CN101508467A - Preparation of high purity manganese sulfate - Google Patents
Preparation of high purity manganese sulfate Download PDFInfo
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- CN101508467A CN101508467A CNA2009100068889A CN200910006888A CN101508467A CN 101508467 A CN101508467 A CN 101508467A CN A2009100068889 A CNA2009100068889 A CN A2009100068889A CN 200910006888 A CN200910006888 A CN 200910006888A CN 101508467 A CN101508467 A CN 101508467A
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Abstract
The invention provides a method for preparing high-purity manganese sulfate. The method comprises that: an impurity-containing manganese sulfate solid is prepared into a solution of manganese sulfate, or manganese ores are leached by sulfuric acid to obtain the solution of manganese sulfate, and the solution of manganese sulfate is added with an impurity removing agent, namely MnF2 to remove impurities such as Ca and Mg, and added with MnS or metal manganese powder which is used as an impurity removing agent for removing heavy metal impurities so as to avoid the introduction of impurities, ensure the impurity removing effect and simultaneously control the pH value to be between 3.5 and 7 in the reaction. The impurity removing agents of the MnF2 and MnS or metal manganese powder can be added at the same time or in order, and then the solution of manganese sulfate is subjected to filtering, normal-pressure concentration, crystallization, dewatering and drying to obtain the high-purity manganese sulfate product. The method has the advantages that: the contents of impurities such as Ca and Mg and heavy metals in the solution of manganese sulfate, which is obtained by using the sulfuric acid to leach the common manganese sulfate product or manganese ores, are obviously reduced, and the contents of Ca, Mg and heavy metal impurities are lower than 50ppm, and the purity of the prepared manganese sulfate reaches more than 99 percent, so that the manganese sulfate prepared by the method can meet the needs for ternary materials in the electronic industry.
Description
Technical field
The present invention relates to a kind of preparation method of high purity manganese sulfate, particularly a kind of manganese sulfate solution after utilizing common manganous sulfate solid or manganese ore with sulfuric acid to leach prepares the method for high purity manganese sulfate.
Background technology
The manganous sulfate solid (containing SILVER REAGENT manganous sulfate solid) of usual way preparation or utilize manganese ore with sulfuric acid to leach after manganese sulfate solution by the manganous sulfate solid of usual way preparation, its Ca, Mg impurity and beavy metal impurity (Co, Ni, Pb etc.) content height, Ca in the manganese ore wherein, Mg content can reach more than the 3000ppm, beavy metal impurity (Co, Ni, Pb, Cd, Cr etc.) content reaches about 300ppm, even SILVER REAGENT manganous sulfate solid, its Ca, Mg content also reaches more than the 100ppm, use general cleaner, even can be with Ca, Mg impurity and beavy metal impurity (Co, Ni, Pb etc.) content reduces, but owing to brought other foreign ion into, the manganese sulfate product purity of preparation is not high, quality product does not reach the requirement of electronic grade product, can not be used for the electronic industry ternary material makes raw material and (requires calcium ions and magnesium ions, beavy metal impurity content is lower than 50ppm, and manganese content is greater than 31.8%).Cause its product quality not high, added value is not high, has influenced its application.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of high purity manganese sulfate.This method can overcome common manganous sulfate preparation method's deficiency, can reduce foreign matter content in the product effectively, improves value-added content of product greatly, and the electronic-grade manganese sulfate product of high-quality low-cost is provided for electron trade.
