CN103011295A - Reduction method for producing manganese tetroxide - Google Patents
Reduction method for producing manganese tetroxide Download PDFInfo
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- CN103011295A CN103011295A CN201210547754XA CN201210547754A CN103011295A CN 103011295 A CN103011295 A CN 103011295A CN 201210547754X A CN201210547754X A CN 201210547754XA CN 201210547754 A CN201210547754 A CN 201210547754A CN 103011295 A CN103011295 A CN 103011295A
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Abstract
The invention discloses a reduction method for producing high-purity manganese tetroxide. The method comprises the following steps: (a) heating a manganese sulfate solution, adding ammonia water or ammonium bicarbonate for reaction, settling and then filtering and washing; (b) calcining the sediment which is obtained after washing in the step (a) at 200 DEG C to 1000 DEG C; and (c) adding water into the solid matters formed after calcination in the step (b), performing size mixing, controlling the liquid/solid ratio to be (3-10) m<3>:1t, controlling the heating temperature to be 50 DEG C to 150 DEG C, controlling pH value to 6-10 with ammonia water, adding hydrazine hydrate until the concentration of hydrazine hydrate in the solution reaches 0.01-2 mol/L, allowing the reaction time to be 1-10 hours, filtering after reacting, washing and drying to obtain the final product of manganese tetroxide. Compared with the prior art, the method disclosed by the invention reduces the cost of raw materials, simplifies the processing steps, and ensures the quality of manganese tetroxide final products through deep purification and sulfur removal by the combination of the wet process and pyrogenic process.
Description
Technical field
The invention belongs to the manganic compound synthesis technical field, be specifically related to a kind of method for preparing the high purity trimanganese tetroxide of reducing.
Background technology
Trimanganese tetroxide belongs to the high performance structures material, is mainly used in electronic industry, is to produce one of required important raw and processed materials of soft magnetic ferrite, and the soft magnetic ferrite that is prepared by trimanganese tetroxide accounts for more than 60% of soft magnetic ferrite total amount.Can be divided into two classes from preparation principle: a class is the at a low price oxidation of manganese; Another kind of is the reduction of value Mn.The at a low price oxidation of manganese is substantially all adopted in the present production of China, and manufacturer 95% adopts electrolytic metal Mn suspension oxidation style, has in addition 5% to be to adopt manganese salt solution thermal oxidation method, and essence all is that the oxidation bivalent manganese prepares trimanganese tetroxide.The research of reduction method is relatively less.According to reported in literature, the preparation of the reduction method of trimanganese tetroxide normally utilizes solid metal manganese powder or manganese salt at roasting MnO
2, Mn
2O
3, the high price Mn oxide such as MnOOH process in add the reducing gas reduction such as methane, hydrogen, carbon monoxide and generate Mn
3O
4, this is owned by France in gas-solid reaction, and reaction conditions control is comparatively harsh, introduces simultaneously flammable explosive gas having relatively high expectations to equipment and operation.And adopt the method for liquid phase water thermal reduction to have no report.
Summary of the invention
Technical problem to be solved by this invention provides a kind of reducible method for preparing the high purity trimanganese tetroxide.
The technical solution adopted for the present invention to solve the technical problems is: reduction prepares the method for trimanganese tetroxide, comprises the steps:
A, with manganese sulfate solution heating, add again the reaction of ammoniacal liquor or bicarbonate of ammonia, filter after the precipitation, washing;
B, being deposited under 200～1000 ℃ the temperature after the step a washing carried out roasting;
C, the solid matter after the step b roasting is added water size mixing, the control liquid-solid ratio is 3～10m
3︰ 1t adds 50～150 ℃ of thermal control temperature, and with ammoniacal liquor control pH value 6～12, it is 0.01～2mol/L that the adding hydrazine hydrate makes its concentration in solution, reaction times 1～10h, and filtration after the reaction, washing, drying obtain the trimanganese tetroxide product.
