WO2011009351A1 - Method for circularly purifying manganese sulfate and manganese carbonate - Google Patents
Method for circularly purifying manganese sulfate and manganese carbonate Download PDFInfo
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- WO2011009351A1 WO2011009351A1 PCT/CN2010/073957 CN2010073957W WO2011009351A1 WO 2011009351 A1 WO2011009351 A1 WO 2011009351A1 CN 2010073957 W CN2010073957 W CN 2010073957W WO 2011009351 A1 WO2011009351 A1 WO 2011009351A1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
Definitions
- the present invention relates to a process for purifying manganese sulfate and manganese carbonate, and more particularly to a cycle purification process for manganese sulfate and manganese carbonate.
- the inventors of the present invention use manganese dioxide ore powder to react with S rS or BaS to obtain manganese oxide. After washing, the manganese oxide is reacted with H 2 S0 4 to prepare a low heavy metal content of 300 to 450 g/ L The manganese acid-saturated solution is acidified and added to H 2 O 2 and then heat treated to remove the sulfide, and filtered to obtain a manganese sulfate clear solution.
- the present invention can also be recycled by using commercially available manganese sulfate as a raw material.
- the invention utilizes the separation ability of impurities in the synthesis process of manganese sulfate and manganese carbonate, and prepares high-quality manganese sulfate and manganese carbonate materials by cyclic separation.
- the alkali metal does not participate in the reaction in this synthesis system, and it remains in the mother liquor during the solid-liquid separation of the synthetic manganese carbonate, thereby achieving the separation purpose.
- the solubility of calcium bicarbonate is extremely large, and it remains in the mother liquor.
- the carbonate of magnesium under ammonia conditions does not precipitate, thereby achieving the purpose of separation.
- manganese carbonate is synthesized from manganese sulfate, and then K, Na, Ca, and Mg are effectively separated when manganese sulfate is prepared.
- the chemical reaction formula mainly involved in the present invention is:
- the manganese sulfate used in the present invention can be obtained in the market, and the manganese sulfate solution is prepared by dissolving manganese sulfate in water.
- the manganese sulfate solution is carbonated with Li 4 HC0 3 solution or solid to control the equimolar amount of the synthetic agent to separate the calcium and magnesium impurities, and the manganese carbonate is washed to remove the entrained (NH 4 ) 2 S0 4 and make it 12 mol/
- the reaction is carried out by LH 2 S0 4 , and the high-quality manganese sulfate material is obtained by filtration and evaporation, and the high-quality manganese carbonate material can be obtained by carbonation synthesis again.
- the schematic diagram of the synthesis process of manganese carbonate and manganese sulfate is shown in FIG.
- the method for recycling and purifying manganese sulfate and manganese carbonate of the present invention is as follows:
- the manganese sulfate solution is stirred at 40 - 80 ° C, preferably 50 - 60 ° C.
- the ammonium hydrogencarbonate is slowly added according to the end point of the synthesis, and the solid is separated and washed with hot water at 80-100 ° C to prepare carbonic acid.
- Manganese, hot water washing can be washed according to 1:5 water ratio; B adding the above manganese carbonate to 6-12mol/L, preferably 6-9mol/LH 2 S0 4 reaction, controlling the pH of the reaction solution to 1-2, heating Boiling, the pH value here is mainly for the full reaction of manganese carbonate and sulfuric acid; C then adding the manganese carbonate prepared above to the reaction solution to adjust the pH value of the solution to 4-5; D solid-liquid separation of the reaction solution, the filtrate obtained (Manganese acid solution) Evaporation crystallization, followed by drying to obtain manganese sulfate, and the obtained filtrate may be used as a manganese sulfate solution to repeat the first step to prepare high-purity manganese carbonate.
- the concentration of [Mn 2+ ] and [CO/-] can be determined by a chemical method to control the reaction end point.
- Figure 1 is a flow chart of the main process of the present invention.
- the washed manganese carbonate was placed in a 5000 ml beaker, beaten with a small amount of deionized water, reacted with 6 mol/L H 2 S0 4 to a pH of 1, heated and boiled, and then washed with MnC0 3 to a pH of 4, with The filter was filtered slowly, filtered, and the filtrate was evaporated. The crystals were dehydrated and dried in an oven at 80-85 ° C for 20 hours to obtain MnS0 4 ⁇ H 2 0 sample 1 # .