The object of the present invention is achieved like this: a kind of preparation method of high purity manganese sulfate, with the manganous sulfate solid of impure (analyzing earlier calcium, magnesium ion content greater than 100ppm) by atomic absorption spectrum be mixed with 100g-300g/l concentration manganese sulfate solution or manganese ore (calcium, magnesium ion content are greater than 3000ppm) with the manganese sulfate solution behind the sulfuric acid to leach (concentration is 100g-300g/l) in adding cleaner MnF
2, deliming, magnesium addition, MnF
2Consumption be the 100%-200% (calculating) of the theoretical consumption of the required cleaner of impurity by reaction equation, keep the pH value 3.5-7 of solution, remain on 60 ℃-100 ℃ temperature following 0.5 hour-2 hours, add cleaner MnS or manganese powder again, remove Co, Ni, Pb, Cd or Cr beavy metal impurity, the consumption of MnS or manganese powder is the 100%-200% of the theoretical consumption of the required cleaner of impurity, keep the pH value 3.5-7 of solution, remain under 60 ℃-100 ℃ the temperature reaction 0.5 hour-2 hours, and used MnF
2Do the introducing that cleaner can be avoided impurity with MnS or manganese powder, guarantee impurity-eliminating effect, filter, normal pressure concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product.Calcium, magnesium and heavy metal ion content can reach below the 50ppm in the product.
The preparation method of another kind of high purity manganese sulfate is mixed with impure manganous sulfate solid in manganese sulfate solution or the manganese sulfate solution after manganese ore is with sulfuric acid to leach and adds cleaner MnF simultaneously in the reaction
2With cleaner MnS or manganese powder, deliming, magnesium and Co, Ni, Pb, Cd or Cr beavy metal impurity are kept the pH value 3.5-7 of solution, remain under 60 ℃-100 ℃ the temperature reaction 0.5 hour-2 hours, use MnF
2Do the introducing that cleaner can be avoided impurity with MnS or manganese powder, guarantee impurity-eliminating effect, filter, normal pressure concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product.Calcium, magnesium and heavy metal ion content can reach below the 50ppm in the product.
The reaction principle of present method is:
The present invention can significantly reduce the amount of contained Ca, Mg impurity and beavy metal impurity (Co, Ni, Pb, Cd, Cr etc.) in common manganese sulfate product or the manganese ore manganese sulfate solution after with sulfuric acid to leach, can make Ca, Mg and beavy metal impurity (Co, Ni, Pb, Cd, Cr etc.) content be lower than 50ppm, simultaneously owing to do not introduce other impurity, the manganese sulfate product purity of producing reaches more than 99%, can satisfy the needs of electron trade ternary material with manganese sulfate product.
Embodiment
A kind of preparation method of high purity manganese sulfate, with the manganous sulfate solid of impure (analyzing earlier calcium, magnesium ion content greater than 100ppm) by atomic absorption spectrum be mixed with 100g-300g/l concentration manganese sulfate solution or manganese ore (calcium, magnesium ion content are greater than 3000ppm) with the manganese sulfate solution behind the sulfuric acid to leach (concentration is 100g-300g/l) in adding cleaner MnF
2, deliming, magnesium addition, MnF
2Consumption be the 100%-200% (calculating) of the theoretical consumption of the required cleaner of impurity by reaction equation, keep the pH value 3.5-7 of solution, remain on 60 ℃-100 ℃ temperature following 0.5 hour-2 hours, add cleaner MnS or manganese powder again, remove Co, Ni, Pb, Cd or Cr beavy metal impurity, the consumption of MnS or manganese powder is the 100%-200% of the theoretical consumption of the required cleaner of impurity, keep the pH value 3.5-7 of solution, remain under 60 ℃-100 ℃ the temperature reaction 0.5 hour-2 hours, and used MnF
2Do the introducing that cleaner can be avoided impurity with MnS or manganese powder, guarantee impurity-eliminating effect, filter, normal pressure concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product.Calcium, magnesium and heavy metal ion content can reach below the 50ppm in the product.
The preparation method of another kind of high purity manganese sulfate is mixed with impure manganous sulfate solid in manganese sulfate solution or the manganese sulfate solution after manganese ore is with sulfuric acid to leach and adds cleaner MnF simultaneously in the reaction
2With cleaner MnS or manganese powder, deliming, magnesium and Co, Ni, Pb, Cd or Cr beavy metal impurity are kept the pH value 3.5-7 of solution, remain under 60 ℃-100 ℃ the temperature reaction 0.5 hour-2 hours, use MnF
2Do the introducing that cleaner can be avoided impurity with MnS or manganese powder, guarantee impurity-eliminating effect, filter, normal pressure concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product.Calcium, magnesium and heavy metal ion content can reach below the 50ppm in the product.
