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WO2011009351A1 - Procédé de purification circulaire du sulfate de manganèse et du carbonate de manganèse - Google Patents

Procédé de purification circulaire du sulfate de manganèse et du carbonate de manganèse 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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WO
WIPO (PCT)
Prior art keywords
manganese
manganese sulfate
manganese carbonate
sulfate
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2010/073957
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English (en)
Chinese (zh)
Inventor
姜志光
华东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SHENZHEN HAOYITONG INVESTMENT AND DEVELOPMENT Co Ltd
Guizhou Redstar Developing Co Ltd
Original Assignee
SHENZHEN HAOYITONG INVESTMENT AND DEVELOPMENT Co Ltd
Guizhou Redstar Developing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SHENZHEN HAOYITONG INVESTMENT AND DEVELOPMENT Co Ltd, Guizhou Redstar Developing Co Ltd filed Critical SHENZHEN HAOYITONG INVESTMENT AND DEVELOPMENT Co Ltd
Publication of WO2011009351A1 publication Critical patent/WO2011009351A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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)

Abstract

La présente invention a pour objet un procédé de purification circulaire du sulfate de manganèse et du carbonate de manganèse, qui comprend les étapes suivantes consistant : (A) à ajouter du bicarbonate d’ammonium dans une solution de sulfate de manganèse à une température de 40 à 80 °C sous agitation pour la synthèse, à amener le point final de la synthèse jusqu’à une réaction équimolaire, à séparer les solides, et à laver avec de l’eau chaude pour obtenir du carbonate de manganèse; (B) à ajouter du carbonate de manganèse dans du H2SO4 à 6 à 12 mol/L pour réagir, à réguler la valeur du pH de la solution réactionnelle jusqu’à 1-2, et à chauffer jusqu’à ébullition; (C) à ajuster la valeur du pH de la solution réactionnelle de l’étape (B) jusqu’à 4-5 par l’ajout du carbonate de manganèse obtenu dans l’étape (A) dans la solution réactionnelle; et (D) à mettre en œuvre une séparation solide-liquide de la solution réactionnelle, à évaporer et à cristalliser le filtrat obtenu, et à sécher pour obtenir du sulfate de manganèse. Du sulfate de manganèse et du carbonate de manganèse de haute pureté ayant de faibles teneurs en calcium et en magnésium et de faibles teneurs en potassium et en sodium peuvent être obtenus par ce procédé.
PCT/CN2010/073957 2009-07-20 2010-06-13 Procédé de purification circulaire du sulfate de manganèse et du carbonate de manganèse Ceased WO2011009351A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN200910161306.4 2009-07-20
CN200910161306A CN101704555A (zh) 2009-07-20 2009-07-20 一种硫酸锰与碳酸锰的循环提纯方法

Publications (1)

Publication Number Publication Date
WO2011009351A1 true WO2011009351A1 (fr) 2011-01-27

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CN (1) CN101704555A (fr)
WO (1) WO2011009351A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114702075A (zh) * 2022-04-11 2022-07-05 中南大学 一种硫酸锰的纯化制备方法

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN103011297B (zh) * 2012-12-07 2014-12-10 中信大锰矿业有限责任公司 软锰矿为原料采用碳火法生产高纯硫酸锰的方法
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
CN108046329B (zh) * 2017-12-01 2019-11-12 盐城市东港药物化工发展有限公司 一种工业废水中回收镁锰元素的工艺
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

Citations (4)

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RO93755A2 (fr) * 1986-03-17 1988-02-29 Unitatea De Cercetare Si Proiectare Pentru Metalurgie Neferoasa,Ro Procede d'obtention du chlorure manganeux
CN1283592A (zh) * 2000-07-08 2001-02-14 中国石油化工股份有限公司巴陵分公司 一种高纯碳酸锰的制造方法
CN1311340A (zh) * 2000-02-28 2001-09-05 邓建成 利用废锰矿浸渣中的硫酸锰生产碳酸锰的方法
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RO93755A2 (fr) * 1986-03-17 1988-02-29 Unitatea De Cercetare Si Proiectare Pentru Metalurgie Neferoasa,Ro Procede d'obtention du chlorure manganeux
CN1311340A (zh) * 2000-02-28 2001-09-05 邓建成 利用废锰矿浸渣中的硫酸锰生产碳酸锰的方法
CN1283592A (zh) * 2000-07-08 2001-02-14 中国石油化工股份有限公司巴陵分公司 一种高纯碳酸锰的制造方法
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114702075A (zh) * 2022-04-11 2022-07-05 中南大学 一种硫酸锰的纯化制备方法

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