Wherein, among the aforesaid method step c, the control liquid-solid ratio is 5～7m
3︰ 1t adds 80～120 ℃ of thermal control temperature, and with ammoniacal liquor control pH value 8～10, it is 0.1～1mol/L that the adding hydrazine hydrate makes its concentration in solution, reaction times 3～6h.
Wherein, among the aforesaid method step b, 700～1000 ℃ of the temperature of roasting, roasting time 3～6h.
Wherein, among the aforesaid method step a, described manganese sulfate solution contains manganese 10～120g/L.
Wherein, among the aforesaid method step a, described manganese sulfate solution is to be obtained through sulfuric acid to leach, removal of impurities by manganese ore.
Further, described manganese sulfate solution contains Ca＜10mg/L, Mg＜50mg/L, Si＜10mg/L, Na＜50mg/L, K＜10mg/L, heavy metal＜10mg/L.
Wherein, among the aforesaid method step a, the temperature that manganese sulfate solution is heated is 40～60 ℃.
Wherein, among the aforesaid method step a, the concentration of described ammoniacal liquor is 6～15%, and the concentration of described bicarbonate of ammonia is 10～30%, and the add-on of described ammoniacal liquor or bicarbonate of ammonia is: make solution terminal point manganese concentration less than 1g/L.
The invention has the beneficial effects as follows: the present invention with manganese sulfate solution with ammoniacal liquor or ammonium bicarbonate precipitation, filtration, washing after roasting, obtain the Mn oxide presoma, deep desulfuration is laid a good foundation for preparing high-purity trimanganese tetroxide; The Mn oxide presoma is sized mixing, control liquid-solid ratio, Heating temperature and pH value, add a certain amount of hydrazine hydrate carry out reduction reaction after filtration, washing, drying make single trimanganese tetroxide product, thereby finally make the high-purity mangano-manganic oxide product.The present invention has reduced raw materials cost with respect to prior art, has simplified processing step, and in conjunction with wet method and the sulphur removal of pyrogenic process deep purifying, final trimanganese tetroxide quality is protected.
Embodiment
The present invention is further described below in conjunction with embodiment.
The present invention reduces the method for preparing trimanganese tetroxide, comprises the steps:
A, with manganese sulfate solution heating, add again the reaction of ammoniacal liquor or bicarbonate of ammonia, filter after the precipitation, washing;
B, being deposited under 200～1000 ℃ the temperature after the step a washing carried out roasting;
C, the solid matter after the step b roasting is added water size mixing, the control liquid-solid ratio is 3～10m
3︰ 1t adds 50～150 ℃ of thermal control temperature, and with ammoniacal liquor control pH value 6～12, it is 0.01～2mol/L that the adding hydrazine hydrate makes its concentration in solution, reaction times 1～10h, and filtration after the reaction, washing, drying obtain the trimanganese tetroxide product.
Step b solid phase high-temperature heat treatment of the present invention is controlled maturing temperature, can very effectively control the content of calcium in the finished product, magnesium and sulphur, lays a good foundation for finally preparing high-purity trimanganese tetroxide.When step b carries out roasting, the part rare gas element can be passed into, in order to controlling manganese oxygen ratio, thereby the content of trimanganese tetroxide in the Mn oxide presoma can be improved.Step c of the present invention rationally controls liquid-solid ratio, Heating temperature and pH value, add a certain amount of hydrazine hydrate carry out reduction reaction after filtration, washing, drying make single trimanganese tetroxide product.Step c of the present invention adds the thermal control temperature at 50～150 ℃, it will be understood by those skilled in the art that when temperature can to reach by the mode of encloses container heating during greater than 100 ℃.
Preferably, among the aforesaid method step c, the control liquid-solid ratio is 5～7m
3︰ 1t adds 80～120 ℃ of thermal control temperature, and with ammoniacal liquor control pH value 8～10, it is 0.1～1mol/L that the adding hydrazine hydrate makes its concentration in solution, reaction times 3～6h.
Preferably, among the aforesaid method step b, 700～1000 ℃ of the temperature of roasting, roasting time 3～6h.