Embodiment 1:
200gMnSO
4(Ca540ppm, Mg360ppm, Co154ppm, Ni76ppm) is dissolved in water to 2000ml, and heated and stirred is warming up to 100 ℃, adds 1gMnF
2Solid, keeping the pH value of solution value is 3.5, insulation reaction is 1 hour under stirring, add 150mgMnS again, stirred insulation reaction 0.5 hour, and filtered, filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 195g, analyzing manganous sulfate content is 99.7%, wherein Ca12ppm, Mg8ppm, Co8ppm, Ni5ppm.
Embodiment 2:
500gMnSO
4(Ca540ppm, Mg360ppm, Co154ppm, Ni76ppm) is dissolved in water to 1700ml, and heated and stirred is warming up to 60 ℃, adds 1.5gMnF
2Solid, adding 100mg manganese powder maintenance pH value of solution value again is 7.0, insulation reaction is 2 hours under stirring, filter, filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 470g, and analyzing manganous sulfate content is 99.5%, wherein Ca5ppm, Mg10ppm, Co5ppm, Ni5ppm.
Embodiment 3:
1000KgMnSO
4(Ca1200ppm, Mg810ppm, Co75ppm, Ni35ppm, Pb10ppm) is dissolved in water to 5m3, and heated and stirred is warming up to 100 ℃, adds 6.5KgMnF
2Solid, keeping the pH value of solution value is 4, insulation reaction is 0.5 hour under stirring, add 500gMnS and 500Kg manganese powder again, stirred insulation reaction 1.5 hours, and filtered, filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 980Kg, analyzing manganous sulfate content is 99.5%, wherein Ca20ppm, Mg15ppm, Co5ppm, Ni4ppm, Pb1ppm.
Embodiment 4:
600gMnSO
4(Ca540ppm, Mg360ppm, Co154ppm, Ni76ppm) is dissolved in water to 2000ml, and heated and stirred is warming up to 80 ℃, adds 2gMnF
2Solid, keeping the pH value of solution value is 5, insulation reaction is 2 hours under stirring, add 300mgMnS again, stirred insulation reaction 2 hours, and filtered, filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 578g, analyzing manganous sulfate content is 99.3%, wherein Ca18ppm, Mg10ppm, Co6ppm, Ni4ppm.
Embodiment 5:
300gMnSO
4(Ca540ppm, Mg360ppm, Co154ppm, Ni76ppm) is dissolved in water to 1000ml, and heated and stirred is warming up to 60 ℃, adds 1.5gMnF
2Solid, keeping the pH value of solution value is 3.5, insulation reaction is 1 hour under stirring, add 150mgMnS again, stirred insulation reaction 1 hour, and filtered, filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 290g, analyzing manganous sulfate content is 99.7%, wherein Ca15ppm, Mg12ppm, Co5ppm, Ni5ppm.
Embodiment 6:
300gMnSO
4(Ca540ppm, Mg360ppm, Co154ppm, Ni76ppm) is dissolved in water to 1000ml, heated and stirred is warming up to 60 ℃, add 1mlHF, 2g manganese carbonate product solid, keeping the pH value of solution value is 4, and insulation reaction is 1 hour under stirring, and adds 150mgMnS again, stirred insulation reaction 1 hour, filter, filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 290g, and analyzing manganous sulfate content is 99.5%.Wherein Ca18ppm, Mg15ppm, Co5ppm, Ni5ppm.
Embodiment 7:
300gMnSO
4(Ca540ppm, Mg360ppm, Co154ppm, Ni76ppm) is dissolved in water to 1000ml, and heated and stirred is warming up to 90 ℃, adds 1.5gMnF
2Solid, 100mgMnS, 50mg manganese powder, keeping the pH value of solution value is 7, stirs down insulation reaction 2 hours, filters, and filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 295g, and analyzing manganous sulfate content is 99.6%.Wherein Ca8ppm, Mg15ppm, Co5ppm, Ni5ppm.