- the washed MnCO 3 was added to a small amount of deionized water to be beaten, reacted with 9 mol/L H 2 S0 4 to a pH of 2, heated and boiled, and then washed back to pH 5 with the washed MnCO 3 and filtered with a slow qualitative filter paper.
- the filter residue is discarded, the filtrate is placed in a 5000ml beaker, the temperature is controlled at 55 °C, and the synthesis is carried out in an equimolar reaction.
- Li 4 HC0 3 The synthesis of Li 4 HC0 3 is carried out , solid-liquid separation, liquid phase recovery (Li 4 ) 2 S0 4 , solid 1 : 5
- the feed water is washed twice more than 100 ° C, dried and placed in a vacuum oven at 85 ° C for 16 hours to obtain MnC0 3 sample 2 # .
- Example 1 was repeated except that 12 mol/L of H 2 S0 4 was added, and the food grade NH 4 HC0 3 was added to the manganese sulfate solution while stirring at a temperature of 60 ° C to obtain MnCO 3 sample 3 # and MnS0 4 ⁇ H 2 0 sample 3 # .
- Example 2 was repeated except that the food grade Li 4 HC0 3 was slowly added with stirring at 80 ° C to obtain MnCO 3 sample 4 # .
Abstract
Provided is a method for circularly purifying manganese sulfate and manganese carbonate, which comprises the following steps: (A) adding ammonium bicarbonate into manganese sulfate solution at 40-80 ℃ as agitating for synthesis, making end point of synthesis as equimolar reaction, separating solids, and washing with hot water to obtain manganese carbonate; (B) adding manganese carbonate into 6-12 mol/L H2SO4 to react, controlling pH value of the reaction solution to 1-2, and heating for boiling; (C) adjusting pH value of the reaction solution of step (B) to 4-5 by adding the manganese carbonate obtained in step (A) into the reaction solution; and (D) carrying out solid-liquid separation of the reaction solution, evaporating and crystallizing the obtained filtrate, and drying to obtain manganese sulfate. High-purity manganese sulfate and manganese carbonate with low calcium and magnesium contents and low potassium and sodium contents can be obtained by this method.
Description
一种硫酸锰与碳酸锰的循环提纯方法 Method for recycling and purifying manganese sulfate and manganese carbonate
技术领域 本发明涉及硫酸锰以及碳酸锰的提纯工艺， 特别涉及硫酸锰和碳酸锰 的循环提纯工艺。 TECHNICAL FIELD The present invention relates to a process for purifying manganese sulfate and manganese carbonate, and more particularly to a cycle purification process for manganese sulfate and manganese carbonate.
背景技术 随着锰酸锂二次电池的发展， 其对硫酸锰和碳酸锰材料的要求也逾来 逾高。 此中除了粒度分布、 重金属含量有较高要求外， 对材料中的碱金属 和碱土金属也有较高的要求， 特别是动力电池对此类材料的要求更加严 格。 现有技术提供的碳酸锰和硫酸锰材料中碱土金属以及碱金属， 特别是 钙镁离子的含量不能满足当前锰酸锂二次电池的发展需要。 Background Art With the development of lithium manganate secondary batteries, the demand for manganese sulfate and manganese carbonate materials has been excessively high. In addition to the higher requirements of particle size distribution and heavy metal content, there are also higher requirements for alkali metals and alkaline earth metals in materials, especially the requirements for such materials in power batteries are more stringent. The content of alkaline earth metals and alkali metals, especially calcium and magnesium ions, in the manganese carbonate and manganese sulfate materials provided by the prior art cannot meet the development needs of current lithium manganate secondary batteries.
对于硫酸锰的制备， 本发明人所在公司是利用二氧化锰矿粉与 S rS或 BaS反应获得氧化亚锰，经洗涤后将氧化亚锰与 H2S04反应制备低重金属含 量的 300 ~ 450g/L 充酸锰溶液， 将此溶液经酸化并加入 H202后加热处理以 除去硫化物， 并经过滤获得硫酸锰澄清溶液。 For the preparation of manganese sulfate, the inventors of the present invention use manganese dioxide ore powder to react with S rS or BaS to obtain manganese oxide. After washing, the manganese oxide is reacted with H 2 S0 4 to prepare a low heavy metal content of 300 to 450 g/ L The manganese acid-saturated solution is acidified and added to H 2 O 2 and then heat treated to remove the sulfide, and filtered to obtain a manganese sulfate clear solution.