Preferably, among the aforesaid method step a, described manganese sulfate solution contains manganese 10～120g/L.
Preferably, for the cost that further economizes in raw materials, among the aforesaid method step a, described manganese sulfate solution is to be obtained through sulfuric acid to leach, removal of impurities by manganese ore.
Preferably, too high on impact of the present invention for fear of foreign matter content, described manganese sulfate solution contains Ca＜10mg/L, Mg＜50mg/L, Si＜10mg/L, Na＜50mg/L, K＜10mg/L, heavy metal＜10mg/L.
Preferably, among the aforesaid method step a, the temperature that manganese sulfate solution is heated is 40～60 ℃; Be heated to the particle form generation that this temperature is conducive to manganous hydroxide.
Preferably, among the aforesaid method step a, the concentration of described ammoniacal liquor is 6～15%, and the concentration of described bicarbonate of ammonia is 10～30%, and the add-on of described ammoniacal liquor or bicarbonate of ammonia is: make solution terminal point manganese concentration less than 1g/L.
Below by embodiment the specific embodiment of the present invention is described further, but therefore protection scope of the present invention is not limited among the embodiment.
Embodiment one
Manganese concentration after purification is qualified is the manganese sulfate solution 5L of 50g/l, puts into reactor, is heated to 50 ℃, slowly adds 6% ammonia precipitation process again, and control terminal point manganese concentration is less than 1g/l.Filtration after precipitation is finished, with deionized water wash repeatedly, until the wash water inspection does not measure sulfate ion.Retort furnace is put in the precipitation of hydroxide of the manganese prepared heated desulfurization with roasting technique, prepare the Mn oxide presoma.Maturing temperature is 500 ℃, and roasting time is 6h.Again the Mn oxide presoma of preparing is put into reactor, adding deionized water sizes mixing, liquid-solid ratio is 6:1, reheat 90 ℃, adding ammoniacal liquor control pH value is 8, filtration behind the adding 1mol hydrazine hydrate hydrothermal reduction processing 4h, washing, drying obtain the trimanganese tetroxide product, and product index is: Mn:71.25%, SiO
2: 0.01%, CaO:0.01%, MgO:0.01%, Na
2O:0.004%, K
2O:0.003%, F
2O
3: 0.06%, S:0.035%, Se: nothing.
Embodiment two
Manganese concentration after purification is qualified is the manganese sulfate solution 5L of 100g/l, puts into reactor, is heated to 70 ℃, slowly adds 12.5% ammonia precipitation process again, and control terminal point manganese concentration is less than 1g/l.Filtration after precipitation is finished, with deionized water wash repeatedly, until the wash water inspection does not measure sulfate ion.Retort furnace is put in the precipitation of hydroxide of the manganese prepared heated desulfurization with roasting technique, prepare the Mn oxide presoma.Maturing temperature is 900 ℃, and roasting time is 3h.Again the Mn oxide presoma of preparing is put into reactor, adding deionized water sizes mixing, liquid-solid ratio is 5:1, reheat 80 ℃, adding ammoniacal liquor control pH value is 9, filtration behind the adding 5mol hydrazine hydrate hydrothermal reduction processing 4h, washing, drying obtain the trimanganese tetroxide product, and product index is: Mn:71.34%, SiO
2: 0.008%, CaO:0.006%, MgO:0.005%, Na
2O:0.003%, K
2O:0.004%, F
2O
3: 0.07%, S:0.045%, Se: nothing.
Embodiment three
Manganese concentration after purification is qualified is the manganese sulfate solution 5L of 60g/l, puts into reactor, is heated to 60 ℃, slowly adds 8% ammonia precipitation process again, and control terminal point manganese concentration is less than 1g/l.Filtration after precipitation is finished, with deionized water wash repeatedly, until the wash water inspection does not measure sulfate ion.The precipitation of hydroxide of the manganese prepared in the nitrogen protection situation, is put into tube furnace and heated desulfurization with roasting technique, prepare the Mn oxide presoma.Maturing temperature is 800 ℃, and roasting time is 5h.Again the Mn oxide presoma of preparing is put into reactor, adding deionized water sizes mixing, liquid-solid ratio is 5:1, reheat 100 ℃, adding ammoniacal liquor control pH value is 7.5, filtration behind the adding 0.5mol hydrazine hydrate hydrothermal reduction processing 4h, washing, drying obtain the trimanganese tetroxide product, and product index is: Mn:71.87%, SiO
2: 0.01%, CaO:0.01%, MgO:0.01%, Na
2O:0.005%, K
2O:0.006%, F
2O
3: 0.06%, S:0.036%, Se: nothing.
