CN100500577C - Method for preparing hybrid oxide of manganese by manganese sulfate solution - Google Patents
Method for preparing hybrid oxide of manganese by manganese sulfate solution Download PDFInfo
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- CN100500577C CN100500577C CNB200610011894XA CN200610011894A CN100500577C CN 100500577 C CN100500577 C CN 100500577C CN B200610011894X A CNB200610011894X A CN B200610011894XA CN 200610011894 A CN200610011894 A CN 200610011894A CN 100500577 C CN100500577 C CN 100500577C
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Abstract
The invention belongs to field of non-ferrous metal material, especially relating to a method for preparing mixed oxide of manganese by using manganese solution. It comprises following steps: employing the cleaning liquor extracted by sulfuric acid from manganes mineral-manganese sulfate as raw material; depositing the manganese sulfate solution to manganese sulfate and basic manganese sulfate with ammonia solution; treaing furtherly to converse basic manganese sulfate to manganese hydroxide; oxiding the manganese hydroxide and slight basic manganese sulfate with oxidant into manganomanganic oxide under condition od continous stirring and a certain temperature and pH. The invention is characterized by low sulfur content in got manganomanganic oxide and low cost.
Description
Technical field
The invention belongs to the nonferrous materials field, particularly a kind of method for preparing the mixed oxide of manganese with manganese sulfate solution.
Background technology
The presoma for preparing four manganese oxide has electrolytic metal Mn, manganous hydroxide, manganous carbonate, electrolytic manganese dioxide etc., and wherein the method for preparing trimanganese tetroxide with the electrolytic metal Mn presoma is the main method of domestic and international industrial production trimanganese tetroxide at present.The cost height of electrolytic metal Mn own, the foreign matter content height is with the trimanganese tetroxide poor product quality that it is produced as presoma, cost height.Yet there are no the report of research at home and abroad as the method for preparing trimanganese tetroxide with the mixed oxide of manganese.On March 3rd, 2006, University of Science ﹠ Technology, Beijing applied for " a kind of method that is used to produce the low trimanganese tetroxide of a sulfur-bearing " patent (application number 200610058715.8), with the sulphuric leachate of manganese ore (pyrolusite or rhodochrosite) scavenging solution---manganese sulfate solution is a raw material, ammoniacal liquor is made precipitation agent the mn ion in the manganese sulfate solution is precipitated as manganous hydroxide and alkali formula manganous sulfate mixed sediment, as far as possible alkali formula manganous sulfate being converted into manganous hydroxide through aftertreatment under certain condition again, is the novel process scheme of trimanganese tetroxide at last with oxygenant oxidation bivalent manganese.This method without electrolysis, has been saved complicated manganese electrolysis process because be with the bivalent manganese direct oxidation, add that the main raw material(s) that uses is manganese sulfate solution, sulfuric acid and ammoniacal liquor, their wide material sources, and inexpensive, thereby be considered to the most rising a kind of preparation method.But directly prepare trimanganese tetroxide with manganous hydroxide, product recovery rate is low.
Summary of the invention
The present invention seeks to the mixed oxide of manganese presoma, help the raising of separate impurities such as silicon, calcium, magnesium, sulphur and product recovery rate as the preparation trimanganese tetroxide.
A kind of method for preparing the mixed oxide of manganese with manganese sulfate solution, sulphuric leachate with manganese ore---manganese sulfate solution is done raw material, under temperature is room temperature～100 ℃, make precipitation agent with ammoniacal liquor, pH value of solution is controlled at 7.5～12, earlier the mn ion in the manganese sulfate solution is hydrolyzed to the hydrolyzate of manganese, again under temperature is 30～100 ℃ and pH8.0～14 conditions, with the hydrolyzate of this manganese of alkaline purification 0.1～10 hour, make it the overwhelming majority and change manganous hydroxide into, with manganous sulfate the complete hydrolysis thing---manganous hydroxide is as presoma, with oxygenant manganous hydroxide is oxidized to and contains Manganse Dioxide, manganic oxide, the mixed oxide of manganese such as trimanganese tetroxide, the mixed oxide content range is: Manganse Dioxide 35%～79%, manganic oxide 1%～5%, trimanganese tetroxide 20%～64%.Processing condition are under 100～600 ℃, with the hydrolyzate of air or oxygen hydrogen oxide manganese oxide, oxidization time: 0.2～34 hour.
With the presoma of this mixed oxide, can produce the high quality trimanganese tetroxide as the preparation trimanganese tetroxide.
Embodiment
Embodiment 1
The hydrolyzate oxyhydroxide of manganous sulfate is used dioxygen oxidation 10 hours under 350 ℃, must contain the mixed oxide of manganese 22% such as Manganse Dioxide 76%, manganic oxide 2%, trimanganese tetroxide.
