 B CN 113060758B CN 202110496415 A CN202110496415 A CN 202110496415A CN 113060758 B CN113060758 B CN 113060758B
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- C01—INORGANIC CHEMISTRY
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- C01G19/00—Compounds of tin
- C01G19/02—Oxides
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- C—CHEMISTRY; METALLURGY
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/10—Sulfates
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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 powdery tin material and sulfuric acid are synthesized into a tin dioxide intermediate product at high temperature and high pressure in an oxidizing atmosphere in a closed container, ammonium bicarbonate is added for neutralization after washing, the solid obtained after liquid-solid separation is dried and calcined to obtain a tin dioxide product, the residual liquid is returned to prepare a sulfuric acid solution until the copper content reaches 48-52 g/l, and a copper sulfate product is obtained by concentration and crystallization. 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.
The Chinese invention patent with the patent number ZL201810135124.9 discloses a method for producing metastannic acid and tin dioxide by a sulfuric acid method. 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 adopts a wet method to prepare metastannic acid and tin dioxide powder, the method is to heat tin and nitric acid to prepare metastannic acid under the conditions of closed oxygenation and pressurization, and to prepare tin dioxide by high-temperature calcination. 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 with the application number of 200810058872.8 also discloses a method for producing alkali metal stannate, which comprises the step of heating metal tin powder to react with potassium (sodium) hydroxide under the closed condition of adding oxygen and pressurizing to produce the 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 taking materials on the sieves, which are sieved by a 40-mesh sieve or a 60-mesh sieve, as flaky tin flowers with low copper content as raw materials for preparing 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; the powdery tin material and sulfuric acid are synthesized into a tin dioxide intermediate product at high temperature and high pressure in an oxidizing atmosphere in a closed container, the tin dioxide intermediate product is washed by water and then neutralized by ammonium carbonate, liquid-solid separation is carried out, the solid is dried and calcined to obtain a tin dioxide product, the residual liquid is returned to prepare a sulfuric acid solution until the copper content reaches 48-52 g/l, and a copper sulfate product is obtained by concentration and crystallization.
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, 0.1-0.46 wt% of Fe, less than or equal to 30 wt% of Cu and less than or equal to 0.1 wt% of Pb.
Furthermore, 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 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, 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 alkaline solution, and returning the filter residue to copper smelting for the iron-containing copper slag.
Further, the powdery tin material and sulfuric acid are synthesized into a tin dioxide intermediate product at high temperature and high pressure in an oxygen atmosphere in a closed container, the mass ratio of the sulfuric acid to the powdery tin material is 4-10, 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 neutralized by ammonium carbonate until the pH value is 7-8, then the tin dioxide intermediate product is subjected to liquid-solid separation, the separated solid is subjected to vacuum drying at the temperature of 100-400 ℃ for 5-12 hours, and is roasted at the temperature of 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) Wet grinding 2000g of tin-copper slag containing 29.14 wt%, 58.21 wt%, 0.022 wt%, 0.46 wt%, 0.25 wt% and 2.3 wt% of copper, by using a rod mill, according to the pulp concentration of 50%, grinding for 40 minutes, screening the ground pulp by using a 60-mesh rotary screen to obtain 212g of oversize material (tin flower) containing 83.64 wt% of tin and 1.78 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 1723.34g of powdery tin material containing 56.12 wt% of tin and 33.26 wt% of copper, and returning the filtrate to a 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 constant temperature for 3 hours, cooling, discharging, filtering, concentrating, crystallizing and centrifuging a leaching solution to obtain 643g of a potassium stannate product, wherein the tin content is 38.24 wt%, and the tin direct yield is 98 wt%, and the product meets the standard requirements of products. 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, 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 99.17wt.%, the iron content is 0.024wt.%, the lead content is 0.0021wt.%, the antimony content is 0.0012wt.%, the direct tin yield is 94.98%, and the standard requirement of the product is met.
Claims (3)
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 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; returning the materials between 60-100 mesh to grind; grinding ore by a rod mill and wet grinding, wherein the mass concentration of ore pulp is 40-70%, and the grinding time is 15-60 minutes; 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; 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 into the tin dioxide intermediate product for washing, adding ammonium carbonate for neutralization, carrying out liquid-solid separation, drying and calcining the solid to obtain a 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 a copper sulfate product;
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, the tin-copper slag contains more than or equal to 55 wt% of Sn, 0.1-0.46 wt% of Fe, less than or equal to 30 wt% of Cu and less than or equal to 0.1 wt% of Pb.
2. 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 liquid-solid mass ratio of the potassium hydroxide solution or sodium hydroxide solution to the tin flower is 7-10, 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, the concentrated mother solution returns to prepare alkaline solution, and the filter residue is iron-containing copper slag and returns to copper smelting.
3. The method for preparing tin dioxide and stannate by using tin-copper slag according to claim 1, wherein the powdery tin material and sulfuric acid are used for synthesizing a tin dioxide intermediate product 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 powdery tin material is 4-10, the initial acidity of the sulfuric acid is less than or equal to 150g/l, the reaction pressure is greater than or equal to 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, concentrated crystallization is carried out to produce a copper sulfate product, the separated tin dioxide intermediate product is washed by adding water and neutralized by ammonium carbonate to pH 7-8, then subjected to liquid-solid separation, the separated solid is subjected to vacuum drying at 100-400 ℃ for 5-12 hours, and is roasted at 600-1000 ℃ for 4-8 hours, and the tin dioxide product is obtained.
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| 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 |
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| KR101201897B1 (en) * | 2008-12-12 | 2012-11-16 | 한국전자통신연구원 | Ultra High Sensitive Gas Sensors Using Semiconductor Oxide Nanofiber and Method for Preparing 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 |
| JP5807377B2 (en) * | 2011-05-10 | 2015-11-10 | 三菱マテリアル株式会社 | Stannous oxide powder for supplying Sn component to Sn alloy plating solution and method for producing the same |
| CN108359805B (en) * | 2018-02-09 | 2019-08-30 | 云南锡业研究院有限公司 | A kind of method of Whote-wet method processing tin copper ashes |
| CN108285170B (en) * | 2018-02-09 | 2020-07-14 | 云南锡业研究院有限公司 | Method for producing metastannic acid and stannic oxide by sulfuric acid method |
| 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 |
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| 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 |
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| Pulse plated Sn-Cu solder coatings from stannate bath;Sharma,Ashutosh1;《Soldering & Surface Mount Technology》;20200203;第32卷;全文 * |
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