CN103011295B - Reduction method for producing manganese tetroxide - Google Patents
Reduction method for producing manganese tetroxide Download PDFInfo
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- CN103011295B CN103011295B CN201210547754.XA CN201210547754A CN103011295B CN 103011295 B CN103011295 B CN 103011295B CN 201210547754 A CN201210547754 A CN 201210547754A CN 103011295 B CN103011295 B CN 103011295B
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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 manganic compound synthesis technical field, be specifically related to a kind of reduction and prepare the method for high purity trimanganese tetroxide.
Background technology
Trimanganese tetroxide belongs to 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 of being prepared by trimanganese tetroxide accounts for the more than 60% of soft magnetic ferrite total amount.Can be divided into two classes from preparation principle: a class is the oxidation of manganese at a low price; Another kind of is the reduction of value Mn.The current production of China substantially all adopts the oxidation of manganese at a low price, 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 is all that oxidation bivalent manganese is prepared trimanganese tetroxide.The research of reduction method is relatively less.According to reported in literature, the reduction method preparation 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 to generate Mn
3o
4, this is owned by France in gas-solid reaction, and reaction conditions control is comparatively harsh, introduces flammable explosive gas having relatively high expectations to equipment and operation simultaneously.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 is to provide a kind of reducible method of preparing high purity trimanganese tetroxide.
The technical solution adopted for the present invention to solve the technical problems is: the method for trimanganese tetroxide is prepared in reduction, comprises the steps:
A, by manganese sulfate solution heating, then add ammoniacal liquor or bicarbonate of ammonia reaction, after precipitation, filter, washing;
B, will step a carry out roasting at the temperature that is deposited in 200～1000 DEG C after washing;
C, the solid matter after step b roasting is added water and sized mixing, control liquid-solid ratio is 3～10m
3︰ 1t, adds 50～150 DEG C of thermal control temperature, and by ammoniacal liquor control pH value 6～12, adding hydrazine hydrate to make its concentration in solution is 0.01～2mol/L, reaction times 1～10h, filtration after reaction, washing, the dry trimanganese tetroxide product that obtains.
Wherein, in aforesaid method step c, control liquid-solid ratio is 5～7m
3︰ 1t, adds 80～120 DEG C of thermal control temperature, and by ammoniacal liquor control pH value 8～10, adding hydrazine hydrate to make its concentration in solution is 0.1～1mol/L, reaction times 3～6h.
Wherein, in aforesaid method step b, 700～1000 DEG C of the temperature of roasting, roasting time 3～6h.
Wherein, in aforesaid method step a, described manganese sulfate solution is containing manganese 10～120g/L.
Wherein, in 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 is containing Ca < 10mg/L, Mg < 50mg/L, Si < 10mg/L, Na < 50mg/L, K < 10mg/L, heavy metal < 10mg/L.
Wherein, in aforesaid method step a, it is 40～60 DEG C by the temperature of manganese sulfate solution heating.
Wherein, in 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 manganese concentration be less than 1g/L.
The invention has the beneficial effects as follows: the present invention, by roasting after manganese sulfate solution ammoniacal liquor or ammonium bicarbonate precipitation, filtration, washing, obtains Mn oxide presoma, and deep desulfuration, lays a good foundation for preparing high-purity trimanganese tetroxide; 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, be dried make single trimanganese tetroxide product, thereby finally make 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
Below in conjunction with embodiment, the present invention is further described.
The method of trimanganese tetroxide is prepared in the present invention's reduction, comprises the steps:
A, by manganese sulfate solution heating, then add ammoniacal liquor or bicarbonate of ammonia reaction, after precipitation, filter, washing;
B, will step a carry out roasting at the temperature that is deposited in 200～1000 DEG C after washing;
C, the solid matter after step b roasting is added water and sized mixing, control liquid-solid ratio is 3～10m
3︰ 1t, adds 50～150 DEG C of thermal control temperature, and by ammoniacal liquor control pH value 6～12, adding hydrazine hydrate to make its concentration in solution is 0.01～2mol/L, reaction times 1～10h, filtration after reaction, washing, the dry trimanganese tetroxide product that obtains.
Step b solid phase high-temperature heat treatment of the present invention, controls 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, part rare gas element can be passed into, in order to control manganese oxygen ratio, thereby the content of trimanganese tetroxide in 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, dry make single trimanganese tetroxide product.Step c of the present invention adds thermal control temperature at 50～150 DEG C, it will be understood by those skilled in the art that the mode that can heat by encloses container in the time that temperature is greater than 100 DEG C reaches.
