CN101318706A - Method for preparing high-purity manganese carbonate with pyrolusite - Google Patents
Method for preparing high-purity manganese carbonate with pyrolusite Download PDFInfo
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- CN101318706A CN101318706A CNA2008100484324A CN200810048432A CN101318706A CN 101318706 A CN101318706 A CN 101318706A CN A2008100484324 A CNA2008100484324 A CN A2008100484324A CN 200810048432 A CN200810048432 A CN 200810048432A CN 101318706 A CN101318706 A CN 101318706A
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Abstract
The invention discloses a method for preparing high-purity manganous carbonate from pyrolusite. The method comprises the following steps that: a pure manganese sulphate solution is prepared by using a manganese sulphate solution which is leached by sulphuric acid after the pyrolusite is added with aniline and removing impurities such as organic matters, heavy metal, calcium, magnesium, silicon and so on, through a purification impurity-removal process; and the manganese sulphate solution is added with micro calcium and magnesium complexing agents and is carbonized by carbonate, washed and dried, and a high-purity manganous carbonate product is prepared. The method has simple process, less investment and low cost; and the quality of the product achieves the HG/T2836-1997 I standard.
Description
Technical field
The present invention relates to a kind of method of high-purity manganese carbonate, particularly a kind of method with preparing high-purity manganese carbonate with pyrolusite.
Background technology
High-purity manganese carbonate is a kind of inorganic chemistry functional materials, and purposes is very widely arranged.Domestic production method all is raw material with the electrolytic metal Mn, and technology is long, investment is big, cost is high.
Summary of the invention
Purpose of the present invention is exactly that a kind of method with preparing high-purity manganese carbonate with pyrolusite will be provided, and it is a raw material with the manganese sulfate solution that pyrolusite leaches, and removes detrimental impurity through impurity and purification technology, the preparation high-purity manganese carbonate.
The object of the present invention is achieved like this: a kind of method with preparing high-purity manganese carbonate with pyrolusite, pyrolusite is added aniline leach manganese sulfate solution for 10%-60% sulfuric acid through weight percent concentration, neutralization is regulated the pH value of manganese sulfate solution to 2-6, be to add 2 grams-10 gram gacs and 1 gram-6 gram vulcanizing agents in per 1000 milliliters of the 4%-15% manganese sulfate solution toward weight percent concentration then, be warming up to 30 ℃ of-70 ℃ of stirring reactions 10 minutes-50 minutes, continue to be warming up to 50 ℃-100 ℃, add 2 grams-10 gram villiaumite or hydrofluoric acid, stirring reaction 1 hour-4 hours, stop to heat up, the oxygenant stirring reaction 15 minutes-120 minutes that adds 1 gram-10 gram inorganic flocculating agents and 2 milliliters-40 milliliters again, add the weight percentage concentration again and be 25% ammoniacal liquor 1 gram-10 gram adjust pHs to 5-7, stirring reaction 1 minute-120 minutes, the organic floculant that adds 50ppm-200ppm again, standing sedimentation 1 hour-12 hours, filter, the calcium that adds 50ppm-200ppm in the filtrate, the magnesium ion complexing agent, under 20 ℃ of-60 ℃ of temperature, add weight percent concentration and be the carbonate reaction 30 minutes of 10%-40%, filter, deionized water wash 3-5 filters all over being 7 to PH, be drying to obtain high-purity manganese carbonate.
Villiaumite is Neutral ammonium fluoride or Sodium Fluoride.
Vulcanizing agent is barium sulphide or ammonium sulfide or dithiocar-bamate.
Oxygenant is potassium permanganate or Manganse Dioxide or hydrogen peroxide or hypochlorous acid.
Inorganic flocculating agent is ferric sulfate or iron trichloride or aluminum chloride.
Organic floculant is the polyacrylic acid amine.
Calcium, magnesium ion complexing agent are organic acid or phosphoric acid salt.
Adopt method of the present invention to produce high-purity manganese carbonate, technology is simple, less investment, cost are low, and quality can reach I type standard.