当然本发明也可以利用市售的硫酸锰作为原料来循环提纯。 Of course, the present invention can also be recycled by using commercially available manganese sulfate as a raw material.
发明内容 Summary of the invention
本发明利用硫酸锰与碳酸锰合成过程中的杂质分离能力， 循环分离制备 高品质硫酸锰与碳酸锰材料。 碱金属在此合成体系中不参加反应， 在合成碳 酸锰固液分离时其留在母液中， 从而达到分离目的。 同时钙的碳酸氢盐溶解 度极大， 也留在了母液中， 镁在氨性条件下的碳酸盐不沉淀， 从而达到分离 目的。 所以本发明从硫酸锰合成碳酸锰， 然后再制备硫酸锰时 K、 Na、 Ca、 Mg就得到了有效分离。 本发明主要涉及的化学反应式有： The invention utilizes the separation ability of impurities in the synthesis process of manganese sulfate and manganese carbonate, and prepares high-quality manganese sulfate and manganese carbonate materials by cyclic separation. The alkali metal does not participate in the reaction in this synthesis system, and it remains in the mother liquor during the solid-liquid separation of the synthetic manganese carbonate, thereby achieving the separation purpose. At the same time, the solubility of calcium bicarbonate is extremely large, and it remains in the mother liquor. The carbonate of magnesium under ammonia conditions does not precipitate, thereby achieving the purpose of separation. Therefore, in the present invention, manganese carbonate is synthesized from manganese sulfate, and then K, Na, Ca, and Mg are effectively separated when manganese sulfate is prepared. The chemical reaction formula mainly involved in the present invention is:
MnS04+2NH4HC03 ^► MnC03+ (丽 4) 2S04+C02† MnS0 4 +2NH 4 HC0 3 ^► MnC0 3 + (Li 4 ) 2 S0 4 +C0 2 †
MnC03+H2S04+H20 ^► MnS04 · H20+C02†
本发明所用的硫酸锰市场中可以获得， 在水中溶解硫酸锰就配制成硫酸 锰溶液了。 MnC0 3 +H 2 S0 4 +H 2 0 ^► MnS0 4 · H 2 0+C0 2 † The manganese sulfate used in the present invention can be obtained in the market, and the manganese sulfate solution is prepared by dissolving manganese sulfate in water.
将硫酸锰溶液与丽 4HC03溶液或固体进行碳酸化合成，控制合成剂等摩尔 以分离钙镁杂质，获得碳酸锰经洗涤除去夹带的（NH4)2S04,并使之与 12mol/L H2S04 进行反应， 经过滤， 蒸发结晶获得高品质硫酸锰材料， 同时也可以再次 进行碳酸化合成获得高品质碳酸锰材料。 为进一步明了本发明的工艺过程， 图 1用筒单的图示表示碳酸锰和硫酸锰的合成工艺路线图。 The manganese sulfate solution is carbonated with Li 4 HC0 3 solution or solid to control the equimolar amount of the synthetic agent to separate the calcium and magnesium impurities, and the manganese carbonate is washed to remove the entrained (NH 4 ) 2 S0 4 and make it 12 mol/ The reaction is carried out by LH 2 S0 4 , and the high-quality manganese sulfate material is obtained by filtration and evaporation, and the high-quality manganese carbonate material can be obtained by carbonation synthesis again. In order to further clarify the process of the present invention, the schematic diagram of the synthesis process of manganese carbonate and manganese sulfate is shown in FIG.