Preferably, in aforesaid method step c, control liquid-solid ratio is 5～7m
3︰ 1t, adds 80～120 DEG C of thermal control temperature, and by ammoniacal liquor control pH value 8～10, adding hydrazine hydrate to make its concentration in solution is 0.1～1mol/L, reaction times 3～6h.
Preferably, in aforesaid method step b, 700～1000 DEG C of the temperature of roasting, roasting time 3～6h.
Preferably, in aforesaid method step a, described manganese sulfate solution is containing manganese 10～120g/L.
Preferably, for the cost that further economizes in raw materials, in 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 is containing Ca < 10mg/L, Mg < 50mg/L, Si < 10mg/L, Na < 50mg/L, K < 10mg/L, heavy metal < 10mg/L.
Preferably, in aforesaid method step a, it is 40～60 DEG C by the temperature of manganese sulfate solution heating; Be heated to the particle form generation that this temperature is conducive to manganous hydroxide.
Preferably, in 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 manganese concentration be 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 embodiment.
Embodiment mono-
The manganese sulfate solution 5L that is 50g/l by the manganese concentration after qualified purification, puts into reactor, is heated to 50 DEG C, more slowly adds 6% ammonia precipitation process, controls terminal manganese concentration and is less than 1g/l.Precipitated rear filtration, with deionized water wash repeatedly, until wash water inspection does not measure sulfate ion.The precipitation of hydroxide of the manganese of preparing is put into retort furnace and heat desulfurization with roasting technique, prepare Mn oxide presoma.Maturing temperature is 500 DEG C, and roasting time is 6h.Again the Mn oxide presoma of preparing is put into reactor, add deionized water to size mixing, liquid-solid ratio is 6:1, reheat 90 DEG C, adding ammoniacal liquor control pH value is 8, add 1mol hydrazine hydrate hydrothermal reduction to process after 4h to filter, washing, dryly obtain trimanganese tetroxide product, 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 bis-
The manganese sulfate solution 5L that is 100g/l by the manganese concentration after qualified purification, puts into reactor, is heated to 70 DEG C, more slowly adds 12.5% ammonia precipitation process, controls terminal manganese concentration and is less than 1g/l.Precipitated rear filtration, with deionized water wash repeatedly, until wash water inspection does not measure sulfate ion.The precipitation of hydroxide of the manganese of preparing is put into retort furnace and heat desulfurization with roasting technique, prepare Mn oxide presoma.Maturing temperature is 900 DEG C, and roasting time is 3h.Again the Mn oxide presoma of preparing is put into reactor, add deionized water to size mixing, liquid-solid ratio is 5:1, reheat 80 DEG C, adding ammoniacal liquor control pH value is 9, add 5mol hydrazine hydrate hydrothermal reduction to process after 4h to filter, washing, dryly obtain trimanganese tetroxide product, 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 tri-
The manganese sulfate solution 5L that is 60g/l by the manganese concentration after qualified purification, puts into reactor, is heated to 60 DEG C, more slowly adds 8% ammonia precipitation process, controls terminal manganese concentration and is less than 1g/l.Precipitated rear filtration, with deionized water wash repeatedly, until wash water inspection does not measure sulfate ion.The precipitation of hydroxide of the manganese of preparing, in nitrogen protection situation, is put into tube furnace and heated desulfurization with roasting technique, prepare Mn oxide presoma.Maturing temperature is 800 DEG C, and roasting time is 5h.Again the Mn oxide presoma of preparing is put into reactor, add deionized water to size mixing, liquid-solid ratio is 5:1, reheat 100 DEG C, adding ammoniacal liquor control pH value is 7.5, add 0.5mol hydrazine hydrate hydrothermal reduction to process after 4h to filter, washing, dryly obtain trimanganese tetroxide product, 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 tetra-
The manganese sulfate solution 5L that is 50g/l by the manganese concentration after qualified purification, puts into reactor, is heated to 50 DEG C, more slowly adds 12% ammonium bicarbonate precipitation, controls terminal manganese concentration and is less than 1g/l.Precipitated rear filtration, with deionized water wash repeatedly, until wash water inspection does not measure sulfate ion.The carbonate compound precipitation of the manganese of preparing is put into retort furnace and heat desulfurization with roasting technique, prepare Mn oxide presoma.Maturing temperature is 700 DEG C, and roasting time is 6h.Again the Mn oxide presoma of preparing is put into reactor, add deionized water to size mixing, liquid-solid ratio is 7:1, reheat 120 DEG C, adding ammoniacal liquor control pH value is 9, add 2mol hydrazine hydrate hydrothermal reduction to process after 4h to filter, washing, dryly obtain trimanganese tetroxide product, 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