Embodiment
Embodiment one, getting pyrolusite, to add weight percent concentration that aniline leaches for 10%-60% sulfuric acid through weight percent concentration be 1000 milliliters of 12% manganese sulfate solutions, with weight percent concentration is that to transfer pH value be 4.5 for 12% ammoniacal liquor, add 5 gram gacs, 3 gram ammonium sulfides, be warming up to 50 ℃-60 ℃, stirring reaction 30 minutes, add 6 gram Neutral ammonium fluorides again, be warming up to 90 ℃, reacted 60 minutes, stop to heat up, adding is the ferrum sulfuricum oxydatum solutum of 5%-10% by the weight percent concentration that 2 gram ferric sulfate are made into, stirring reaction 20 minutes, add weight percent concentration and be 5 milliliters in 30% hydrogen peroxide, stirring reaction 20 minutes, with weight percent concentration is that 25% ammoniacal liquor is transferred pH value to 6.8, reacted 30 minutes, adding the weight percentage concentration is 20 milliliters of 1 ‰ polyacrylic acid amine aqueous solutions, stirred 30 minutes, left standstill 4 hours, and filtered, it is 20 milliliters of 1 ‰ polyacrylic acid amine aqueous solutions that filtrate adds the weight percentage concentration again, left standstill 8 hours, filter, filtrate adds 0.02 gram tartrate (wiring solution-forming), stirring reaction 20 minutes, with weight percent concentration is that to be neutralized to pH value be 7 for 20% ammonium bicarbonate soln, reacted 30 minutes, and filtered, filter cake deionized water wash 4 times, 80 ℃ of hot-air dries get high-purity manganese carbonate product 84 grams.
Embodiment two, getting pyrolusite, to add weight percent concentration that aniline leaches for 10%-60% sulfuric acid through heavy percentage concentration concentration be 5000 milliliters of 12% manganese sulfate solutions, with weight percent concentration is that to transfer pH value be 5 for 12% ammoniacal liquor, add 25 gram gacs, 15 gram nabams, be warming up to 50 ℃-60 ℃, stirring reaction 30 minutes, add 40 gram Sodium Fluorides again, be warming up to 90 ℃, reacted 50 minutes, stop to heat up, adding is the ferrum sulfuricum oxydatum solutum of 5%-10% by the weight percent concentration that 12 gram ferric sulfate are made into, stirring reaction 20 minutes, add weight percent concentration and be 25 milliliters of 30% potassium permanganate solutions, stirring reaction 20 minutes, with weight percent concentration is that 25% ammoniacal liquor is transferred pH value to 6.5, reacted 30 minutes, adding the weight percentage concentration is 120 milliliters of 1 ‰ polyacrylic acid amine aqueous solutions, stirred 15 minutes, left standstill 2 hours, and filtered, it is 100 milliliters of 1 ‰ polyacrylic acid amine aqueous solutions that filtrate adds the weight percentage concentration again, left standstill 12 hours, filter, filtrate adds 0.2 gram tripoly phosphate sodium STPP (wiring solution-forming), stirring reaction 20 minutes, with weight percent concentration is that to be neutralized to pH value be 7.2 for 20% ammonium bicarbonate soln, reacted 30 minutes, and filtered, filter cake deionized water wash 4 times, 80 ℃ of hot-air dries get high-purity manganese carbonate product 84.5 grams.
Embodiment three, getting pyrolusite, to add weight percent concentration that aniline leaches for 10%-60% sulfuric acid through heavy percentage concentration be 10 cubic metres of 12% manganese sulfate solutions, with weight percent concentration is that to transfer pH value be 3 for 12% ammoniacal liquor, add 50 kilograms of gacs, 30 kilograms of ammonium sulfides, be warming up to 50 ℃-60 ℃, stirring reaction 30 minutes, add 50 kilograms of Neutral ammonium fluorides again, be warming up to 75 ℃, reacted 1.5 hours, stop to heat up, the weight percent concentration that adding is made into by 2 kilograms of iron(ic) chloride is 8% ferric chloride Solution, and stirring reaction 2 hours adds weight percent concentration and be 50 liters in 30% hydrogen peroxide, stirring reaction 40 minutes, ammoniacal liquor with weight percent concentration 25% is transferred pH value to 6.5, reacts 50 minutes, adds poly amic acid 20 grams, stirred 30 minutes, left standstill 1.5 hours, and filtered, filtrate adds poly amic acid 10 grams again, left standstill 10 hours, filter, filtrate adds 2 kilograms of tripoly phosphate sodium STPPs (wiring solution-forming), stirring reaction 40 minutes, with weight percent concentration is that to be neutralized to pH value be 7.2 for 20% ammonium bicarbonate soln, reacted 30 minutes, and filtered, filter cake deionized water wash 4 times, 80 ℃ of hot-air dries get 900 kilograms of high-purity manganese carbonate products.