Embodiment 2
The hydrolyzate oxyhydroxide of manganous sulfate is used dioxygen oxidation 12 hours under 150 ℃, must contain the mixed oxide of manganese 52% such as Manganse Dioxide 46%, manganic oxide 2%, trimanganese tetroxide.
Embodiment 3
The hydrolyzate oxyhydroxide of manganous sulfate is used dioxygen oxidation 2 hours under 500 ℃, must contain the mixed oxide of manganese 63% such as Manganse Dioxide 36%, manganic oxide 1%, trimanganese tetroxide.
Embodiment 4
The hydrolyzate oxyhydroxide of manganous sulfate is used dioxygen oxidation 32 hours under 200 ℃, must contain the mixed oxide of manganese 43% such as Manganse Dioxide 53%, manganic oxide 4%, trimanganese tetroxide.
Embodiment 5
The hydrolyzate oxyhydroxide of manganous sulfate is used dioxygen oxidation 26 hours under 400 ℃, must contain the mixed oxide of manganese 20% such as Manganse Dioxide 79%, manganic oxide 3%, trimanganese tetroxide.
Claims (1)
1. method for preparing the mixed oxide of manganese with manganese sulfate solution, sulphuric leachate with manganese ore---manganese sulfate solution is done raw material, under temperature is room temperature～100 ℃, make precipitation agent with ammoniacal liquor, pH value of solution is controlled at 7.5～12, earlier the mn ion in the manganese sulfate solution is hydrolyzed to the hydrolyzate of manganese, again under temperature is 30～100 ℃ and pH8.0～14 conditions, with the hydrolyzate of this manganese of alkaline purification 0.1～10 hour, make it the overwhelming majority and change manganous hydroxide into, it is characterized in that with manganous sulfate the complete hydrolysis thing---manganous hydroxide is as presoma, with oxygenant manganous hydroxide is oxidized to and contains Manganse Dioxide, manganic oxide, the mixed oxide of trimanganese tetroxide, the mixed oxide content range is: Manganse Dioxide 35%～79%, manganic oxide 1%～5%, trimanganese tetroxide 20%～64%; Processing condition are under 100～600 ℃, with the hydrolyzate of air or oxygen hydrogen oxide manganese oxide, oxidization time: 0.2～34 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610011894XA CN100500577C (en) | 2006-05-15 | 2006-05-15 | Method for preparing hybrid oxide of manganese by manganese sulfate solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610011894XA CN100500577C (en) | 2006-05-15 | 2006-05-15 | Method for preparing hybrid oxide of manganese by manganese sulfate solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1843939A CN1843939A (en) | 2006-10-11 |
| CN100500577C true CN100500577C (en) | 2009-06-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB200610011894XA Expired - Fee Related CN100500577C (en) | 2006-05-15 | 2006-05-15 | Method for preparing hybrid oxide of manganese by manganese sulfate solution |
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| CN (1) | CN100500577C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269841B (en) * | 2008-04-15 | 2010-06-02 | 北京大学 | Manganese oxide for dephenolization and method for processing high concentration phenol wastewater |
| CN104445423B (en) * | 2014-12-15 | 2016-05-18 | 中信大锰矿业有限责任公司大新锰矿分公司 | A kind of preparation method of high-purity manganese dioxide |
| CN107032410B (en) * | 2017-04-24 | 2019-04-05 | 长沙兴嘉生物工程股份有限公司 | The preparation method and applications of alkali formula manganese sulfate |
| CN108975408B (en) * | 2018-10-10 | 2021-04-06 | 北京科技大学 | Method for preparing mangano-manganic oxide |
| CN110540242A (en) * | 2019-09-06 | 2019-12-06 | 辽宁星空新能源发展有限公司 | method for preparing two-dimensional basic manganese oxide nanosheet through rapid precipitation |
-
2006
- 2006-05-15 CN CNB200610011894XA patent/CN100500577C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 用硫酸锰溶液不经电解直接制备四氧化三锰的过程中除硫的研究. 邹兴等.中国稀土学报，第22卷. 2004 |
| 用硫酸锰溶液不经电解直接制备四氧化三锰的过程中除硫的研究. 邹兴等.中国稀土学报，第22卷. 2004 * |
| 用硫酸锰溶液直接制备高纯四氧化三锰的难点和进展. 邹兴等.冶金研究中心2005年"冶金工程科学论坛"论文集. 2005 |
| 用硫酸锰溶液直接制备高纯四氧化三锰的难点和进展. 邹兴等.冶金研究中心2005年"冶金工程科学论坛"论文集. 2005 * |
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| CN1843939A (en) | 2006-10-11 |
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Granted publication date: 20090617 Termination date: 20130515 |