The manganese sulfate solution 5L that is 100g/l by the manganese concentration after qualified purification, puts into reactor, is heated to 60 DEG C, more slowly adds 25% ammonium bicarbonate precipitation, controls terminal manganese concentration and is less than 1g/l.Precipitated rear filtration, with deionized water wash repeatedly, until wash water inspection does not measure sulfate ion.The carbonate compound precipitation of the manganese of preparing is put into retort furnace and heat desulfurization with roasting technique, prepare Mn oxide presoma.Maturing temperature is 900 DEG C, and roasting time is 5h.Again the Mn oxide presoma of preparing is put into reactor, add deionized water to size mixing, liquid-solid ratio is 5:1, reheat 80 DEG C, adding ammoniacal liquor control pH value is 10, add 2mol hydrazine hydrate hydrothermal reduction to process after 4h to filter, washing, dryly obtain trimanganese tetroxide product, 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
The manganese sulfate solution 5L that is 70g/l by the manganese concentration after qualified purification, puts into reactor, is heated to 30 DEG C, more slowly adds 15% ammonium bicarbonate precipitation, controls terminal manganese concentration and is less than 1g/l.Precipitated rear filtration, with deionized water wash repeatedly, until wash water inspection does not measure sulfate ion.The carbonate compound of the manganese of preparing is deposited in nitrogen protection situation, puts into tube furnace and heat desulfurization with roasting technique, prepare Mn oxide presoma.Maturing temperature is 1000 DEG C, and roasting time is 3h.Again the Mn oxide presoma of preparing is put into reactor, add deionized water to size mixing, liquid-solid ratio is 5:1, reheat 90 DEG C, adding ammoniacal liquor control pH value is 8, add 0.2mol hydrazine hydrate hydrothermal reduction to process after 3h to filter, washing, dryly obtain trimanganese tetroxide product, 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 (6)
1. the method for trimanganese tetroxide is prepared in reduction, it is characterized in that comprising the steps:
A, by manganese sulfate solution heating, then add ammoniacal liquor or bicarbonate of ammonia reaction, after precipitation, filter, washing; Described manganese sulfate solution is containing manganese 10～120g/L; 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 manganese concentration be less than 1g/L;
B, will step a carry out roasting at the temperature that is deposited in 200～1000 DEG C after washing;
C, the solid matter after step b roasting is added water and sized mixing, controlling liquid-solid ratio is 3～10 m
3︰ 1t, adds 50～150 DEG C of thermal control temperature, and by ammoniacal liquor control pH value 6～12, adding hydrazine hydrate to make its concentration in solution is 0.01～2mol/L, reaction times 1～10h, filtration after reaction, washing, the dry trimanganese tetroxide product that obtains.
2. the method for trimanganese tetroxide is prepared in reduction according to claim 1, it is characterized in that: in step c, control liquid-solid ratio is 5～7m
3︰ 1t, adds 80～120 DEG C of thermal control temperature, and by ammoniacal liquor control pH value 8～10, adding hydrazine hydrate to make its concentration in solution is 0.1～1mol/L, reaction times 3～6h.
3. the method for trimanganese tetroxide is prepared in reduction according to claim 1, it is characterized in that: in step b, and 700～1000 DEG C of the temperature of roasting, roasting time 3～6h.
4. the method for preparing trimanganese tetroxide according to the reduction described in claim 1,2 or 3, is characterized in that: in step a, described manganese sulfate solution is to be obtained through sulfuric acid to leach, removal of impurities by manganese ore.
5. the method for trimanganese tetroxide is prepared in reduction according to claim 4, it is characterized in that: described manganese sulfate solution is containing Ca < 10mg/L, Mg < 50mg/L, Si < 10mg/L, Na < 50mg/L, K < 10mg/L, heavy metal < 10mg/L.
6. the method for preparing trimanganese tetroxide according to the reduction described in claim 1,2 or 3, is characterized in that: in step a, be 40～60 DEG C by the temperature of manganese sulfate solution heating.
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| CN103274469B (en) * | 2013-06-05 | 2015-05-27 | 浙江大学 | Trimanganese tetroxide nanocrystal 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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