CN102586804A - Method for removing fluorine ion from manganese sulfate solution for producing electrolytic manganese metal - Google Patents
Method for removing fluorine ion from manganese sulfate solution for producing electrolytic manganese metal Download PDFInfo
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Abstract
The invention provides a method for removing fluorine ion from manganese sulfate solution for producing electrolytic manganese metal, which comprises the following step of: when the manganese sulfate solution for producing the electrolytic manganese metal is prepared from rhodochrosite, pyrolusite, pyrite and vitriol, adding fluorine removing agent calcium carbonate and kieselguhr to remove the fluorine ion from the solution, so that the fluorine ion content in the manganese sulfate solution is less than or equal to 60mug/g. The method is simple to operate, the loss of the manganese in the solution can be avoided when the fluorine ion is removed, a cathode can not be corroded when a metal sheet is produced by the fluorine ion-free manganese sulfate solution in an electrolysis way, and the single plate is high in yield.
Description
Technical field
The present invention relates to the production of electrolytic metal Mn, especially a kind of electrolytic metal Mn production is with the fluoride ion removing method in the manganese sulfate solution.
Background technology
In existing electrolytic metal Mn industrial production, use the manganous sulfate and the vitriolic aqueous solution as electrolytic solution.Adopt stainless steel plate as negative electrode; Plumbous antimony tin silver quad alloy is as anode, the manganese sulfate solution in the electrolytic solution from two kinds of ores of manganous carbonate and Manganse Dioxide through the processing pulverize after, after soaking, obtain with sulfuric acid reaction is molten; The production of existing conventional production electrolytic metal Mn is dissolved the general manganese sulfate solution that adopts manganese carbonate ore and sulfuric acid to generate with manganous sulfate; Along with the production capacity expansion of electrolytic metal Mn, the increasing demand of manganese carbonate ore increases, and it is low to cause manganese carbonate ore to go out the present price higher-grade; In order to seek utilization the best of resource, the technology variation is produced electrolytic metal Mn production and is used manganese sulfate solution.Make it to occur use manganese carbonate ore, dioxide ore for manganese, sulfurous iron ore hybrid system and produced the manganese sulfate solution of manganese sulfate solution and two ore deposit single stage method (sulfurous iron ore and dioxide ore for manganese) production.But in existing sulfide removal of impurities process, can only remove copper, cobalt, nickel, lead, iron), zinc, fluorine is removed, the sulfide removal of impurities can not be removed.Content of fluoride ion reaches more than the 150ppm in the manganese sulfate solution that manganese sulfate solution that use manganese carbonate ore, dioxide ore for manganese, three kinds of ores of sulfurous iron ore are produced and two ore deposit single stage method (sulfurous iron ore and dioxide ore for manganese) are produced; In the electrolytic metal Mn production process; Content of fluoride ion in the manganese sulfate solution is too high, and (F->=90ppm) can the accelerated corrosion positive plate; Reduce current efficiency, influence quality product, severe patient can not be produced.
In the existing industrial production; Method as defluorination in the known manganese sulfate solution commonly used is to carry out through adding milk of lime, is to make calcium hydroxide and fluorion form insoluble Calcium Fluoride (Fluorspan), and adsorbs through silicon-dioxide in the solution; The shortcoming of this method is in adding ash charge breast process, to understand solution local pH value greater than more than 7; Cause the manganous sulfate loss, and anti-dissolving of the insoluble Calcium Fluoride (Fluorspan) that when PH is following less than 6, forms, cause the fluorion of removing to exist in solution with the ionic form again; And dioxide-containing silica can not be added by the external world in the manganese sulfate solution, just is difficult to remove when fluoride ion removing is to 100ppm in the manganese sulfate solution.Can not satisfy in the electrolytic metal production fluorion in the manganese sulfate solution≤60ug/g requirement.
Summary of the invention
The purpose of this invention is to provide a kind of a kind of method that can remove with fluorion in the manganese sulfate solution of manganese carbonate ore, dioxide ore for manganese, sulfurous iron ore and gas washing in SA production; Content of fluoride ion is lower than 60ug/g in the making manganese sulfate solution; Minimizing is because of the too high corrosion negative plate of content of fluoride ion in the manganese sulfate solution; Improve current efficiency, increase veneer output.
Technical scheme of the present invention:
For reaching the invention described above purpose; Take following solution to the problems described above; Add defluorinating agent lime carbonate and a kind of method of zeyssatite (adding high calcium zeyssatite in case of necessity) removal fluorion when adopting manganese carbonate ore, dioxide ore for manganese, sulfurous iron ore and sulfuric acid to produce electrolytic metal Mn with manganese sulfate solution; Add the reaction of defluorinating agent lime carbonate and zeyssatite and remove fluorion, make the content of fluoride ion≤60ug/g in the manganese sulfate solution.