本发明的硫酸锰与碳酸锰循环提纯方法具体如下： The method for recycling and purifying manganese sulfate and manganese carbonate of the present invention is as follows:
A将硫酸锰溶液在 40 - 80°C , 优选为 50 - 60°C下搅拌按照合成终点为等 摩尔反应緩慢加入碳酸氢铵，分离固体，用 80-100°C的热水洗涤制成碳酸锰， 热水洗涤可以按 1: 5料水比洗涤； B将上述碳酸锰加入 6-12mol/L, 优选为 6-9mol/L H2S04反应， 控制反应溶液 PH值为 1-2, 加热煮沸， 此处所调 PH值 主要是为了碳酸锰与硫酸充分反应； C 然后用上述制得的碳酸锰加入反应溶 液中将溶液 PH值回调为 4-5; D 将反应溶液固液分离， 所得滤液（ 酸锰溶 液） 蒸发结晶， 然后烘干获硫酸锰， 也可以将所得滤液作为硫酸锰溶液重复 第一步制备高纯碳酸锰。 对于以上各步骤中涉及到按照合成终点为等摩尔反 应加入碳酸氢铵的控制可以利用化学法测定 [Mn2+]和 [CO/—]的浓度来控制反 应终点。 A. The manganese sulfate solution is stirred at 40 - 80 ° C, preferably 50 - 60 ° C. The ammonium hydrogencarbonate is slowly added according to the end point of the synthesis, and the solid is separated and washed with hot water at 80-100 ° C to prepare carbonic acid. Manganese, hot water washing can be washed according to 1:5 water ratio; B adding the above manganese carbonate to 6-12mol/L, preferably 6-9mol/LH 2 S0 4 reaction, controlling the pH of the reaction solution to 1-2, heating Boiling, the pH value here is mainly for the full reaction of manganese carbonate and sulfuric acid; C then adding the manganese carbonate prepared above to the reaction solution to adjust the pH value of the solution to 4-5; D solid-liquid separation of the reaction solution, the filtrate obtained (Manganese acid solution) Evaporation crystallization, followed by drying to obtain manganese sulfate, and the obtained filtrate may be used as a manganese sulfate solution to repeat the first step to prepare high-purity manganese carbonate. For the above-mentioned control involving the addition of ammonium hydrogencarbonate in an equimolar reaction according to the end point of the synthesis, the concentration of [Mn 2+ ] and [CO/-] can be determined by a chemical method to control the reaction end point.
附图说明 图 1为本发明的主要工艺流程图。 BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart of the main process of the present invention.
具体实施方式 实施例 1 DETAILED DESCRIPTION OF THE INVENTION Example 1
将 354g/L MnS04溶液 4000ml置于 5000ml烧杯中， 控制温度 50°C, 搅拌 下緩慢加入食品级 丽 4HC03 1514g，吸滤分离， 滤液回收（丽 4) 2S04, 固体按 1: 5料水比 80°C热洗二次， 取部分烘干成 MnC03 1#。
将上述洗涤后的碳酸锰置于 5000ml烧杯中， 加入少量去离子水打浆， 用 6mol/L H2S04反应至 PH值为 1, 加热煮沸后用洗涤后的 MnC03回调 PH值为 4, 用慢速定性滤纸过滤， 滤渣弃， 滤液蒸发结晶， 结晶脱水后置于 80~85°C烘 箱中烘干 20小时， 获得 MnS04 · H20样品 1#。 4000ml of 354g/L MnS0 4 solution was placed in a 5000ml beaker, the temperature was controlled at 50 °C, and the food grade Li 4 HC0 3 1514g was slowly added under stirring. The filtrate was separated by suction filtration, and the filtrate was recovered (Li 4 ) 2 S0 4 , and the solid was 1: 5 The feed water is hot washed twice at 80 ° C, and partially dried to MnC0 3 1 # . The washed manganese carbonate was placed in a 5000 ml beaker, beaten with a small amount of deionized water, reacted with 6 mol/L H 2 S0 4 to a pH of 1, heated and boiled, and then washed with MnC0 3 to a pH of 4, with The filter was filtered slowly, filtered, and the filtrate was evaporated. The crystals were dehydrated and dried in an oven at 80-85 ° C for 20 hours to obtain MnS0 4 · H 2 0 sample 1 # .
实施例 2 Example 2
将 354g/L MnS04溶液 4000ml置于 5000ml烧杯中， 控制温度 55 °C, 搅拌 下緩慢加入食品级 丽 4HC03 1514g，吸滤分离， 滤液回收（丽 4) 2S04, 固体按 1: 5料水比 100°C热洗二次。 4000ml of 354g/L MnS0 4 solution was placed in a 5000ml beaker, the temperature was controlled at 55 °C, and the food grade Li 4 HC0 3 1514g was slowly added with stirring, separated by suction filtration, and the filtrate was recovered (Li 4 ) 2 S0 4 , and the solid was 1: 5 feed water is washed twice more than 100 ° C.
