WO2011120273A1 - 一种制备一水合硫酸锰的方法 - Google Patents

一种制备一水合硫酸锰的方法 Download PDF

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Publication number
WO2011120273A1
WO2011120273A1 PCT/CN2010/075312 CN2010075312W WO2011120273A1 WO 2011120273 A1 WO2011120273 A1 WO 2011120273A1 CN 2010075312 W CN2010075312 W CN 2010075312W WO 2011120273 A1 WO2011120273 A1 WO 2011120273A1
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solution
solid
reaction
solid phase
mns0
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PCT/CN2010/075312
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English (en)
French (fr)
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姜志光
华东
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贵州红星发展股份有限公司
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Priority to US13/578,708 priority Critical patent/US8747802B2/en
Priority to JP2012549231A priority patent/JP5369239B2/ja
Priority to EP10848733.1A priority patent/EP2557067B1/en
Priority to KR1020127017454A priority patent/KR101377851B1/ko
Publication of WO2011120273A1 publication Critical patent/WO2011120273A1/zh

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D1/00—Evaporating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/38—Liquid-membrane separation

Definitions

  • the present invention relates to a process for the preparation of manganese sulfate monohydrate, and more particularly to a process for the preparation of manganese sulfate monohydrate using MnO. Background technique
  • MnS0 4 . H 2 0 is usually used in the preparation of cathode materials for automotive power batteries.
  • impurity ions such as K, Na, Ca, Mg, Fe and various heavy metal ions in MnS0 4 . H 2 0
  • the content has higher requirements.
  • the prior art method for producing MnS0 4 ⁇ H 2 0 is accompanied by a large amount of by-products for impurity separation, such as: BaS0 4, etc. These by-products have a certain market capacity, but compared with the requirements of automotive power batteries, this part The total market demand for by-products is small, so it is urgent to design a higher-capacity method to prepare MnS0 4 ⁇ 0 products.
  • the Mn0 2 ore in nature is generally divided into high grade and low grade.
  • the high grade is generally used in the ferroalloy industry, and the application of low grade Mn0 2 has always been a problem to be solved.
  • the grade of MnO produced by its raw materials is also higher. low. At present, there is no effective utilization method for MnO with a weight percentage of less than 20%, both at home and abroad. Summary of the invention
  • the invention provides a method for preparing MnS0 4 ⁇ H 2 0, which utilizes MnO to prepare manganese sulfate monohydrate, and particularly can be carried out using low-grade MnO as a raw material.
  • the main chemical reactions involved in the present invention include:
  • the method includes the following steps:
  • the raw material of the reaction may be any kind of MnO, or even a lower content of MnO, such as a weight percentage of 10- 20% of MnO, such as manganese dioxide ore and reducing sulfide produced by the patent application No. 200910157921.
  • a solution of MnS0 4 is obtained, which produces ammonia gas.
  • the end point of the application is that the gas is no longer produced, and there are some impurities such as Ca, Mg, K, Na, Fe in the solution.
  • the ammonia gas generated in the step 1) can be recovered by a bubble absorption device, and the invention can be realized by using a two-stage bubble absorption device.
  • the device is heated to 100 ° C for 30-60 minutes. , then stop heating.
  • step 1) measuring step 1) the concentration of MnS0 4 in the obtained solution, adding an equimolar reaction of the ammonium sulfide solution under stirring, separating the obtained product into a solid liquid, washing the solid phase;
  • the concentration of the MnS0 4 solution is first determined by a chemical method, and ammonium sulfide is commercially available, and the reaction is carried out in an equimolar ratio to obtain a corresponding concentration, and a mixture of MnS and (Li 4 ) 2 S0 4 is obtained after the reaction.
  • MnS mainly exists in the solid phase
  • (Li 4 ) 2 S0 4 mainly exists in the liquid phase, wherein some impurities are also included in the liquid phase and the solid phase, and the step of washing the solid phase is mainly for separating the solid phase.
  • Soluble impurity ions such as: K+, 3 ⁇ 4+, Mg 2+ , Ca 2+ , etc.
  • the step of washing the solid phase after the solid-liquid separation in the step 2) can be washed with hot water at 60-80 ° C, the ratio of material to water is generally 1:4-1:5, and the washing time is generally 2 hours.
  • step 2) The solid phase obtained in step 2) is dissolved by concentrated acid, hydrogen peroxide is added to the obtained solution, the temperature is raised and boiled, the pH of the solution is adjusted to 5-6, the solid phase is removed by precision filtration, and the filtrate is evaporated and dried.