Embodiment four
Manganese concentration after purification is qualified is the manganese sulfate solution 5L of 50g/l, puts into reactor, is heated to 50 ℃, slowly adds 12% ammonium bicarbonate precipitation again, and control terminal point manganese concentration is less than 1g/l.Filtration after precipitation is finished, with deionized water wash repeatedly, until the wash water inspection does not measure sulfate ion.The carbonate compound precipitation of the manganese prepared is put into retort furnace heat desulfurization with roasting technique, prepare the Mn oxide presoma.Maturing temperature is 700 ℃, and roasting time is 6h.Again the Mn oxide presoma of preparing is put into reactor, adding deionized water sizes mixing, liquid-solid ratio is 7:1, reheat 120 ℃, adding ammoniacal liquor control pH value is 9, filtration behind the adding 2mol hydrazine hydrate hydrothermal reduction processing 4h, washing, drying obtain the trimanganese tetroxide product, and product index is: Mn:71.09%, SiO
2: 0.01%, CaO:0.006%, MgO:0.005%, Na
2O:0.007%, K
2O:0.004%, F
2O
3: 0.04%, S:0.05%, Se: nothing.
Embodiment five
Manganese concentration after purification is qualified is the manganese sulfate solution 5L of 100g/l, puts into reactor, is heated to 60 ℃, slowly adds 25% ammonium bicarbonate precipitation again, and control terminal point manganese concentration is less than 1g/l.Filtration after precipitation is finished, with deionized water wash repeatedly, until the wash water inspection does not measure sulfate ion.The carbonate compound precipitation of the manganese prepared is put into retort furnace heat desulfurization with roasting technique, prepare the Mn oxide presoma.Maturing temperature is 900 ℃, and roasting time is 5h.Again the Mn oxide presoma of preparing is put into reactor, adding deionized water sizes mixing, liquid-solid ratio is 5:1, reheat 80 ℃, adding ammoniacal liquor control pH value is 10, filtration behind the adding 2mol hydrazine hydrate hydrothermal reduction processing 4h, washing, drying obtain the trimanganese tetroxide product, and product index is: Mn:71.89%, SiO
2: 0.009%, CaO:0.008%, MgO:0.007%, Na
2O:0.007%, K
2O:0.006%, F
2O
3: 0.07%, S:0.045%, Se: nothing.
Embodiment six
Manganese concentration after purification is qualified is the manganese sulfate solution 5L of 70g/l, puts into reactor, is heated to 30 ℃, slowly adds 15% ammonium bicarbonate precipitation again, and control terminal point manganese concentration is less than 1g/l.Filtration after precipitation is finished, with deionized water wash repeatedly, until the wash water inspection does not measure sulfate ion.The carbonate compound of the manganese prepared is deposited in the nitrogen protection situation, puts into tube furnace and heat desulfurization with roasting technique, prepare the Mn oxide presoma.Maturing temperature is 1000 ℃, and roasting time is 3h.Again the Mn oxide presoma of preparing is put into reactor, adding deionized water sizes mixing, liquid-solid ratio is 5:1, reheat 90 ℃, adding ammoniacal liquor control pH value is 8, filtration behind the adding 0.2mol hydrazine hydrate hydrothermal reduction processing 3h, washing, drying obtain the trimanganese tetroxide product, and product index is: Mn:71.54%, SiO
2: 0.008%, CaO:0.01%, MgO:0.01%, Na
2O:0.01%, K
2O:0.007%, F
2O
3: 0.07%, S:0.035%, Se: nothing.