In addition, characteristic of the present invention also has, and defluorinating agent lime carbonate and diatomaceous weight proportion are 2: 1.
In addition, characteristic of the present invention also has, and solution temperature is controlled at 50 ℃-90 ℃ when adding defluorinating agent.
In addition, characteristic of the present invention also has, and the pH value of solution value is controlled at 3-6.5 when adding defluorinating agent.
In addition, characteristic of the present invention also has, and the adding defluorinating agent afterreaction time was controlled at 30-50 minute.
In addition, characteristic of the present invention also has, and insoluble Calcium Fluoride (Fluorspan) that forms in the solution behind the adding defluorinating agent and Sellaite fine particle are rapidly by diatomite adsorption.
Provided by the present inventionly be; Adopt manganese carbonate ore, dioxide ore for manganese, sulfurous iron ore and sulfuric acid to produce electrolytic metal Mn and under said temperature, pH value and reaction times condition, add defluorinating agent lime carbonate and a kind of method of zeyssatite (2: 1) removal fluorion, adopt this method to make electrolytic metal Mn with the fluorine in the manganese sulfate solution (F) ion content≤60ug/g with manganese sulfate solution.
Advantage of the present invention:
1, the used defluorinating agent of the present invention is that lime carbonate and zeyssatite are removed the fluorion in the manganese sulfate solution of electrolytic metal Mn production usefulness, can not cause manganese loss in the solution.
2, of the present invention with fluoride ion removing to less than 60ug/g, can not corrode electrolytic metal production and use the negative electrode stainless steel plate.
3, veneer output of the present invention is higher than simultaneous test, can under identical shared device device, improve usage ratio of equipment, reduces the investment of shared device.
4, the removal of fluorion of the present invention and traditional treatment method compare, and be workable, non-environmental-pollution.
Embodiment
Adding defluorinating agent lime carbonate of the present invention and zeyssatite (2: 1) are removed and are adopted manganese carbonate ore, dioxide ore for manganese, sulfurous iron ore and sulfuric acid to leach electrolytic metal Mn to use the manganese sulfate solution fluorion.
Behind the adding defluorinating agent of the present invention, the manganese sulfate solution temperature is controlled at 50 ℃-90 ℃, and the pH value is controlled at 3-6.5, and the reaction times was controlled at 30-50 minute.
Embodiment 1
Add manganese carbonate ore, dioxide ore for manganese, sulfurous iron ore, the molten leaching of sulfuric acid reaction manganese sulfate solution in the bucket (7 meters of diameters, high 6.5 meters) molten soaking; Add defluorinating agent lime carbonate and zeyssatite (2: 1) and remove fluorion; Various raw material consumptions are seen table 1-1; Calcium contents in the lime carbonate>=50% wherein, dioxide-containing silica in the zeyssatite>=90%, calcium contents≤5%.
After adding defluorinating agent, the manganese sulfate solution temperature is controlled at 50 ℃, and pH is controlled at 3.0, and the reaction times was controlled at 50 minutes.
After by above-mentioned condition manganese sulfate solution being removed fluorine, subsequent handling is produced qualified manganese sulfate solution by former electrolytic metal Mn operation operation, is used for electrolytic metal Mn production, and the cycle is 30 days.
Manganese sulfate solution physico-chemical analysis result is shown in table 1-2 (its result is each experiment bucket 30 day average); Veneer output (its result is each experiment bucket 30 day average) and negative plate corrosion situation (30 days cycles) are shown in table 1-3; The experiment barrel number is 1-3, and corresponding electrolyzer number is 7-9; The simultaneous test defluorinating agent adopts milk of lime, and all the other conditions are identical with the experiment bucket, and barrel number is 4-6, and the electrolyzer of correspondence number is 10-12.
Table 1-1
Table 1-2
Table 1-3
Among the table 1-2: content of fluoride ion detects with fluorine ionometer
Can know that electrolytic metal Mn of the present invention obviously is superior to the contrast experiment with fluoride ion removing effect in the manganese sulfate solution, manganese (Mn in the solution from table 1-2, table 1-3
2+) do not lose.Spend remove fluorion after this sulphuric acid soln electrolysis production manganese metal sheet veneer output apparently higher than the contrast experiment, and can the production of corroding metal manganese not use the negative electrode stainless steel plate through 30 days continuous production.