  • the MnS0 4 ⁇ H 2 0 product was obtained.
  • step 3 hydrogen peroxide is added in step 3) to remove impurities such as iron, and on the other hand, a small amount of sulfide can be oxidized without introducing other impurities; precision filtration is to remove impurities in the form of precipitates, for example: colloid of iron And fine sulfur and so on.
  • a basic compound of manganese Mn(0H) 2 or MnCO 3 or the like.
  • the pH may be adjusted between 1-2, and the step is still preferably (011) 2 or (0 3 ). This is because when the acidity is too large.
  • the amount of impurities such as hydrogen peroxide to remove iron may affect the quality of the product.
  • the H 2 S produced in the step 3) can be absorbed by the secondary NH 4 0H solution of the secondary bubbling absorption device, and the product of the H 2 S is absorbed by the Li 4 0H (Li 4 ) 2 S
  • the reaction can be carried out by introducing the (Li 4 ) 2 S solution in step 2) to achieve the effect of recycling the raw materials, but if the equimolar reaction is to be ensured, the ammonium sulfide concentration should be re-measured before the reaction between the ammonium sulfide and the manganese sulfate.
  • the precision filtration in the step 3) can be carried out by using a filter having a diameter of 0.2 to 0.45 ⁇ m, and can be realized by a filter press.
  • FIG. 1 The main process flow chart of the method of the present invention is shown in FIG.
  • the manganese sulfate solution produced by the reaction of ⁇ with (NH 4 ) 2 S0 4 is subjected to a vulcanization process to separate impurities while reducing the amount of by-products and increasing the productivity of manganese sulfate, which is MnS0 4 ⁇ H 20 0 products have created conditions for large-scale industrial production.
  • the cycle purification process adopted by the invention solves the problem of capacity limitation by recycling the auxiliary material while purifying the MnS0 4 .
  • Example 1 The crude product containing MnO obtained by reacting manganese dioxide ore powder of Guizhou Red Star Co., Ltd. with SrS or BaS solution was used as a raw material to carry out the reaction in the examples.
  • Example 1 The crude product containing MnO obtained by reacting manganese dioxide ore powder of Guizhou Red Star Co., Ltd. with SrS or BaS solution was used as a raw material to carry out the reaction in the examples.
  • MnO weight content 17.51%) obtained by combining 1500 g of Ba-Mn (ie, manganese dioxide ore powder and BaS solution) was placed in a 5000 mL beaker, and 3490 mL of a solution of 147 g/L (Li 4 ) 2 S0 4 was added. The reaction was heated under stirring, and the generated gas was recovered by a secondary bubbling absorption device, and the device was heated to 10 (TC was maintained for 60 minutes, and heating was stopped;
  • the solution was incubated with a small amount of deionized water, and the filtrate was combined to determine the concentration of the MnS0 4 solution was 221.8 g/L, the volume was 2443 mL, and the concentration was 1.47 mol / L (NH 4 ).
  • 2 S solution 2441ml equimolar reaction stirring for 30 minutes, suction filtration, the filtrate was discarded, the filter cake was washed with 60 ° C hot water, 1: 5 ratio of water, 2 hours, separated by suction filtration, the filtrate was discarded;
  • the filter cake was dissolved in 200 ml of concentrated acid, and the generated H 2 S was absorbed by a second-grade 40 ° solution.
  • the filtrate was added to a concentration of 27 ml of a weight percent of 27.5% of industrial hydrogen peroxide to boil, maintaining a slight boiling for 15 minutes.
  • the filter press is precisely filtered, wherein the filter membrane diameter is 0. 24 ⁇ ⁇ , the clarified filtrate is evaporated, and dried at 85 ° C. MnS0 4 ⁇ H 2 0 sample 1# was obtained after 16 hours of drying.
  • MnO weight content 9.71%) obtained by combining 1500 g of Ba_Sr (ie, manganese dioxide ore powder and SrS solution) was placed in a 5000 mL beaker, and 2084 mL of a solution of 130 g/L (Li 4 ) 2 S0 4 was added, and the reaction was heated under stirring. The generated gas was recovered by a secondary bubble absorption device, and the device was heated to 10 (TC was maintained for 30 minutes, and heating was stopped.
  • Ba_Sr ie, manganese dioxide ore powder and SrS solution
  • the solution was separated by suction filtration, the funnel was rinsed with a small amount of deionized water, and the filtrate was combined to determine the concentration of the MnS0 4 solution was 206. lg/L, the volume was 1458 mL, and the concentration was 1.52 mol/L (Li 4 ) 2 under stirring. S solution 1309ml equimolar reaction, stirring for 30 minutes, suction separation, the filtrate was discarded, filter cake with 80 °C hot water, 1: 4 ratio of water, washing for 2 hours, suction filtration separation, the filtrate was discarded;
  • the method of the present invention can produce a higher purity