Claims (8)
1. reduction prepares the method for trimanganese tetroxide, it is characterized in that comprising the steps:
A, with manganese sulfate solution heating, add again the reaction of ammoniacal liquor or bicarbonate of ammonia, filter after the precipitation, washing;
B, being deposited under 200～1000 ℃ the temperature after the step a washing carried out roasting;
C, the solid matter after the step b roasting is added water size mixing, the control liquid-solid ratio is 3～10m
3︰ 1t adds 50～150 ℃ of thermal control temperature, and with ammoniacal liquor control pH value 6～12, it is 0.01～2mol/L that the adding hydrazine hydrate makes its concentration in solution, reaction times 1～10h, and filtration after the reaction, washing, drying obtain the trimanganese tetroxide product.
2. reduction according to claim 1 prepares the method for trimanganese tetroxide, it is characterized in that: among the step c, the control liquid-solid ratio is 5～7m
3︰ 1t adds 80～120 ℃ of thermal control temperature, and with ammoniacal liquor control pH value 8～10, it is 0.1～1mol/L that the adding hydrazine hydrate makes its concentration in solution, reaction times 3～6h.
3. reduction according to claim 1 prepares the method for trimanganese tetroxide, it is characterized in that: among the step b, and 700～1000 ℃ of the temperature of roasting, roasting time 3～6h.
4. according to claim 1,2 or 3 described reduction prepare the method for trimanganese tetroxide, it is characterized in that: among the step a, described manganese sulfate solution contains manganese 10～120g/L.
5. according to claim 1,2 or 3 described reduction prepare the method for trimanganese tetroxide, it is characterized in that: among the step a, described manganese sulfate solution is to be obtained through sulfuric acid to leach, removal of impurities by manganese ore.
6. reduction according to claim 5 prepares the method for trimanganese tetroxide, it is characterized in that: described manganese sulfate solution contains Ca＜10mg/L, Mg＜50mg/L, Si＜10mg/L, Na＜50mg/L, K＜10mg/L, heavy metal＜10mg/L.
7. according to claim 1,2 or 3 described reduction prepare the method for trimanganese tetroxide, it is characterized in that: among the step a, be 40～60 ℃ with the temperature of manganese sulfate solution heating.
8. according to claim 1,2 or 3 described reduction prepare the method for trimanganese tetroxide, it is characterized in that: among the step a, the concentration of described ammoniacal liquor is 6～15%, the concentration of described bicarbonate of ammonia is 10～30%, and the add-on of described ammoniacal liquor or bicarbonate of ammonia is: make solution terminal point manganese concentration less than 1g/L.
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Cited By (3)
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| CN103274469A (en) * | 2013-06-05 | 2013-09-04 | 浙江大学 | Trimanganese tetroxide nanocrystal and preparation method thereof |
| CN105883925A (en) * | 2016-06-25 | 2016-08-24 | 上海大学 | Mesoporous trimanganese tetraoxide and preparation method thereof |
| CN115140774A (en) * | 2022-08-09 | 2022-10-04 | 贵州金瑞新材料有限责任公司 | Preparation method of mangano-manganic oxide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103274469A (en) * | 2013-06-05 | 2013-09-04 | 浙江大学 | Trimanganese tetroxide nanocrystal and preparation method thereof |
| CN103274469B (en) * | 2013-06-05 | 2015-05-27 | 浙江大学 | Trimanganese tetroxide nanocrystal and preparation method thereof |
| CN105883925A (en) * | 2016-06-25 | 2016-08-24 | 上海大学 | Mesoporous trimanganese tetraoxide and preparation method thereof |
| CN105883925B (en) * | 2016-06-25 | 2019-02-01 | 上海大学 | A kind of mesoporous mangano-manganic oxide and preparation method thereof |
| CN115140774A (en) * | 2022-08-09 | 2022-10-04 | 贵州金瑞新材料有限责任公司 | Preparation method of mangano-manganic oxide |
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