Embodiment 8:
300gMnSO
4(Ca540ppm, Mg360ppm, Co154ppm, Ni76ppm) is dissolved in water to 1000ml, and heated and stirred is warming up to 100 ℃, adds 0.8gMnF
2Solid, 100mgMnS, keeping the pH value of solution value is 7, stirs down insulation reaction 0.5 hour, filters, and filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 289g, and analyzing manganous sulfate content is 99.6%.Wherein Ca24ppm, Mg30ppm, Co15ppm, Ni8ppm.
Embodiment 9:
300gMnSO
4(Ca2200ppm, Mg1500ppm, Co140ppm, Ni55ppm) is dissolved in water to 1000ml, and heated and stirred is warming up to 80 ℃, adds 3.5gMnF
2Solid, 200mg manganese powder, keeping the pH value of solution value is 5, stirs down insulation reaction 1 hour, filters, and filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 292g, and analyzing manganous sulfate content is 99.6%.Wherein Ca30ppm, Mg16ppm, Co10ppm, Ni7ppm.
Embodiment 10:
300gMnSO
4(Ca2200ppm, Mg1500ppm, Co140ppm, Ni55ppm) is dissolved in water to 1000ml, heated and stirred is warming up to 60 ℃, add 3mlHF, 6g manganese carbonate product solid, 120mg manganese powder, keeping the pH value of solution value is 7, insulation reaction is 1 hour under stirring, filter, filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 294g, and analyzing manganous sulfate content is 99.8%.Wherein Ca24ppm, Mg10ppm, Co8ppm, Ni8ppm.
Embodiment 11:
Manganese ore is through the MnSO of sulfuric acid to leach
4Solution 5m
3, MnSO
4Content is 160g/l (relatively manganous sulfate solid impurity content be Ca4200ppm, Mg3000ppm, Co350ppm, Ni550ppm), and heat temperature raising to 75 ℃ adds 20kgMnF
2Solid, keeping the pH value of solution value is 6.5, stirs down insulation reaction 2 hours, adds 2.5KgMnS again, stirs insulation reaction 0.5 hour, filters, and filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 690Kg, and analyzing manganous sulfate content is 99.8%.Wherein Ca35ppm, Mg15ppm, Co10ppm, Ni10ppm.
Embodiment 12:
Manganese ore is through the MnSO of sulfuric acid to leach
4Solution 1m
3, MnSO
4Content is 300g/l (relatively manganous sulfate solid impurity content be Ca4200ppm, Mg3000ppm, Co350ppm, Ni550ppm), and heat temperature raising to 100 ℃ adds 7kgMnF
2Solid, keeping the pH value of solution value is 3.5, stirs down insulation reaction 0.5 hour, adds 1kgMnS again, stirs insulation reaction 2 hours, filters, and filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 355Kg, and analyzing manganous sulfate content is 99.4%.Wherein Ca20ppm, Mg12ppm, Co8ppm, Ni10ppm.
Embodiment 13:
Manganese ore is through the MnSO of sulfuric acid to leach
4Solution 1m
3, MnSO
4Content is 100g/l (manganous sulfate solid impurity content is Ca4200ppm, Mg3000ppm, Co350ppm, Ni550ppm relatively), heat temperature raising to 100 ℃, add 900mlHF, 3.5kg manganese carbonate product solid, keeping the pH value of solution value is 7, and insulation reaction is 0.5 hour under stirring, and adds 300gMnS again, stirred insulation reaction 2 hours, filter, filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 355Kg, and analyzing manganous sulfate content is 99.5%.Wherein Ca28ppm, Mg20ppm, Co10ppm, Ni7ppm.