Description

一种制备一水合硫酸锰的方法
技术领域
本发明涉及一种制备一水合硫酸锰的方法， 尤其涉及一种利用 MnO制备 一水合硫酸锰的方法。 背景技术
MnS04 . H20 通常被用于汽车动力电池正极材料的制备， 在应用过程中， 对 MnS04 . H20 中杂质离子如： K、 Na、 Ca、 Mg、 Fe及多种重金属离子的含量 有较高的要求。 现有技术生产 MnS04 · H20的方法， 为了进行杂质分离会伴有 较大量的副产品， 如： BaS04等， 这些副产品具有一定的市场容量， 然而相比 汽车动力电池所需， 该部分副产品的市场总需求较小， 因此急需设计出产能 较高的方法， 制备 MnS04 · 0产品。
自然界中的 Mn02矿一般分为高品位和低品位， 高品位的一般用于铁合金 行业， 而低品位的 Mn02的应用一直是个有待解决的问题， 以其为原料生产的 MnO 的品位也较低。 目前， 无论是国内外， 对于重量百分比含量小于 20%的 MnO均没有有效的利用方法。 发明内容
本发明提供一种制备 MnS04 · H20的方法， 该方法利用 MnO制备一水合硫 酸锰， 尤其可以以低品位 MnO为原料进行。
本发明所涉及的主要化学反应包括：
MnO + (丽 4) 2S04 → MnS04 +丽 3 1
MnS04 + (丽 4) 2S → MnS + (丽 4) 2S04
MnS + H2S04 → MnS04 + H2S t
该方法包括以下步骤：
1 )将 MnO与（丽 4) 2S04溶液进行加热反应， 将所得产物固液分离； 此反应的原料可以为任何一种 MnO，甚至是含量较低的 MnO , 如重量百分 比含量为 10- 20%的 MnO ,例如申请号为 200910157921. 8的专利申请中的二氧 化锰矿和还原性硫化物生成的 Mn0。 反应之后得到 MnS04溶液， 产生氨气， 反 应的终点为气体不再产生为止， 此时溶液中还有部分的 Ca、 Mg、 K、 Na、 Fe 等杂质。
优选地， 所述步骤 1 )产生的氨气可以利用鼓泡吸收装置回收， 本发明 采用二级鼓泡吸收装置即可实现， 具体操作时先将该装置升温至 100°C维持 30-60分钟， 然后停止加热。
2 )测定步骤 1 )所得溶液中 MnS04的浓度， 搅拌下加入硫化铵溶液等摩 尔反应， 将得到的产物固液分离， 洗涤固相；
此反应步骤先利用化学法测定 MnS04溶液的浓度， 而硫化铵为市售可得， 按照等摩尔比例配制成相应的浓度进行反应， 反应之后得到 MnS 与（丽 4)2S04 的混合物， 其中 MnS主要存在于固相之中， 而（丽 4) 2S04主要存在于液相之中， 其中液相和固相中还包括一些杂质， 洗涤固相步骤主要是为了分离固相中的 可溶性杂质离子， 如： K+、 ¾+、 Mg2+、 Ca2+等。
优选地， 所述步骤 2 ) 中固液分离后的洗涤固相步骤， 可以利用 60-80 °C热水洗涤， 料水比一般为 1: 4-1: 5, 洗涤时间一般为 2小时。
3 )将步骤 2)所得固相利用浓^ £酸溶解， 在所得溶液中加入过氧化氢， 升温煮沸， 调节溶液 PH值至 5-6, 精密过滤去除固相部分， 滤液经蒸发、 烘 干获得 MnS04 · H20产品。
其中， 在步骤 3 ) 中加入过氧化氢是为了除去铁等杂质， 另一方面还可 以氧化少量的硫化物， 同时不引入其他杂质； 精密过滤是为了去除沉淀形式 的杂质， 例如： 铁的胶体及细微的硫磺等。 行， 例如锰的碱性化合物， Mn(0H)2或 MnC03等。
优选地， 所述步骤 3 ) 中加入过氧化氢之前， 可以先调节 PH值在 1-2之 间， 此步骤仍然优选 （011)2或 (03进行。 此举是因为酸度过大时， 加入适 量的过氧化氢除铁等杂质后， 再用 Mn(0H)2或 MnC03中和时带入的铁等杂质的 量较多， 会影响产品的品质。
