CN115650300A - Method for combined production of manganese carbonate and nano barium sulfate - Google Patents
Method for combined production of manganese carbonate and nano barium sulfate Download PDFInfo
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Abstract
The invention relates to the technical field of inorganic chemical industry, and particularly discloses a method for jointly producing manganese carbonate and nano barium sulfate, which comprises the following steps: (1): reacting pyrolusite powder with barium sulfide solution, and carrying out solid-liquid separation on reaction products; (2): reacting the solid phase obtained in the step (1) with sulfuric acid, and carrying out solid-liquid separation on a reaction product; (3): reacting the liquid phase obtained in the step (2) with a barium sulfide solution twice, and performing solid-liquid separation twice; (4): washing a solid phase obtained in the second solid-liquid separation in the step (3) by using hot deionized water, and carrying out solid-liquid separation; (5): adding water into the solid phase obtained in the step (4), introducing oxygen for oxidation, and carrying out solid-liquid separation on the reaction product to obtain a solid phase which is barium sulfate; (6): reacting the liquid phase obtained in the step (5) with hydrogen peroxide, adjusting the pH value to 5.0-6.0, and carrying out solid-liquid separation; (7): and (4) neutralizing the liquid phase obtained in the step (7) with a mixture of ammonia water and ammonium bicarbonate, and carrying out solid-liquid separation on a reaction product to obtain a solid phase of manganese carbonate.
Description
Technical Field
The invention relates to the technical field of inorganic chemical industry, in particular to a method for jointly producing manganese carbonate and nano barium sulfate.
Background
The high-purity manganese carbonate is mainly used for manufacturing magnetic conductive materials in communication equipment, and alkali metals such as potassium and sodium, alkaline earth metals such as calcium and magnesium and sulfates contained in the manganese carbonate serving as a manganese source substance have remarkable influence on the magnetization characteristics. At present, the domestic production of high-purity manganese carbonate generally takes manganese metal or manganese dioxide as a raw material, manganese nitrate solution is obtained by dissolving the manganese metal or the manganese dioxide in a nitric acid solution system, and then soluble carbonate is used as a precipitator for preparation.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for jointly producing manganese carbonate and nano barium sulfate, so as to reduce the content of other metal ions in the manganese carbonate and simultaneously produce a by-product of barium sulfate.
The invention relates to a basic chemical reaction:
MnO 2 +BaS+H 2 O→Ba(OH) 2 +MnO↓+S↓
MnO+H 2 SO 4 →MnSO 4 +H 2 O
MnSO 4 +BaS→MnS↓+BaSO 4 ↓
MnS+O 2 +H 2 O→MnSO 4
MnSO 4 +NH 4 OH+NH 4 HCO 3 →(NH4) 2 SO 4 +H 2 O+MnCO 3 ↓
the technical scheme of the invention is as follows:
a method for jointly producing manganese carbonate and nano barium sulfate comprises the following steps:
(1): stirring and reacting pyrolusite powder and a barium sulfide solution, and carrying out solid-liquid separation on a reaction product, wherein the main components of the pyrolusite are manganese dioxide and a small amount of other metal oxides (iron, cobalt, nickel, copper, zinc, aluminum, potassium, sodium, calcium, magnesium and the like, wherein most of the oxides are iron oxides), and after reacting with the barium sulfide, a liquid phase is a barium hydroxide solution, and a solid phase is a mixed precipitate of manganese monoxide and sulfur and other impurities (other metal oxides);
(2): reacting the solid phase obtained in the step (1) with sulfuric acid, and carrying out solid-liquid separation on a reaction product, wherein the obtained solid phase is sulfur, and the liquid phase is a manganese sulfate solution and contains a small amount of other metal ions (most iron ions);
(3): reacting the liquid phase obtained in the step (2) with a barium sulfide solution, wherein the barium sulfide solution reacts with the liquid phase obtained in the step (2) in two batches, after a small amount of barium sulfide solution reacts with the liquid phase obtained in the step (2) in the first batch, first solid-liquid separation is carried out, most of other metal ions generate sulfides and are precipitated, the manganese sulfate solution is purified, the liquid phase obtained by the first solid-liquid separation reacts with the barium sulfide solution in the second batch, second solid-liquid separation is carried out, the reaction product is subjected to solid-liquid separation, a mixed precipitate of manganese sulfide and barium sulfate is obtained as a solid phase, and the liquid phase is discarded;
(4): washing the solid phase obtained in the step (3) with hot deionized water, and performing solid-liquid separation, wherein other metal ions (potassium, calcium, sodium and magnesium) in the precipitate can be further removed through hot washing;
(5): adding water into the solid phase obtained in the step (4) for pulping, introducing oxygen for oxidation, oxidizing manganese sulfide into manganese sulfate, transferring manganese ions into liquid, and carrying out solid-liquid separation on a reaction product to obtain a liquid phase manganese sulfate solution and a solid phase barium sulfate;
(6): carrying out acid washing, neutralization, drying and crushing on the solid phase obtained in the step (5) to obtain a barium sulfate product;
(7): reacting the liquid phase obtained in the step (5) with hydrogen peroxide, adjusting the pH value to 5.0-6.0, separating solid from liquid, adding hydrogen peroxide, and completely precipitating iron ions and aluminum ions in the manganese sulfate solution to obtain a pure manganese sulfate solution;
(8): and (4) neutralizing the liquid phase obtained in the step (7) with a mixture of ammonia water and ammonium bicarbonate, carrying out solid-liquid separation on a reaction product, and washing and drying the obtained solid phase to obtain a manganese carbonate product.
