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Defluorination method for zinc sulphate solution

A zinc sulfate solution and removal technology, which is applied in the direction of zinc sulfate, chemical instruments and methods, and rare earth metal compounds, can solve the problems of large amount of fluorine absorbing and desorbing agent, limited ability to absorb fluorine, and unsatisfactory removal effect. High recovery rate and quality, strong pertinence, short and easy fluoride removal process

Inactive Publication Date: 2012-02-01
孙位成
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The common methods for removing fluorine from high-fluorine raw materials include fire method and wet method. The fire method uses a rotary kiln or a multi-hearth furnace to roast the raw material to volatilize the fluorine in the raw material. Although this method is mature in technology, there is a relatively high energy consumption per unit. High, unsatisfactory removal effect and large pollution, this method is not ideal in the environment of rising global energy prices and advocating energy conservation and emission reduction; the wet method uses alkaline solution to wash the raw material to dissolve the fluorine in the raw material In solution, although this method has low energy consumption and good working environment, the process is complicated, and different process parameters are required for raw materials from different sources, so the operability is poor.
[0004] In order to overcome the above problems and develop a method with good operability, low energy consumption and ideal defluorination effect, various metal smelting enterprises and individuals have done a lot of research, such as "A fluorine absorbing agent for electrolyte in zinc electrolytic smelting and a method for removing fluorine using a fluorine absorbing agent" disclosed in Chinese patent literature (publication number: CN101001693, publication date: 2007.07.18), which discloses four types of zinc The fluorine absorbing and desorbing agent for the electrolyte and the fluorine removal method using the fluorine absorbing and desorbing agent are respectively alkaline ferric sulfate fluorine absorbing and desorbing agent, ferric peroxyhydroxide fluorine absorbing and desorbing agent, iron oxide fluorine absorbing and desorbing agent, hydrogen Iron oxide fluorine absorbing agent, due to the limited ability of the absorbing agent to absorb fluorine, the amount of fluorine absorbing agent used is huge, a large amount of waste water is generated during desorption, the pollution is serious, and the process is long, the investment in equipment is large, and the production cost of the enterprise High; another example is the "Fluorine and Chlorine Removal Technology by Ion Exchange Method for Zinc Wet Metallurgy Industrialization" disclosed in Chinese patent literature (publication number: CN101492772, publication date: 2009.07.29), which adopts the adsorption and desorption cycle process of anion exchange resin D201, Removing the fluorine in the high-fluorine zinc sulfate solution, this method is similar to the technology with the publication number CN101001693, and has the disadvantages of large wastewater discharge and serious pollution during desorption; another example is the "zinc sulfate solution defluorination process" disclosed in Chinese patent documents (Publication No.: CN1966407, Publication Date: 2007.05.23), which discloses a method of producing Al2(PO3F)3 precipitate A method for removing fluorine in a high-fluorine zinc sulfate solution, the method adopts Al2(SO4)3·12H2O and Na3PO4 · 12H2O as raw materials, there are large amounts of raw materials added, large amount of slag and zinc sulfate solution Disadvantages of large loss of zinc
[0005] To sum up, at present, my country's metal smelting industry is deeply troubled by excessive fluoride ions in hydrometallurgy, and lacks a good solution. A Simple, Pollution-free, Economical, Reliable and Practicable Method for Removing Fluoride in Zinc Sulfate Solution

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  • Defluorination method for zinc sulphate solution
  • Defluorination method for zinc sulphate solution
  • Defluorination method for zinc sulphate solution

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Embodiment 1

[0024] A method for removing fluorine in zinc sulfate solution, comprising the steps in the following order: A. ball milling process: adopt ceramic ball mill, add coarse Ce in the ball mill 2 (CO 3 ) 3 , add water to the ball mill, Ce in the ball mill 2 (CO 3 ) 3 The mass ratio of Ce to water is 1:1, and the Ce 2 (CO 3 ) 3 Wet milling, ball milling to make Ce 2 (CO 3 ) 3 Particle size 2 (CO 3 ) 3 Form slurry, slurry is used for precipitation defluorination process; B. precipitation defluorination: the slurry 243Kg (dry weight) of step A is added to 60 m 3 In the zinc sulfate solution with fluorine content of 0.311g / L and pH value of 5.0, the added Ce 2 (CO 3 ) 3 The mass ratio of fluorine to the zinc sulfate solution is 13:1, add sulfuric acid, the sulfuric acid is industrial sulfuric acid with a mass percentage concentration > 92%, adjust the pH value of the zinc sulfate solution to 3.0, control the temperature of the zinc sulfate solution to 60 ° C, pass Ce 2...