But the substitution of materials of enumerating in the villiaumite that relates among the above embodiment, vulcanizing agent, oxygenant, the inorganic flocculating agent by specification.In the material that organic floculant, calcium ions and magnesium ions complexing agent refer to enumerate in the specification sheets any one.
Claims (7)
1, a kind of method with preparing high-purity manganese carbonate with pyrolusite, it is characterized in that: pyrolusite is added aniline leach manganese sulfate solution for 10%-60% sulfuric acid through weight percent concentration, neutralization is regulated the pH value of manganese sulfate solution to 2-6, be to add 2 grams-10 gram gacs and 1 gram-6 gram vulcanizing agents in per 1000 milliliters of the 4%-15% manganese sulfate solution toward weight percent concentration then, be warming up to 30 ℃ of-70 ℃ of stirring reactions 10 minutes-50 minutes, continue to be warming up to 50 ℃-100 ℃, add 2 grams-10 gram villiaumite or hydrofluoric acid, stirring reaction 1 hour-4 hours, stop to heat up, the oxygenant stirring reaction 15 minutes-120 minutes that adds 1 gram-10 gram inorganic flocculating agents and 2 milliliters-40 milliliters again, add the weight percentage concentration again and be 25% ammoniacal liquor 1 gram-10 gram adjust pHs to 5-7, stirring reaction 1 minute-120 minutes, the organic floculant that adds 50ppm-200ppm again, standing sedimentation 1 hour-12 hours, filter, the calcium that adds 50ppm-200ppm in the filtrate, the magnesium ion complexing agent, under 20 ℃ of-60 ℃ of temperature, add weight percent concentration and be the carbonate reaction 30 minutes of 10%-40%, filter, deionized water wash 3-5 filters all over being 7 to PH, be drying to obtain high-purity manganese carbonate.
2, a kind of method with preparing high-purity manganese carbonate with pyrolusite according to claim 1, it is characterized in that: villiaumite is Neutral ammonium fluoride or Sodium Fluoride.
3, a kind of method with preparing high-purity manganese carbonate with pyrolusite according to claim 1, it is characterized in that: vulcanizing agent is barium sulphide or ammonium sulfide or dithiocar-bamate.
4, a kind of method with preparing high-purity manganese carbonate with pyrolusite according to claim 1, it is characterized in that: oxygenant is potassium permanganate or Manganse Dioxide or hydrogen peroxide or hypochlorous acid.
5, a kind of method with preparing high-purity manganese carbonate with pyrolusite according to claim 1, it is characterized in that: inorganic flocculating agent is ferric sulfate or iron trichloride or aluminum chloride.
6, a kind of method with preparing high-purity manganese carbonate with pyrolusite according to claim 1, it is characterized in that: organic floculant is the polyacrylic acid amine.
