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WO2011009351A1 - 一种硫酸锰与碳酸锰的循环提纯方法 - Google Patents

一种硫酸锰与碳酸锰的循环提纯方法 Download PDF

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Publication number
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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Prior art keywords
manganese
manganese sulfate
manganese carbonate
sulfate
solution
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English (en)
French (fr)
Inventor
姜志光
华东
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SHENZHEN HAOYITONG INVESTMENT AND DEVELOPMENT Co Ltd
Guizhou Redstar Developing Co Ltd
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SHENZHEN HAOYITONG INVESTMENT AND DEVELOPMENT Co Ltd
Guizhou Redstar Developing Co Ltd
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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
    • 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 # .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Description

一种硫酸锰与碳酸锰的循环提纯方法
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。
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。
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。
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。
发明内容
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：
MnS04+2NH4HC03 ^► MnC03+ (丽 4) 2S04+C02†
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。
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。
本发明的硫酸锰与碳酸锰循环提纯方法具体如下：
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。
附图说明 图 1为本发明的主要工艺流程图。
具体实施方式 实施例 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#。
实施例 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。
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#。
实施例 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#。
实施例 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#。
以上各实施例所得样品 MnC03含量以及杂质含量数据如下表：
P
Figure imgf000006_0001
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Claims

权 利 要 求 书
1. 一种硫酸锰与碳酸锰循环提纯方法， 其包括步骤：
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；
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；
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
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。
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。
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。
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。
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。
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。
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。
PCT/CN2010/073957 2009-07-20 2010-06-13 一种硫酸锰与碳酸锰的循环提纯方法 Ceased WO2011009351A1 (zh)

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CN101704555A (zh) * 2009-07-20 2010-05-12 贵州红星发展股份有限公司 一种硫酸锰与碳酸锰的循环提纯方法
CN101875507B (zh) * 2010-08-04 2012-10-24 湖南汇通科技有限责任公司 高纯一水硫酸锰的制备方法
CN102674467B (zh) * 2012-05-23 2014-02-12 贵州红星发展股份有限公司 一种硫酸锰的制备方法及其制得的硫酸锰产品
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CN104528831B (zh) * 2014-12-27 2017-02-22 西安交通大学 一种采用双重洗涤法制备高纯度一水合硫酸锰的方法
CN104891576B (zh) * 2015-05-06 2016-08-31 陕西省紫阳县湘贵锰业有限公司 一种一水合硫酸锰的制备方法
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CN111908511B (zh) * 2019-05-16 2021-10-01 清华大学 一种高纯硫酸锰生产中去除钙镁离子的方法
CN113716613A (zh) * 2020-05-25 2021-11-30 四川沃林山水环保科技有限公司 一种高纯硫酸锰的制备方法
CN114408978B (zh) * 2022-03-07 2024-08-23 科立鑫(珠海)新能源有限公司 一种利用钴原料中的锰制备电池级硫酸锰的工艺

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