Embodiment 2

[0026] A method for removing fluorine in zinc sulfate solution, comprising the steps in the following order: A. ball milling process: adopt ceramic ball mill, add coarse Ce in the ball mill 2 (CO 3 ) 3 , add water to the ball mill, Ce in the ball mill 2 (CO 3 ) 3 The mass ratio to water is 1.5:1, the Ce 2 (CO 3 ) 3 Wet milling, ball milling to make Ce 2 (CO 3 ) 3 Particle size 2 (CO 3 ) 3 Form the slurry, which is used for precipitation defluorination process; B. precipitation defluorination: the slurry 361Kg (dry weight) of step A is added to 60 m 3 In the zinc sulfate solution with fluorine content of 0.43g / L and pH value of 5.2, the added Ce 2 (CO 3 ) 3 The mass ratio of fluorine to the zinc sulfate solution is 14:1, add sulfuric acid, the sulfuric acid is industrial sulfuric acid with a mass percentage concentration > 92%, adjust the pH value of the zinc sulfate solution to 4.0, control the temperature of the zinc sulfate solution to 70 ° C, pass Ce 2 (CO ...

Embodiment 3

[0028] A method for removing fluorine in zinc sulfate solution, comprising the steps in the following order: A. ball milling process: adopt ceramic ball mill, add coarse Ce in the ball mill 2 (CO 3 ) 3 , add water to the ball mill, Ce in the ball mill 2 (CO 3 ) 3 The mass ratio of Ce to water is 2:1, and the Ce 2 (CO 3 ) 3 Wet milling, ball milling to make Ce 2 (CO 3 ) 3 Particle size 2 (CO 3 ) 3 Form slurry, slurry is used for precipitation defluorination process; B. precipitation defluorination: the slurry 434Kg (dry weight) of step A is added to 60 m 3 In the zinc sulfate solution with fluorine content of 0.482g / L and pH value of 5.4, the added Ce 2 (CO 3 ) 3 The mass ratio of fluorine to the zinc sulfate solution is 15:1, add sulfuric acid, the sulfuric acid is industrial sulfuric acid with a mass percentage concentration > 92%, adjust the pH value of the zinc sulfate solution to 4.5, and control the temperature of the zinc sulfate solution to 80°C. Ce 2 (C...

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Abstract

The invention discloses a defluorination method for a zinc sulphate solution, comprising the following ordered steps of: A, a ball-milling process: milling coarse grains Ce2(CO3) with water by a ball mill, wherein the Ce2(CO3) is milled to have the grain size of less than 1 micrometer so as to form slurry, and the slurry is used for a sedimentation defluorination process; B, the sedimentation defluorination process: adding the slurry formed by the step A into the zinc sulphate solution with the pH value of 5.0-5.4, adding sulfuric acid to regulate the pH value to be 3.0-4.5, making the Ce2(CO3) react with the fluorine in the zinc sulphate solution to generate the CeCO3F sediment, wherein the concentration of fluorine ions in the solution is reduced to be less than 0.1g / L, the solution is filtered, the filtrate is used for regular zinc hydrometallurgy, and the filter residue is used for a sedimentation residue filtering and washing process; C, the sedimentation residue filtering and washing process: adding water for filtering and washing the filter residue obtained by the step B, wherein the filtered and washed liquid is used for the regular zinc hydrometallurgy, and the filtered and washed residue is sold. The method provided by the invention is featured by being short and easy, low in energy consumption, pollution free, low in technical operation difficulty, excellent in defluorination effect, low in operating cost, remarkable in economic benefits, and the like.

Description

Technical field [0001] The present invention is a wet metallurgical field in non -ferrous metal metallurgical. It specially involves a method of removing fluoride in a zinc sulfate solution. It is particularly suitable for dec no treatment of high fluorine zinc sulfate solution. Background technique [0002] At present, metal zinc is basically produced in wet -fired zinc.However, in the process of wetting zinc, it is necessary to strictly control the fluorine content in the electrolytic solution. If the fluorine content is too high (F - > 0.1 g / L), the cathode zinc and cathode aluminum plates produced by the electrolyte will cause the production failure such as cathode zinc, which will cause the production capacity of the enterprise to reduce the production capacity.Excessive fluoride content will also severely corrode the cathode aluminum plate, which will accelerate the damage of the cathode plate, which will cause the production cost of the enterprise to increase. This make...

Claims

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Application Information

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IPC IPC(8): C01G9/06C01F17/00
Inventor 孙位成
Owner 孙位成
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