7, a kind of method with preparing high-purity manganese carbonate with pyrolusite according to claim 1, it is characterized in that: calcium, magnesium ion complexing agent are organic acid or phosphoric acid salt.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875507A (en) * | 2010-08-04 | 2010-11-03 | 湖南汇通科技有限责任公司 | High purity manganese sulfate monohydrate and preparation method thereof |
| CN102070198A (en) * | 2011-02-28 | 2011-05-25 | 湖南科技大学 | Method for preparing high-purity manganese sulfate and high-purity manganese carbonate by reduction leaching of pyrolusite through scrap iron |
| CN102560156A (en) * | 2012-02-23 | 2012-07-11 | 中国恩菲工程技术有限公司 | Method for recycling manganese from P204 manganese back extraction solution in nickel laterite hydrometallurgical process |
| CN105036197A (en) * | 2015-06-17 | 2015-11-11 | 刘平 | Method for preparing high purity manganese carbonate |
| CN106145199A (en) * | 2015-03-20 | 2016-11-23 | 谢文刚 | A kind of method preparing electron level manganese carbonate for raw material with manganese spar |
| CN106191918A (en) * | 2016-08-19 | 2016-12-07 | 来宾华锡冶炼有限公司 | A kind of method preparing manganese sulfate solution removing impurities agent |
| CN108910959A (en) * | 2018-07-18 | 2018-11-30 | 重庆上甲电子股份有限公司 | A method of manganese sulfate is produced using hydroquinone reduction electrolytic manganese anode mud |
| CN109437309A (en) * | 2018-11-26 | 2019-03-08 | 郝新丽 | A kind of synthetic method of shuttle-type structure manganese carbonate nano material |
| CN111876600A (en) * | 2020-08-07 | 2020-11-03 | 贵州中伟资源循环产业发展有限公司 | Method for removing calcium and magnesium ions in sulfate solution and sulfate solution |
| CN113912127A (en) * | 2021-11-26 | 2022-01-11 | 中伟新材料股份有限公司 | Method for removing silicon from manganese sulfate solution |
-
2008
- 2008-07-17 CN CNA2008100484324A patent/CN101318706A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875507A (en) * | 2010-08-04 | 2010-11-03 | 湖南汇通科技有限责任公司 | High purity manganese sulfate monohydrate and preparation method thereof |
| CN101875507B (en) * | 2010-08-04 | 2012-10-24 | 湖南汇通科技有限责任公司 | preparation method of high purity manganese sulfate monohydrate |
| CN102070198A (en) * | 2011-02-28 | 2011-05-25 | 湖南科技大学 | Method for preparing high-purity manganese sulfate and high-purity manganese carbonate by reduction leaching of pyrolusite through scrap iron |
| CN102070198B (en) * | 2011-02-28 | 2012-09-05 | 湖南科技大学 | Method for preparing high-purity manganese sulfate and high-purity manganese carbonate by reduction leaching of pyrolusite through scrap iron |
| CN102560156A (en) * | 2012-02-23 | 2012-07-11 | 中国恩菲工程技术有限公司 | Method for recycling manganese from P204 manganese back extraction solution in nickel laterite hydrometallurgical process |
| CN106145199A (en) * | 2015-03-20 | 2016-11-23 | 谢文刚 | A kind of method preparing electron level manganese carbonate for raw material with manganese spar |
| CN105036197A (en) * | 2015-06-17 | 2015-11-11 | 刘平 | Method for preparing high purity manganese carbonate |
| CN106191918A (en) * | 2016-08-19 | 2016-12-07 | 来宾华锡冶炼有限公司 | A kind of method preparing manganese sulfate solution removing impurities agent |
| CN106191918B (en) * | 2016-08-19 | 2018-08-10 | 来宾华锡冶炼有限公司 | A method of preparing manganese sulfate solution removing impurities agent |
| CN108910959A (en) * | 2018-07-18 | 2018-11-30 | 重庆上甲电子股份有限公司 | A method of manganese sulfate is produced using hydroquinone reduction electrolytic manganese anode mud |
| CN109437309A (en) * | 2018-11-26 | 2019-03-08 | 郝新丽 | A kind of synthetic method of shuttle-type structure manganese carbonate nano material |
| CN109437309B (en) * | 2018-11-26 | 2021-04-30 | 河北地质大学 | Synthetic method of shuttle-shaped structure manganese carbonate nano material |
| CN111876600A (en) * | 2020-08-07 | 2020-11-03 | 贵州中伟资源循环产业发展有限公司 | Method for removing calcium and magnesium ions in sulfate solution and sulfate solution |
| CN113912127A (en) * | 2021-11-26 | 2022-01-11 | 中伟新材料股份有限公司 | Method for removing silicon from manganese sulfate solution |
| CN113912127B (en) * | 2021-11-26 | 2023-09-08 | 中伟新材料股份有限公司 | Method for removing silicon from manganese sulfate solution |
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