将上述洗涤后 MnC03加入少量去离子水打浆， 用 9mol/L H2S04反应至 PH 值为 2,加热煮沸后用洗涤后的 MnC03回调至 PH值为 5,用慢速定性滤纸过滤， 滤渣弃， 滤液置于 5000ml 烧杯中， 控制温度 55°C范围， 緩慢按照合成终点 为等摩尔反应加入丽 4HC03合成， 固液分离， 液相回收（丽 4) 2S04, 固体按 1: 5 料水比 100°C热洗二次，脱水后置于 85°C真空烘箱中烘干 16小时，获得 MnC03 样品 2#。 The washed MnCO 3 was added to a small amount of deionized water to be beaten, reacted with 9 mol/L H 2 S0 4 to a pH of 2, heated and boiled, and then washed back to pH 5 with the washed MnCO 3 and filtered with a slow qualitative filter paper. The filter residue is discarded, the filtrate is placed in a 5000ml beaker, the temperature is controlled at 55 °C, and the synthesis is carried out in an equimolar reaction. The synthesis of Li 4 HC0 3 is carried out , solid-liquid separation, liquid phase recovery (Li 4 ) 2 S0 4 , solid 1 : 5 The feed water is washed twice more than 100 ° C, dried and placed in a vacuum oven at 85 ° C for 16 hours to obtain MnC0 3 sample 2 # .
实施例 3 Example 3
重复实施例 1, 不同的是加入的 12mol/L H2S04, 在温度为 60°C下搅拌緩 慢在硫酸锰液中加入食品级 NH4HC03, 得 MnC03样品 3#和 MnS04 · H20样品 3#。 Example 1 was repeated except that 12 mol/L of H 2 S0 4 was added, and the food grade NH 4 HC0 3 was added to the manganese sulfate solution while stirring at a temperature of 60 ° C to obtain MnCO 3 sample 3 # and MnS0 4 · H 2 0 sample 3 # .
实施例 4 Example 4
重复实施例 2, 不同的是在 80°C下， 搅拌緩慢加入食品级丽 4HC03, 获得 MnC03样品 4#。 Example 2 was repeated except that the food grade Li 4 HC0 3 was slowly added with stirring at 80 ° C to obtain MnCO 3 sample 4 # .
以上各实施例所得样品 MnC03含量以及杂质含量数据如下表：
Samples obtained above embodiments MnC0 3 content and the impurity content of the data in the following table:
P P
Claims
1. 一种硫酸锰与碳酸锰循环提纯方法， 其包括步骤： A method for recycling and purifying manganese sulfate and manganese carbonate, comprising the steps of:
A将硫酸锰溶液在 40 - 80 °C温度范围下搅拌加入碳酸氢铵进行合成， 控 制合成终点为等摩尔反应， 分离固体， 热水洗涤制成碳酸锰； A. The manganese sulfate solution is stirred and added to the ammonium hydrogencarbonate at a temperature of 40-80 ° C for synthesis, and the end point of the synthesis is controlled to equimolar reaction, and the solid is separated and washed with hot water to form manganese carbonate;
B将上述制成的碳酸锰加入 6-12mo l /L H2S04反应， 控制反应溶液 PH值为 1-2 , 加热煮沛； B adding the above-mentioned manganese carbonate to 6-12mol / LH 2 S0 4 reaction, controlling the pH of the reaction solution to 1-2, heating and boiling;
C用步骤 A制成的碳酸锰加入步骤 B的反应溶液中， 将溶液 PH值回调为 C. The manganese carbonate prepared in step A is added to the reaction solution of step B, and the pH value of the solution is adjusted back to
4-5 ; 4-5;
D将步骤 C所得反应溶液固液分离， 所得滤液蒸发结晶， 然后烘干得硫 酸锰。 D. The reaction solution obtained in the step C is subjected to solid-liquid separation, and the obtained filtrate is evaporated to crystallize, and then dried to obtain manganese sulfate.
2. 如权利要求 1所述的硫酸锰与碳酸锰循环提纯方法，将步骤 D所得 滤液作为硫酸锰溶液重复步骤 1制备碳酸锰。 The method for cyclic purification of manganese sulfate and manganese carbonate according to claim 1, wherein the filtrate obtained in the step D is used as a manganese sulfate solution to repeat step 1 to prepare manganese carbonate.
3. 如权利要求 1或 2所述的硫酸锰与碳酸锰循环提纯方法，其中 A步 骤中所述的温度范围为 50 - 60 °C。 The method for cyclic purification of manganese sulfate and manganese carbonate according to claim 1 or 2, wherein the temperature in the step A ranges from 50 to 60 °C.