Embodiment 2
Add manganese carbonate ore, dioxide ore for manganese, sulfurous iron ore, the molten leaching of sulfuric acid reaction manganese sulfate solution in the bucket (7 meters of diameters, high 6.5 meters) molten soaking; Add defluorinating agent lime carbonate and zeyssatite (2: 1) and remove fluorion; Various raw material consumptions are seen table 2-1; Calcium contents in the lime carbonate>=50% wherein, dioxide-containing silica in the zeyssatite>=90%, calcium contents≤5%.
After adding defluorinating agent, the manganese sulfate solution temperature is controlled at 60 ℃, and pH is controlled at 4.0, and the reaction times was controlled at 40 minutes.
After by above-mentioned condition manganese sulfate solution being removed fluorine, subsequent handling is produced qualified manganese sulfate solution by former electrolytic metal Mn operation operation, is used for electrolytic metal Mn production, and the cycle is 30 days.
Manganese sulfate solution physico-chemical analysis result is shown in table 2-2 (its result is each experiment bucket 30 day average); Veneer output (its result is each experiment bucket 30 day average) and negative plate corrosion situation (30 days cycles) are shown in table 2-3; The experiment barrel number is 13-15, and corresponding electrolyzer number is 19-21; The simultaneous test defluorinating agent adopts milk of lime, and all the other conditions are identical with the experiment bucket, and barrel number is 16-18, and the electrolyzer of correspondence number is 22-24.
Table 2-1
Table 2-2
Table 2-3
Among the table 2-2: content of fluoride ion detects with fluorine ionometer
Can know that electrolytic metal Mn of the present invention obviously is superior to the contrast experiment with fluoride ion removing effect in the manganese sulfate solution, manganese (Mn in the solution from table 2-2, table 2-3
2+) do not lose.Spend remove fluorion after this sulphuric acid soln electrolysis production manganese metal sheet veneer output apparently higher than the contrast experiment, and can the production of corroding metal manganese not use the negative electrode stainless steel plate through 30 days continuous production.
Embodiment 3
Add manganese carbonate ore, dioxide ore for manganese, sulfurous iron ore, the molten leaching of sulfuric acid reaction manganese sulfate solution in the bucket (7 meters of diameters, high 6.5 meters) molten soaking; Add defluorinating agent lime carbonate and zeyssatite (2: 1) and remove fluorion; Various raw material consumptions are seen table 3-1; Calcium contents in the lime carbonate>=50% wherein, dioxide-containing silica in the zeyssatite>=90%, calcium contents≤5%.
After adding defluorinating agent, the manganese sulfate solution temperature is controlled at 70 ℃, and pH is controlled at 5.0, and the reaction times was controlled at 35 minutes.
After by above-mentioned condition manganese sulfate solution being removed fluorine, subsequent handling is produced qualified manganese sulfate solution by former electrolytic metal Mn operation operation, is used for electrolytic metal Mn production, and the cycle is 30 days.
Manganese sulfate solution physico-chemical analysis result is shown in table 3-2 (its result is each experiment bucket 30 day average); Veneer output (its result is each experiment bucket 30 day average) and negative plate corrosion situation (30 days cycles) are shown in table 3-3; The experiment barrel number is 25-27, and corresponding electrolyzer number is 31-33; The simultaneous test defluorinating agent adopts milk of lime, and all the other conditions are identical with the experiment bucket, and barrel number is 28-30, and the electrolyzer of correspondence number is 34-36.
Table 3-1
Table 3-2
Table 3-3
Among the table 3-2: content of fluoride ion detects with fluorine ionometer
Can know that electrolytic metal Mn of the present invention obviously is superior to the contrast experiment with fluoride ion removing effect in the manganese sulfate solution, manganese (Mn in the solution from table 3-2, table 3-3
2+) do not lose.Spend remove fluorion after this sulphuric acid soln electrolysis production manganese metal sheet veneer output apparently higher than the contrast experiment, and can the production of corroding metal manganese not use the negative electrode stainless steel plate through 30 days continuous production.
Embodiment 4
Add manganese carbonate ore, dioxide ore for manganese, sulfurous iron ore, the molten leaching of sulfuric acid reaction manganese sulfate solution in the bucket (7 meters of diameters, high 6.5 meters) molten soaking; Add defluorinating agent lime carbonate, high calcium zeyssatite (2: 1) removal fluorion; Various raw material consumptions are seen table 4-1; Calcium contents in the lime carbonate >=50% wherein, dioxide-containing silica in the high calcium zeyssatite >=90%, calcium contents >=5%.