Further, the reaction temperature in the step (1) is controlled to be 45-50 ℃, and the stirring time is 55-60 min.
Furthermore, the solid-to-liquid ratio of the solid phase to the sulfuric acid in the step (2) is 1:4, and the reaction temperature is controlled to be 66-80 ℃.
The invention has the beneficial effects that: manganese sulfate is generated by reacting pyrolusite powder with barium sulfide, manganese sulfate and barium sulfide are obtained by reacting manganese sulfate with barium sulfide, other metal ions in pyrolusite are effectively removed in the process, the purity of the final product manganese carbonate is guaranteed, manganese sulfate and barium sulfate are separated in an oxidation mode, a large amount of waste residues cannot be generated, the by-product barium sulfate can be obtained, the recovery rate of barium is high, raw materials are easy to obtain, and the production cost is effectively reduced.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments disclosed herein are within the scope of the invention.
Example 1:
a method for jointly producing manganese carbonate and nano barium sulfate comprises the following steps:
(1): the pyrolusite powder (mainly comprising manganese dioxide containing a small amount of other metal oxides such as iron, cobalt, nickel, copper, zinc, aluminum, potassium, sodium, calcium, magnesium and the like, wherein the majority of the oxides are iron oxides) and a barium sulfide solution are stirred to react, the reaction temperature is controlled to be 45-50 ℃, the molar ratio of the manganese dioxide to the barium sulfide is 3:1, the content of the barium sulfide is controlled to be 40g/L, the reaction time is 55-60 min, the reaction product is subjected to solid-liquid separation and reacts with the barium sulfide to generate a liquid phase which is a barium hydroxide solution, and the solid phase which is a mixed precipitate of manganese monoxide and sulfur and other impurities (other metal oxides) is maintained at a high temperature, so that the concentration of barium hydroxide in the product can be increased, the reaction temperature is controlled to be 45-50 ℃, the conversion rate of the barium hydroxide is increased along with the increase of the molar ratio of the manganese dioxide to the barium sulfide, and the molar ratio of the pyrolusite powder to the barium sulfide is 3:1, and the high conversion rate of the barium hydroxide can be obtained;
(2): reacting the solid phase obtained in the step (1) with sulfuric acid, wherein the solid-liquid ratio of the solid phase to the sulfuric acid is 1:4, the reaction temperature is controlled at 66-80 ℃, the reaction time is 2 hours, the solid and the liquid of the reaction product are separated, the obtained solid phase is sulfur, the liquid phase is a manganese sulfate solution and contains a small amount of other metal ions (the iron ions are the most), and the solid-liquid ratio is 1:4, so that the leaching rate can be ensured;
(3): reacting the manganese sulfate solution obtained in the step (2) with a barium sulfide solution, wherein the barium sulfide solution is reacted with the manganese sulfate solution in two batches:
first batch: reacting a small amount of barium sulfide solution with a manganese sulfate solution, and filtering, wherein the temperature is controlled at 95 ℃, the reaction time is 4 hours, the molar ratio of metal impurities in the manganese sulfate solution to sulfur in the barium sulfide is 1:2, and iron, copper, cobalt, nickel, lead, arsenic, chromium, cadmium, mercury and other ions in the manganese sulfate solution can be precipitated with sulfur ions, so that the manganese sulfate solution is purified;
and (3) second batch: reacting the manganese sulfate solution obtained by the first solid-liquid separation with a barium sulfide solution, wherein the molar ratio of manganese sulfate to barium sulfide is 1:1, the temperature is 95 ℃, the reaction time is 4 hours, carrying out the second solid-liquid separation to obtain a solid phase which is a mixed precipitate of manganese sulfide and barium sulfate, and discarding the liquid phase;
(4): washing the manganese sulfide and barium sulfate obtained in the step (3) with hot deionized water, wherein the solid-liquid ratio is 1:7, the temperature is controlled at 80 ℃, the time is 7 hours, then carrying out solid-liquid separation, and further removing other metal ions (potassium, calcium, sodium and magnesium) in the manganese sulfide and barium sulfate precipitate through hot washing;
(5): adding water into the solid phase obtained in the step (4) for pulping, introducing oxygen for oxidation, pulping for 1 hour according to 400kg of filter cake per cubic meter of water, reacting for 9 hours at the temperature of 60 ℃, oxidizing manganese sulfide into manganese sulfate, transferring manganese ions into liquid, and performing solid-liquid separation on a reaction product to obtain a liquid phase which is a manganese sulfate solution and a solid phase which is barium sulfate;
(6): acid washing, neutralizing, drying and crushing the barium sulfate obtained in the step (5) to obtain a barium sulfate product;
(7): reacting the manganese sulfate solution obtained in the step (5) with hydrogen peroxide, adjusting the pH value to 5.0-6.0, performing solid-liquid separation, adding hydrogen peroxide, and completely precipitating other residual metal ions, mainly iron ions and aluminum ions, in the manganese sulfate solution to obtain a pure manganese sulfate solution;
(8): and (3) neutralizing the manganese sulfate solution obtained in the step (7) with a mixture of ammonia water and ammonium bicarbonate, wherein the molar ratio of manganese sulfate to ammonia water and the molar ratio of manganese sulfate to ammonium bicarbonate are both 1:1, the reaction temperature is 60 ℃, the pH value is controlled to be 7, the reaction time is 1h, the aging time is 6 h, the solid and liquid of the reaction product are separated, the obtained solid phase is high-purity manganese carbonate, centrifugally precipitating and dehydrating the manganese carbonate, drying at the temperature of 80 ℃, and crushing to obtain the high-purity manganese carbonate product.