Embodiment 14:
Manganese ore is through the MnSO of sulfuric acid to leach
4Solution 1000ml, MnSO
4Content is 300g/l (relatively manganous sulfate solid impurity content be Ca4200ppm, Mg3000ppm, Co350ppm, Ni550ppm), and heat temperature raising to 60 ℃ adds 7gMnF
2Solid, keeping the pH value of solution value is 5, stirs down insulation reaction 1.5 hours, adds 1gMnS again, stirs insulation reaction 1 hour, filters, and filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 262g, and analyzing manganous sulfate content is 99.7%.Wherein Ca24ppm, Mg20ppm, Co15ppm, Ni27ppm.
Embodiment 15:
Manganese ore is through the MnSO of sulfuric acid to leach
4Solution 1000ml, MnSO
4Content is 100g/l (relatively manganous sulfate solid impurity content be Ca4200ppm, Mg3000ppm, Co350ppm, Ni550ppm), and heat temperature raising to 60 ℃ adds 2gMnF
2Solid, keeping the pH value of solution value is 3.5, stirs down insulation reaction 2 hours, adds the 500mg manganese powder again, stirs insulation reaction 0.5 hour, filters, and filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 44g, and analyzing manganous sulfate content is 99.3%.Wherein Ca10ppm, Mg16ppm, Co10ppm, Ni12ppm.
Embodiment 16:
Manganese ore is through the MnSO of sulfuric acid to leach
4Solution 2000ml, MnSO
4Content is 200g/l (relatively manganous sulfate solid impurity content be Ca4200ppm, Mg3000ppm, Co350ppm, Ni550ppm), and heat temperature raising to 60 ℃ adds 10gMnF
2Solid, keeping the pH value of solution value is 7, stirs down insulation reaction 1 hour, adds 1g manganese powder, 1gMnS again, stirs insulation reaction 2 hours, filters, and filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 348g, and analyzing manganous sulfate content is 99.5%.Wherein Ca12ppm, Mg16ppm, Co8ppm, Ni8ppm.
Embodiment 17:
Manganese ore is through the MnSO of sulfuric acid to leach
4Solution 2000ml, MnSO
4Content is 200g/l (relatively manganous sulfate solid impurity content be Ca4200ppm, Mg3000ppm, Co350ppm, Ni550ppm), and heat temperature raising to 100 ℃ adds 5gMnF
2Solid adds 1g manganese powder, 500mgMnS again, and keeping the pH value of solution value is 7, stirs insulation reaction 2 hours, filters, and filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 350g, and analyzing manganous sulfate content is 99.3%.Wherein Ca34ppm, Mg24ppm, Co15ppm, Nil5ppm.
Embodiment 18:
Manganese ore is through the MnSO of sulfuric acid to leach
4Solution 2000ml, MnSO
4Content is 200g/l (relatively manganous sulfate solid impurity content be Ca4200ppm, Mg3000ppm, Co350ppm, Ni550ppm), and heat temperature raising to 80 ℃ adds 8gMnF
2Solid adds 2gMnS again, and keeping the pH value of solution value is 4, stirs insulation reaction 1 hour, filters, and filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 345g, and analyzing manganous sulfate content is 99.4%.Wherein Ca28ppm, Mg25ppm, Co10ppm, Ni15ppm.
Embodiment 19:
Manganese ore is through the MnSO of sulfuric acid to leach
4Solution 2000ml, MnSO
4Content is 200g/l (manganous sulfate solid impurity content is Ca4200ppm, Mg3000ppm, Co350ppm, Ni550ppm relatively), heat temperature raising to 60 ℃, add 2mlHF, 7g manganese carbonate product solid, add 1gMnS again, keeping the pH value of solution value is 5, stirs insulation reaction 1 hour, filters, filtrate concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product 345g, and analyzing manganous sulfate content is 99.4%.Wherein Ca20ppm, Mg25ppm, Co18ppm, Ni25ppm.