After adding defluorinating agent, the manganese sulfate solution temperature is controlled at 80 ℃, and pH is controlled at 6.0, and the reaction times was controlled at 30 minutes.
After by above-mentioned condition manganese sulfate solution being removed fluorine, subsequent handling is produced qualified manganese sulfate solution by former electrolytic metal Mn operation operation, is used for electrolytic metal Mn production, and the cycle is 30 days.
Manganese sulfate solution physico-chemical analysis result is shown in table 4-2 (its result is each experiment bucket 30 day average); Veneer output (its result is each experiment bucket 30 day average) and negative plate corrosion situation (30 days cycles) are shown in table 4-3; The experiment barrel number is 37-39, and corresponding electrolyzer number is 43-45; The simultaneous test defluorinating agent adopts milk of lime, and all the other conditions are identical with the experiment bucket, and barrel number is 40-42, and the electrolyzer of correspondence number is 46-48.
Table 4-1
Table 4-2
Table 4-3
Among the table 4-2: content of fluoride ion detects with fluorine ionometer
Can know that electrolytic metal Mn of the present invention obviously is superior to the contrast experiment with fluoride ion removing effect in the manganese sulfate solution, manganese (Mn in the solution from table 4-2, table 4-3
2+) do not lose.Spend remove fluorion after this sulphuric acid soln electrolysis production manganese metal sheet veneer output apparently higher than the contrast experiment, and can the production of corroding metal manganese not use the negative electrode stainless steel plate through 30 days continuous production.
Embodiment 5
Add manganese carbonate ore, dioxide ore for manganese, sulfurous iron ore, the molten leaching of sulfuric acid reaction manganese sulfate solution in the bucket (7 meters of diameters, high 6.5 meters) molten soaking; Add defluorinating agent lime carbonate and zeyssatite (2: 1) and remove fluorion; Various raw material consumptions are seen table 5-1; Calcium contents in the lime carbonate>=50% wherein, dioxide-containing silica in the zeyssatite>=90%, calcium contents≤5%.
After adding defluorinating agent, the manganese sulfate solution temperature is controlled at 90 ℃, and pH is controlled at 6.5, and the reaction times was controlled at 30 minutes.
After by above-mentioned condition manganese sulfate solution being removed fluorine, subsequent handling is produced qualified manganese sulfate solution by former electrolytic metal Mn operation operation, is used for electrolytic metal Mn production, and the cycle is 30 days.
Manganese sulfate solution physico-chemical analysis result is shown in table 5-2 (its result is each experiment bucket 30 day average); Veneer output (its result is each experiment bucket 30 day average) and negative plate corrosion situation (30 days cycles) are shown in table 5-3; The experiment barrel number is 49-51, and corresponding electrolyzer number is 52-54; The simultaneous test defluorinating agent adopts milk of lime, and all the other conditions are identical with the experiment bucket, and barrel number is 55-57, and the electrolyzer of correspondence number is 58-60.
Table 5-1
Table 5-2
Table 5-3
Among the table 5-2: content of fluoride ion detects with fluorine ionometer
Can know that from table 5-2, table 5-3 electrolytic metal Mn of the present invention obviously is superior to the contrast experiment with fluoride ion removing effect in the manganese sulfate solution, manganese in the solution (Mn2+) does not lose.Spend remove fluorion after this sulphuric acid soln electrolysis production manganese metal sheet veneer output apparently higher than the contrast experiment, and can the production of corroding metal manganese not use the negative electrode stainless steel plate through 30 days continuous production.
Claims (4)
1. an electrolytic metal Mn is with the removal method of fluorion in the manganese sulfate solution; It is characterized in that: when adopting rhodochrosite, pyrolusite, sulfurous iron ore and sulfuric acid to produce electrolytic metal Mn to use manganese sulfate solution; Add defluorinating agent lime carbonate and zeyssatite and remove fluorion in the solution, make the content of fluoride ion≤60ug/g in the manganese sulfate solution.
2. electrolytic metal Mn as claimed in claim 1 is characterized in that with the removal method of fluorion in the manganese sulfate solution: defluorinating agent lime carbonate and diatomaceous weight proportion are 2:1.
3. according to claim 1 or claim 2 electrolytic metal Mn is with the removal method of fluorion in the manganese sulfate solution, and it is characterized in that: solution temperature is controlled at 50 ℃-90 ℃ when adding defluorinating agent, and the pH value is controlled at 3-6.5, and the reaction times was controlled at 30-50 minute.