优选地， 所述步骤 3 )产生的 H2S 可以用所述二级鼓泡吸收装置的二级 NH40H溶液吸收， 并且所述丽 40H吸收 H2S的产物（丽 4) 2S可以导入步骤 2 ) 中 的（丽 4) 2S溶液中继续进行反应， 以达到循环使用原料的效果， 只是如果要确 保等摩尔反应则应在硫化铵与硫酸锰反应之前重新测定硫化铵的浓度。 优选地， 所述步骤 3 ) 中的精密过滤可采用直径为 0. 24-0. 45 μ ηι的滤膜 进行， 并可通过压滤机实现。
其中， 以上各步骤中所涉及的主要工艺条件以及反应设备均为现有技术 中所通用的， 也并不是本发明的发明点， 在此不再赘述。
本发明方法的主要工艺流程图如图 1所示。
本发明通过 ΜηΟ与（NH4) 2S04的反应， 产生的硫酸锰溶液经过硫化等工序 处理， 对杂质进行分离的同时减少了副产品的数量， 提高了硫酸锰的产能， 为 MnS04 · H20产品大规模工业化生产创造了条件。
本发明采用的循环提纯工艺路线， 在对 MnS04进行提纯的同时， 循环回用 辅助材料， 从而解决了产能制约问题。 附图说明
本发明方法的主要工艺流程图如图 1所示。 具体实施方式
将贵州红星股份有限公司二氧化锰矿粉和 SrS或 BaS溶液反应获得的含 MnO的粗产品， 作为原料进行实施例中的反应。 实施例 1
取 1500gBa-Mn结合（即二氧化锰矿粉和 BaS溶液反应 )获得的 MnO (重 量含量 17. 51% ) 置于 5000mL烧杯中， 加入浓度为 147g/L 的（丽 4) 2S04溶液 3490mL , 搅拌下加热反应， 产生的气体用二级鼓泡吸收装置回收， 将该装置 升温至 10 (TC维持 60分钟， 停止加热；
将上述溶液吸滤分离， 漏斗用少量去离子水淋洗， 合并滤液， 测定 MnS04 溶液浓度为 221. 8g/L体积为 2443mL ,搅拌下加入浓度为 1. 47mo l /L的 (NH4) 2S 溶液 2441ml等摩尔反应， 维持搅拌 30分钟后吸滤分离， 滤液弃， 滤饼用 60 °C热水， 1 : 5料水比例， 洗涤 2小时， 吸滤分离， 滤液弃；
滤饼用 200ml浓^ £酸溶解， 产生的 H2S用二级丽 40H溶液吸收， 滤液加入 10ml重量百分浓度 27. 5%工业级过氧化氢加热煮沸， 维持轻微沸腾 15分钟， 利用压滤机精密过滤， 其中滤膜直径为 0. 24 μ ηι, 澄清滤液经蒸发、 85 °C烘 干 16小时获得 MnS04 · H20样品 1#。
实施例 2
取 1500gBa_Sr结合（即二氧化锰矿粉和 SrS溶液反应 )获得的 MnO (重 量含量 9.71%) 置于 5000mL 烧杯中， 加入浓度为 130g/L 的（丽 4) 2S04溶液 2084mL, 搅拌下加热反应， 产生的气体用二级鼓泡吸收装置回收， 将该装置 升温至 10 (TC维持 30分钟， 停止加热。
将上述溶液吸滤分离， 漏斗用少量去离子水淋洗， 合并滤液， 测定 MnS04 溶液浓度为 206. lg/L,体积为 1458mL,搅拌下加入浓度为 1.52mol/L的 (丽 4) 2S 溶液 1309ml等摩尔反应， 维持搅拌 30分钟后吸滤分离， 滤液弃， 滤饼用 80 °C热水， 1: 4料水比例， 洗涤 2小时， 吸滤分离， 滤液弃；
滤饼用 111ml浓^ £酸溶解， 调节溶液 PH值为 1, 产生的 H2S用二级 NH40H 溶液吸收， 二级丽 40H溶液形成的（丽 4) 2S溶液可以导入 MnS04溶液继续反应 , 但应在重新测定（丽 4)2S 溶液浓度之后进行， 滤液加入 10ml 重量百分浓度 27.5%工业级过氧化氢加热煮沸， 维持轻微沸腾 15分钟， 采用直径为 0.45 μ m的滤膜精密过滤， 澄清滤液经蒸发， 85°C烘干 16小时获得 MnS04 · H20样品 2#。
各实施例所得样品中的各成分的重量含量如下表:
Figure imgf000006_0001
通过上表可以看出， 利用本发明的方法可以生产出纯度较高的
酸锰， 各种金属杂质的含量显著降低。

