CN1083803C - Roasting process of preparing very pure mangano-manganic oxide and its use - Google Patents
Roasting process of preparing very pure mangano-manganic oxide and its use Download PDFInfo
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- CN1083803C CN1083803C CN98112437A CN98112437A CN1083803C CN 1083803 C CN1083803 C CN 1083803C CN 98112437 A CN98112437 A CN 98112437A CN 98112437 A CN98112437 A CN 98112437A CN 1083803 C CN1083803 C CN 1083803C
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Abstract
The present invention relates to a method for baking and preparing high-purity manganic manganous oxide, which adopts the raw materials of manganese sulfate and ammonium bicarbonate. The present invention has the technological process that manganese carbonate obtained from the reaction of the manganese sulfate and the ammonium bicarbonate is converted into manganese monoxide with a face-centered cubic structure and manganese dioxide with a square structure in order under an oxygenic condition, then the manganese dioxide is reduced to manganic oxide and beta-manganic manganous oxide with a square structure in order, and finally, gamma-manganic manganous oxide with a face-centered cubic structure is obtained. The manganic manganous oxide prepared by the method has high specific gravity, moisture absorption resistance and oxidation resistance.
Description
The invention belongs to the field of the following:
the invention relates to a roasting manufacturing method of high-purity mangano-manganic oxide.
Background art:
manganous manganic oxide is one of the important raw materials for producing soft magnetic ferrite in the electronic industry. In order to ensure the quality of the soft magnetic ferrite core, the adopted manganous-manganic oxide has the requirements of high purity, large specific surface area and good activity. In the prior art, the production method of high-purity trimanganese tetroxide includes four types, namely a roasting method, an oxidation method, a reduction method, an electrolysis method and the like. The roasting method, the reduction method and the electrolytic method are used for manufacturing high-purity trimanganese tetroxide and are still in the experimental preparation stage. The current domestic industrial production of high-purity trimanganese tetroxide almost adopts an oxidation method, namely expensive electrolytic manganese powder is taken as a raw material, ammonium salt is taken as an additive, and gamma-type trimanganese tetroxide with brown crystal grains is prepared by filtering, washing and drying after the reaction is finished, the method has large equipment investment and high production cost, also contains certain water content, sulfur content and ignition loss, is easy to absorb oxygen in the air and oxidized, and is easy to agglomerate when being used and stored in an air humid area; for example, when the brown mangano-manganic oxide produced by oxidation in a certain factory is used in Taiwan, the phenomenon of deterioration caused by moisture absorption and agglomeration occurs. And the brown mangano-manganic oxide has a loose grain structure, and the magnetic core prepared by taking the brown mangano-manganic oxide as a raw material has unsatisfactory quality. The Chinese manganese industry (4)1990 introduces a method for preparing trimanganese tetroxide: the analytical pure manganese carbonate is used as a raw material to prepare the trimanganese tetroxide by roasting, the method still stays in a laboratory discussion stage, but proves the feasibility of preparing the high-purity trimanganese tetroxide by roasting the manganese carbonate as the raw material.
The invention content is as follows:
the invention aims to provide a method for preparing high-purity trimanganese tetroxide with excellent quality, difficult moisture absorption, caking and difficult oxidation.
In order to accomplish the above task, the technical solution of the present invention is designed as follows.
Mixing manganese sulfate and ammonium bicarbonate after impurity removal to react in a solution to generate manganese carbonate precipitate, controlling the temperature at 20-60 ℃, separating the manganese carbonate precipitate, decomposing the manganese carbonate at 80-150 ℃ to obtain manganese monoxide with a face-centered cubic structure, roasting and oxidizing the manganese monoxide with the face-centered cubic structure at 150-500 ℃ to obtain manganese dioxide with a square structure, sequentially reducing the manganese dioxide with the square structure under the oxygen-free condition to obtain body-centered cubic structure α -manganous oxide and square structure β -manganous oxide, finally obtaining gamma-manganous oxide with the face-centered cubic structure, cooling the gamma-manganous oxide to normal temperature under the oxygen-free condition to obtain a black high-purity manganous oxide finished product, wherein the process temperature conditions are that the manganese dioxide with the square structure is reduced to α -manganous oxide with the body-centered cubic structure, the temperature is controlled at 500-850 ℃, the temperature is controlled at 600 ℃, the temperature is controlled at α -manganous oxide with the body-centered cubic structure is reduced to β -manganous oxide with the square structure, and the temperature is controlled at 850-850 ℃ to 850 ℃.
The reaction formula of the material change in each process step is as follows:
manganese sulfate and ammonium bicarbonate react in solution to produce manganese carbonate precipitate Manganese carbonate is decomposed into manganese monoxide with face-center vertical surface structure
The manganese monoxide with the face-centered cubic structure is oxidized into manganesedioxide with a square structure.The manganese dioxide with the tetragonal structure is reduced into α -manganese sesquioxide with a body-centered cubic structure.α -manganese sesquioxide with body-centered cubic structure is reduced into β -tetragonTrimanganese oxide. Manganese sesquioxide β -manganomanganic oxide
β -manganomanganic oxide with a tetragonal structure is converted into gamma-manganomanganic oxide with a body-centered cubic structure.
The high-purity gamma-manganic manganous oxide prepared by the process is one of the main raw materials for producing the manganese-zinc-iron oxide magnetic core, so the high-purity gamma-manganic manganous oxide is mainly used for producing the soft magnetic ferrite magnetic core.