4. electrolytic metal Mn as claimed in claim 1 is characterized in that with the removal method of fluorion in the manganese sulfate solution: lime carbonate (calcium contents>=50%) and zeyssatite (calcium contents≤5%, dioxide-containing silica>=90%)
Calcium contents in the lime carbonate>=50%, dioxide-containing silica in the zeyssatite>=90%, calcium contents≤5%.
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Cited By (11)
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| CN103014760A (en) * | 2013-01-09 | 2013-04-03 | 广西有色金属集团汇元锰业有限公司 | Production method of electrolytic manganese metal |
| CN103074490A (en) * | 2013-01-09 | 2013-05-01 | 广西有色金属集团汇元锰业有限公司 | Purification method in electrolytic metal manganese production process by multi-mine method |
| CN103779617A (en) * | 2012-10-25 | 2014-05-07 | 梁达保 | Method for adding carbonate into lead electrolyte to treat hydrofluoric acid |
| CN103779616A (en) * | 2012-10-25 | 2014-05-07 | 梁达保 | Method for inhibiting the generation of hydrofluoric acid by adding glass fibers into lead electrolyte |
| CN103864078A (en) * | 2012-12-17 | 2014-06-18 | 沁阳市昊达实业有限公司 | A method of removing residue hydrogen fluoride in fluosilicic acid |
| CN104891577A (en) * | 2015-05-20 | 2015-09-09 | 中南大学 | Method for removing fluorinion from high-purity manganese sulfate solution |
| CN105002521A (en) * | 2015-08-07 | 2015-10-28 | 长沙矿冶研究院有限责任公司 | Method for removing magnesium impurities in electrolytic manganese system through fluorine-bearing minerals |
| CN105540935A (en) * | 2016-01-29 | 2016-05-04 | 铜陵有色金属集团股份有限公司铜冠冶化分公司 | Method for removing fluorin ions, sulfate radical ions and iron ions from organic amine liquor |
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| CN107130258A (en) * | 2017-05-24 | 2017-09-05 | 中南大学 | A kind of method of the fluorine removal from fluorine-containing solution of zinc sulfate |
| CN112267023A (en) * | 2020-09-25 | 2021-01-26 | 衢州华友钴新材料有限公司 | Two-stage defluorination method for fluorine-containing material |
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| CN103779616A (en) * | 2012-10-25 | 2014-05-07 | 梁达保 | Method for inhibiting the generation of hydrofluoric acid by adding glass fibers into lead electrolyte |
| CN103779617B (en) * | 2012-10-25 | 2016-08-17 | 梁达保 | The method adding processes of carbonate treatment Fluohydric acid. in lead electrolytic solution |
| CN103864078A (en) * | 2012-12-17 | 2014-06-18 | 沁阳市昊达实业有限公司 | A method of removing residue hydrogen fluoride in fluosilicic acid |
| CN103864078B (en) * | 2012-12-17 | 2016-02-24 | 沁阳市昊达实业有限公司 | A kind of method removing residual fluorinated hydrogen in silicofluoric acid |
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| CN103014760B (en) * | 2013-01-09 | 2015-04-15 | 广西有色金属集团汇元锰业有限公司 | Production method of electrolytic manganese metal |
| CN103014760A (en) * | 2013-01-09 | 2013-04-03 | 广西有色金属集团汇元锰业有限公司 | Production method of electrolytic manganese metal |
| CN104891577A (en) * | 2015-05-20 | 2015-09-09 | 中南大学 | Method for removing fluorinion from high-purity manganese sulfate solution |
| CN104891577B (en) * | 2015-05-20 | 2019-01-04 | 中南大学 | The minimizing technology of fluorine ion in high-purity sulphuric acid manganese solution |
| CN105002521A (en) * | 2015-08-07 | 2015-10-28 | 长沙矿冶研究院有限责任公司 | Method for removing magnesium impurities in electrolytic manganese system through fluorine-bearing minerals |
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| CN105859540B (en) * | 2016-04-26 | 2019-07-19 | 南通宝凯化工有限公司 | A kind of chloroacetic synthesis and production process of difluoro |
| CN107130258A (en) * | 2017-05-24 | 2017-09-05 | 中南大学 | A kind of method of the fluorine removal from fluorine-containing solution of zinc sulfate |
| CN112267023A (en) * | 2020-09-25 | 2021-01-26 | 衢州华友钴新材料有限公司 | Two-stage defluorination method for fluorine-containing material |
| CN112267023B (en) * | 2020-09-25 | 2022-07-08 | 衢州华友钴新材料有限公司 | Two-stage defluorination method for fluorine-containing material |
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Application publication date: 20120718 |