Claims

权 利 要 求 书
1、 一种制备一水合硫酸锰的方法， 包括步骤：
1 ) 将 MnO与（丽 4) 2S04溶液进行加热反应， 将所得产物固液分离；
2) 测定步骤 1 )所得溶液中 MnS04的浓度， 搅拌下加入硫化铵溶液等 摩尔反应， 将得到的产物固液分离， 洗涤固相；
3) 将步骤 2)所得固相利用浓^ £酸溶解， 在所得溶液中加入过氧化氢， 升温煮沸， 调节溶液 PH值至 5-6, 精密过滤去除固相部分， 滤液经蒸发、 烘 干获得 MnS04 · H20产品。
2、 如权利要求 1所述的方法， 其特征在于， 所述步骤 1 ) 中的 MnO为重 量百分比含量 10-20%的 Mn0。
3、 如权利要求 1所述的方法， 其特征在于， 所述步骤 1 )产生的氨气利 用鼓泡吸收装置回收。
4、 如权利要求 3所述的方法， 其特征在于， 所述步骤 1 )吸收氨气的步 骤为先将该鼓泡吸收装置升温至 100°C维持 30-60分钟， 然后停止加热。
5、 如权利要求 1所述的方法， 其特征在于， 所述步骤 2) 中固液分离后 的洗涤固相步骤， 利用 60-80°C热水洗涤， 料水比为 1: 4-1: 5。
6、 如权利要求 1所述的方法， 其特征在于， 所述步骤 3) 中加入过氧化 氢前， 先调节 PH值在 1-2之间。
7、 如权利要求 1或 6所述的方法， 其特征在于， 所述步骤 3 )的调节 PH 值步骤用 MnC03或 Mn (OH) 2进行。
8、 如权利要求 1所述的方法， 其特征在于， 所述步骤 3)产生的 H2S用 所述二级鼓泡吸收装置的二级丽4011溶液吸收。
9、如权利要求 8所述的方法， 其特征在于，还包括将所述丽 40H吸收 H2S 的产物 (丽 4)2S导入步骤 2 ) 中的 (丽 4)2S溶液中反应的步骤。
10、 如权利要求 1所述的方法， 其特征在于， 所述步骤 3) 中的精密过 滤采用直径为 0.24-0.45 μηι的滤膜进行。
PCT/CN2010/075312 2010-03-31 2010-07-20 一种制备一水合硫酸锰的方法 WO2011120273A1 (zh)

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US13/578,708 US8747802B2 (en) 2010-03-31 2010-07-20 Method for preparing manganese sulfate monohydrate
JP2012549231A JP5369239B2 (ja) 2010-03-31 2010-07-20 硫酸マンガン一水和物の製造方法
EP10848733.1A EP2557067B1 (en) 2010-03-31 2010-07-20 Method for preparing manganese sulfate monohydrate
KR1020127017454A KR101377851B1 (ko) 2010-03-31 2010-07-20 황산 망간 일수화물의 제조방법

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CN114229906A (zh) * 2022-01-24 2022-03-25 广西锰华新能源科技发展有限公司 一种低碳工艺制备高纯硫酸锰的方法和应用

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CN114229906A (zh) * 2022-01-24 2022-03-25 广西锰华新能源科技发展有限公司 一种低碳工艺制备高纯硫酸锰的方法和应用
CN114229906B (zh) * 2022-01-24 2024-04-05 广西锰华新能源科技发展有限公司 一种低碳工艺制备高纯硫酸锰的方法和应用

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CN101838017B (zh) 2012-02-15
EP2557067A1 (en) 2013-02-13
EP2557067B1 (en) 2014-04-16
JP5369239B2 (ja) 2013-12-18
US8747802B2 (en) 2014-06-10
KR101377851B1 (ko) 2014-03-25
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