Claims (2)
1, a kind of preparation method of high purity manganese sulfate is characterized in that: impure manganous sulfate solid is mixed with adding cleaner MnF in manganese sulfate solution or the manganese sulfate solution after manganese ore is with sulfuric acid to leach
2, deliming, magnesium addition, MnF
2Consumption be the 100%-200% of the theoretical consumption of the required cleaner of impurity, keep the pH value 3.5-7 of solution, remain on 60 ℃-100 ℃ temperature following 0.5 hour-2 hours, add cleaner MnS or manganese powder again, remove Co, Ni, Pb, Cd or Cr beavy metal impurity, the consumption of MnS or manganese powder is the 100%-200% of the theoretical consumption of the required cleaner of impurity, keeps the pH value 3.5-7 of solution, remain under 60 ℃-100 ℃ the temperature reaction 0.5 hour-2 hours, and used MnF
2Do the introducing that cleaner can be avoided impurity with MnS or manganese powder, guarantee impurity-eliminating effect, filter, normal pressure concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product.
2, a kind of preparation method of high purity manganese sulfate is characterized in that: impure manganous sulfate solid is mixed with in manganese sulfate solution or the manganese sulfate solution after manganese ore is with sulfuric acid to leach in the reaction adds cleaner MnF simultaneously
2With cleaner MnS or manganese powder, deliming, magnesium and Co, Ni, Pb, Cd or Cr beavy metal impurity are kept the pH value 3.5-7 of solution, remain under 60 ℃-100 ℃ the temperature reaction 0.5 hour-2 hours, use MnF
2Do the introducing that cleaner can be avoided impurity with MnS or manganese powder, guarantee impurity-eliminating effect, filter, normal pressure concentrates, crystallization, dehydration, dry high-purity sulphuric acid manganese product.
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2008
- 2008-11-18 CN CNA2008101976769A patent/CN101412543A/en active Pending
-
2009
- 2009-03-02 CN CNA2009100068889A patent/CN101508467A/en active Pending
- 2009-03-02 CN CN200910006889A patent/CN101519227A/en active Pending
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CN101798119B (en) * | 2010-03-29 | 2011-12-21 | 贵州红星发展股份有限公司 | Method for preparing manganese sulfate monohydrate |
CN101798119A (en) * | 2010-03-29 | 2010-08-11 | 贵州红星发展股份有限公司 | Method for preparing manganese sulfate monohydrate |
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 |
CN102674468A (en) * | 2012-05-24 | 2012-09-19 | 贵州红星发展股份有限公司 | Method for preparing barium sulfate while purifying manganese sulfate |
CN102674468B (en) * | 2012-05-24 | 2014-11-26 | 贵州红星发展股份有限公司 | Method for preparing barium sulfate while purifying manganese sulfate |
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 |
CN105481020A (en) * | 2015-12-18 | 2016-04-13 | 长沙矿冶研究院有限责任公司 | Method for removing alkaline-earth metal impurities in manganese sulfate solution |
CN106629857A (en) * | 2017-01-04 | 2017-05-10 | 贵州红星发展大龙锰业有限责任公司 | Separation method for impurity magnesium in manganese sulfate solution |
CN109665501A (en) * | 2019-01-29 | 2019-04-23 | 吴红 | A kind of sulfate liquor fluorine circulation de-magging technique and system |
CN111186863A (en) * | 2020-02-27 | 2020-05-22 | 中国恩菲工程技术有限公司 | Impurity removal device and method for soluble manganese salt solution |
CN113663356A (en) * | 2021-08-23 | 2021-11-19 | 广西埃索凯新材料科技有限公司 | Crystallization impurity removal monitoring system applied to manganese sulfate production |
CN114480886A (en) * | 2021-12-23 | 2022-05-13 | 四川中哲新材料科技有限公司 | Method for producing electrolytic manganese metal from manganese carbonate ore with high magnesium impurity |
CN116081693A (en) * | 2023-01-10 | 2023-05-09 | 何长荣 | Method for refining manganese sulfate product by removing impurities from calcium and magnesium |
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CN101412543A (en) | 2009-04-22 |
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