The black gamma-mangano-manganic oxide produced by the invention has the density of 4870Kg/m detected by related departments3The specific gravity of brown trimanganese tetroxide produced by the oxidation method is 4250Kg/m3Therefore, the shrinkage rate of the gamma-manganomanganic oxide produced by the invention is small, the produced magnetic core is not easy to deform, the product percent of pass can be improved by more than 10%, and the method is particularly beneficial to producing large magnetic coresHigh conductivity, which is rare in the current magnetic core industry. In addition, the preparation method has simple production equipment, less investment and easy formation of industrial production, and the product is stable in the air, difficult to agglomerate and oxidize and convenient to store.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to specific examples.
Mixing and reacting the manganese sulfate and ammonium bicarbonate after impurity removal in the solution, controlling the temperature at 20-60 ℃ to obtain manganese carbonate precipitate, wherein the chemical reaction formula is as follows: manganese sulfate ammonium bicarbonate ammonium sulfate manganese carbonate
Separating the manganese carbonate precipitate from the solution, and heating and decomposing at 80-150 ℃ to obtain the manganese monoxide of the face-centered cubic body, wherein the chemical reaction formula is as follows:
under the condition of oxygen, manganese monoxide is oxidized into manganese dioxide with a cubic structure when heated to 150-500 ℃, and the chemical reaction formula is as follows:
manganese dioxide is reduced into manganese sesquioxide with a body-centered cubic structure under the conditions of no oxygen and the temperature of 500-600 ℃. The chemical reaction formula is as follows:
the manganous oxide is reduced into β -manganous oxide with a tetragonal structure at the oxygen-free temperature of 600-850 ℃.
β -manganomanganic oxide is converted into gamma-manganomanganic oxide at the temperature of 850-1100 ℃.
Claims (1)
1. A process for calcining high-purity trimanganese tetroxide includes such steps as preparing the manganous carbonate from the reaction of manganous sulfate and ammonium hydrogen carbonate, sequentially converting it to face-centered cubic manganese oxide and tetragonal manganese dioxide under aerobic condition, sequentially preparing α -manganous oxide and tetragonal β -trimanganese tetroxide from said manganese dioxide under anaerobic condition, preparing the face-centered cubic gamma-trimanganese tetroxide, mixing them in solution to obtain manganese carbonate deposit, controlling the temp at 20-60 deg.C, decomposing said manganous carbonate to become trimanganese monoxide at 80-150 deg.C, oxidizing face-centered cubic manganese oxide to tetragonal manganese dioxide at 150-500 deg.C, converting it to α -manganous oxide at 500-600 deg.C, reducing face-centered cubic manganese oxide to tetragonal manganese oxide at β -800 deg.C, and converting it to tetragonal cubic manganous oxide at 800-539 deg.C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112437A CN1083803C (en) | 1998-04-17 | 1998-04-17 | Roasting process of preparing very pure mangano-manganic oxide and its use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98112437A CN1083803C (en) | 1998-04-17 | 1998-04-17 | Roasting process of preparing very pure mangano-manganic oxide and its use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1232788A CN1232788A (en) | 1999-10-27 |
| CN1083803C true CN1083803C (en) | 2002-05-01 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN98112437A Expired - Fee Related CN1083803C (en) | 1998-04-17 | 1998-04-17 | Roasting process of preparing very pure mangano-manganic oxide and its use |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011294A (en) * | 2012-12-17 | 2013-04-03 | 攀枝花市立宇矿业有限公司 | Preparation method of manganese tetraoxide |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102849800B (en) * | 2012-08-24 | 2015-12-09 | 长沙隆泰微波热工有限公司 | A kind of preparation method of trimanganese tetroxide |
| CN105060349B (en) * | 2015-09-17 | 2017-01-18 | 湖南蒙达新能源材料有限公司 | Method for preparing high-purity great proportion spherical manganous-manganic oxide |
| CN108807970A (en) * | 2018-04-27 | 2018-11-13 | 苏州宇量电池有限公司 | A kind of mangano-manganic oxide negative material and preparation method thereof based on microwave-hydrothermal method |
| CN111362306B (en) * | 2020-03-20 | 2022-06-17 | 湖南特种金属材料有限责任公司 | Preparation method and preparation equipment of spherical porous manganous-manganic oxide |
| CN115367807B (en) * | 2022-08-22 | 2023-04-18 | 重庆上甲电子股份有限公司 | Low-temperature roasting method for producing trimanganese tetroxide for soft magnetism |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647375A (en) * | 1969-10-22 | 1972-03-07 | Japan Metals & Chem Co Ltd | Method of producing manganese dioxide |
| RO105561B1 (en) * | 1990-05-07 | 1992-09-25 | Inst De Metale Neferoase Si Ra | Preparation process for mangana-manganic oxide |
| CN1163232A (en) * | 1996-04-22 | 1997-10-29 | 马鞍山市新月科技发展有限责任公司 | Process for producing mangano-manganic oxide |
-
1998
- 1998-04-17 CN CN98112437A patent/CN1083803C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647375A (en) * | 1969-10-22 | 1972-03-07 | Japan Metals & Chem Co Ltd | Method of producing manganese dioxide |
| RO105561B1 (en) * | 1990-05-07 | 1992-09-25 | Inst De Metale Neferoase Si Ra | Preparation process for mangana-manganic oxide |
| CN1163232A (en) * | 1996-04-22 | 1997-10-29 | 马鞍山市新月科技发展有限责任公司 | Process for producing mangano-manganic oxide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103011294A (en) * | 2012-12-17 | 2013-04-03 | 攀枝花市立宇矿业有限公司 | Preparation method of manganese tetraoxide |
| CN103011294B (en) * | 2012-12-17 | 2014-08-13 | 攀枝花市立宇矿业有限公司 | Preparation method of manganese tetraoxide |
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| Publication number | Publication date |
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| CN1232788A (en) | 1999-10-27 |
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