4. 如权利要求 1或 2所述的硫酸锰与碳酸锰循环提纯方法，其中 B步 骤中加入 H2S04的摩尔浓度为 6_9mo l /L。 The method for cyclic purification of manganese sulfate and manganese carbonate according to claim 1 or 2, wherein the molar concentration of H 2 SO 4 added in the step B is 6-9 mol/L.
5. 如权利要求 1或 2所述的硫酸锰与碳酸锰循环提纯方法， 其中， B 步骤中利用化学法测定 [Mn2+]和 [CO/—]的浓度来控制反应终点。 The method for cyclic purification of manganese sulfate and manganese carbonate according to claim 1 or 2, wherein in the step B, the concentration of [Mn 2+ ] and [CO/-] is determined by a chemical method to control the reaction end point.
6. 如权利要求 1或 2所述的硫酸锰与碳酸锰循环提纯方法， 其中， 所 述热水洗涤的温度为 80-100 °C。 The method for cyclic purification of manganese sulfate and manganese carbonate according to claim 1 or 2, wherein the temperature of the hot water washing is 80 to 100 °C.
7. 如权利要求 1或 2所述的硫酸锰与碳酸锰循环提纯方法， 其中， 步 骤 A中所得的固体按 1 : 5料水比洗涤。
The method for cyclic purification of manganese sulfate and manganese carbonate according to claim 1 or 2, wherein the solid obtained in the step A is washed at a ratio of 1:5.
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| CN200910161306A CN101704555A (en) | 2009-07-20 | 2009-07-20 | Method for circularly purifying manganese sulfate and manganese carbonate |
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| CN114702075A (en) * | 2022-04-11 | 2022-07-05 | 中南大学 | Purification preparation method of manganese sulfate |
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| CN101704555A (en) * | 2009-07-20 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for circularly purifying manganese sulfate and manganese carbonate |
| 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 |
| CN102674467B (en) * | 2012-05-23 | 2014-02-12 | 贵州红星发展股份有限公司 | Preparation method of manganese sulfate and manganese sulfate product prepared by same |
| CN103011297B (en) * | 2012-12-07 | 2014-12-10 | 中信大锰矿业有限责任公司 | Method for production of high purity manganese sulfate by using pyrolusite as raw material |
| CN104528831B (en) * | 2014-12-27 | 2017-02-22 | 西安交通大学 | Method for preparing high-purity hydrated manganese sulfate employing dual washing method |
| CN104891576B (en) * | 2015-05-06 | 2016-08-31 | 陕西省紫阳县湘贵锰业有限公司 | A kind of preparation method of Manganous sulfate monohydrate |
| CN108046329B (en) * | 2017-12-01 | 2019-11-12 | 盐城市东港药物化工发展有限公司 | The technique of magnesium manganese element is recycled in a kind of industrial wastewater |
| CN111908511B (en) * | 2019-05-16 | 2021-10-01 | 清华大学 | Method for removing calcium and magnesium ions in production of high-purity manganese sulfate |
| CN113716613A (en) * | 2020-05-25 | 2021-11-30 | 四川沃林山水环保科技有限公司 | Preparation method of high-purity manganese sulfate |
| CN114408978A (en) * | 2022-03-07 | 2022-04-29 | 珠海市科立鑫金属材料有限公司 | Process for preparing battery-grade manganese sulfate by using manganese in cobalt raw material |
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| CN1311340A (en) * | 2000-02-28 | 2001-09-05 | 邓建成 | Method for producing manganese carbonate from manganese sulfate in waste manganese mud |
| CN101704555A (en) * | 2009-07-20 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for circularly purifying manganese sulfate and manganese carbonate |
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| RO93755A2 (en) * | 1986-03-17 | 1988-02-29 | Unitatea De Cercetare Si Proiectare Pentru Metalurgie Neferoasa,Ro | MANUFACTURING PROCESS FOR MANGAN |
| CN1311340A (en) * | 2000-02-28 | 2001-09-05 | 邓建成 | Method for producing manganese carbonate from manganese sulfate in waste manganese mud |
| CN1283592A (en) * | 2000-07-08 | 2001-02-14 | 中国石油化工股份有限公司巴陵分公司 | Process for preparing high-purity manganese carbonate |
| CN101704555A (en) * | 2009-07-20 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for circularly purifying manganese sulfate and manganese carbonate |
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| CN114702075A (en) * | 2022-04-11 | 2022-07-05 | 中南大学 | Purification preparation method of manganese sulfate |
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