According to the method, the pyrolusite powder and the barium sulfide react to generate the manganese sulfate, and then the manganese sulfate and the barium sulfide react to obtain the manganese sulfide and the barium sulfate, so that other metal ions in the pyrolusite are effectively removed in the process, the purity of the final product manganese carbonate is ensured, the manganese sulfate and the barium sulfate are separated in an oxidation mode, a large amount of waste residues are not generated, the by-product barium sulfate can be obtained, the recovery rate of barium is high, the raw materials are easy to obtain, and the production cost is effectively reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, but rather as the intention of all modifications, equivalents, improvements within the spirit and scope of the invention.
Claims (3)
1. The method for jointly producing the manganese carbonate and the nano barium sulfate is characterized by comprising the following steps of:
(1): stirring and reacting pyrolusite powder and barium sulfide solution, and carrying out solid-liquid separation on reaction products;
(2): reacting the solid phase obtained in the step (1) with sulfuric acid, and carrying out solid-liquid separation on a reaction product;
(3): reacting the liquid phase obtained in the step (2) with a barium sulfide solution, wherein the barium sulfide solution reacts with the liquid phase obtained in the step (2) in two batches, after a small amount of barium sulfide solution reacts with the liquid phase obtained in the step (2) in the first batch, carrying out first solid-liquid separation, reacting the liquid phase obtained by the first solid-liquid separation with the barium sulfide solution in the second batch, and carrying out second solid-liquid separation;
(4): washing a solid phase obtained in the second solid-liquid separation in the step (3) by using hot deionized water, and carrying out solid-liquid separation;
(5): adding water into the solid phase obtained in the step (4), introducing oxygen for oxidation, and carrying out solid-liquid separation on the reaction product;
(6): carrying out acid washing, neutralization, drying and crushing on the solid phase obtained in the step (5) to obtain a barium sulfate product;
(7): reacting the liquid phase obtained in the step (5) with hydrogen peroxide, adjusting the pH value to 5.0-6.0, and carrying out solid-liquid separation;
(8): and (4) neutralizing the liquid phase obtained in the step (7) with a mixture of ammonia water and ammonium bicarbonate, carrying out solid-liquid separation on a reaction product, and washing and drying the obtained solid phase to obtain a manganese carbonate product.
2. The method for jointly producing manganese carbonate and nano barium sulfate according to claim 1, wherein the reaction temperature in the step (1) is controlled to be 45-50 ℃, the molar ratio of manganese dioxide to barium sulfide in pyrolusite powder is 3:1, and the stirring time is 55-60 min.
3. The method for jointly producing manganese carbonate and nano barium sulfate according to claim 1, wherein the solid-to-liquid ratio of the solid phase to the sulfuric acid in the step (2) is 1:4, and the reaction temperature is controlled to be 70-80 ℃.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425613A (en) * | 2003-01-28 | 2003-06-25 | 天津理工学院 | Process for united producing barium hydroxide and manganese sulfate |
| CN101704554A (en) * | 2009-07-16 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for preparing manganese sulfate |
| 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 |
| CN103361669A (en) * | 2013-07-30 | 2013-10-23 | 贵州红星发展股份有限公司 | High-performance electrolytic manganese dioxide, preparation method and application thereof |
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- 2022-10-14 CN CN202211260079.2A patent/CN115650300A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1425613A (en) * | 2003-01-28 | 2003-06-25 | 天津理工学院 | Process for united producing barium hydroxide and manganese sulfate |
| CN101704554A (en) * | 2009-07-16 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for preparing manganese sulfate |
| 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 |
| CN103361669A (en) * | 2013-07-30 | 2013-10-23 | 贵州红星发展股份有限公司 | High-performance electrolytic manganese dioxide, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| 徐旺生等: "软锰矿氧化硫化钡制高纯碳酸锰和氢氧化钡工艺研究", 河南化工, no. 05, pages 10 - 12 * |
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