CN101428859B - Production process of trimanganese tetroxide with carbon-manganese alloy - Google Patents
Production process of trimanganese tetroxide with carbon-manganese alloy Download PDFInfo
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- CN101428859B CN101428859B CN2008102039689A CN200810203968A CN101428859B CN 101428859 B CN101428859 B CN 101428859B CN 2008102039689 A CN2008102039689 A CN 2008102039689A CN 200810203968 A CN200810203968 A CN 200810203968A CN 101428859 B CN101428859 B CN 101428859B
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- trimanganese tetroxide
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Abstract
The invention relates to a method for preparing trimanganese tetroxide from a carbon-manganese alloy, belonging to the technical field of functional materials. The method comprises the following steps: melting 91% to 94.5% (mass percentage) of electrolytic manganese and 5.5% to 9% (mass percentage) of graphite by an induction furnace in the air, pouring the melted furnace burden in an ingot mold and cooling to obtain the carbon-manganese alloy; then, reacting in the water for 15 to 30 hours to obtain the superfine milk white manganese hydroxide powder; and oxidizing the superfine powder at the room temperature in the air to obtain the superfine brown trimanganese tetroxide. The method has the advantages of simple process, convenient operation, mass production and easily controlled reaction process, compared with the electrolytic manganese metal powder suspension oxidation process and the manganese ore chemical leaching process for preparing trimanganese tetroxide, the method of the invention is really a green manufacturing technique; the granules of the prepared trimanganese tetroxide product are small and spherical; and the grain size distribution is narrow.
Description
Technical field
The present invention relates to a kind of method of producing trimanganese tetroxide, function of dominant material technology field with carbon manganese alloy.
Background technology
Mangano-manganic oxide Mn
3O
4It is the important raw and processed materials of producing manganese-zinc ferrite, manganese-zinc ferrite have narrow remanence curve, can remagnetization, dc resistivity height, can avoid the more characteristics such as eddy current loss, be widely used in the fields such as electronics, electrical equipment, electric power and new and high technology; Nano manganic manganous oxide can be used as cheap catalyst; It is found that recently mangano-manganic oxide also can be used for preparing lithium ion anode material LiMn
2O
4, its performance is better than MnO
2
Produce high-quality Mn-Zn ferrite, the quality of trimanganese tetroxide should step to a new level, and granular size is to estimate an important indicator of trimanganese tetroxide quality, reduces particle diameter aborning as far as possible, and has flourishing hole and promptly form honeycomb or spongy.Domestic since building up with electrolytic metal Mn production trimanganese tetroxide article one production line the nineties in last century, throughput has reached 6～70,000 tons at present, domestic trimanganese tetroxide production line adopts electrolytic metal manganese powder suspension oxidation style mostly, utilize air or oxygen as oxygenant, under certain temperature and amine salt additive concentration, prepare trimanganese tetroxide, typical process flow: powder process-oxidation-washing-drying.This technological advantage: output height, technology are simple; Shortcoming: the foreign matter content height, specific surface area is little, size-grade distribution is wide, the high selenium micron trimanganese tetroxide of production common grade basically.Can't compete with the no selenium high-specific surface area mangano-manganic oxide that the foreign countries such as the U.S., Japan and South Africa produce.
Being raw material with Primary Mn Ores, through leaching and chemical subtraction is produced mangano-manganic oxide, be a feasible method, but this method removal of impurities is not thorough, and final mangano-manganic oxide product impurity content is higher than the product of electrolytic metal manganese powder suspension oxidizing process production.Compare with conventional micron trimanganese tetroxide, nano manganic manganous oxide has characteristics such as particle is tiny, specific surface area is big, surfactivity height, is the focus of recent people's research.
Summary of the invention
The purpose of this invention is to provide a kind of method of producing trimanganese tetroxide with carbon manganese alloy.
For achieving the above object, the present invention adopts following technical scheme:
A kind of method of producing trimanganese tetroxide with carbon manganese alloy is characterized in that this method has following process and step:
A) by percentage to the quality, the electrolytic manganese with 91～94.5% and 5.5～9% graphite are used induction furnace melting in air, treat to pour in the ingot mould after furnace charge melts and cool off, and obtain the carbon manganese alloy of fragility, and through X-ray diffraction analysis, principal phase is manganess carbide Mn
5C
2Alloy.
B) carbon manganese alloy is broken into pieces, particle diameter is put into the container that fills suitable quantity of water less than 2 millimeters carbon manganese alloy, at room temperature at once just there is bubble to occur, the smell that is similar to acetylene is arranged, and emit with a small amount of reaction heat, through reaction in 15～30 hours, carbon manganese alloy became ultra-fine off-white powder and is deposited in container bottom, through X-ray diffraction analysis, ultra-fine off-white powder is mainly manganous hydroxide Mn (OH)
2, also have a small amount of mangano-manganic oxide Mn
3O
4This reaction and carbide of calcium and water reacting phase seemingly only react so not fierce, and stirring can increase speed of reaction, reduces the reaction times.
C) with ultra-fine off-white powder at room temperature in the air through oxidation in 4～10 hours, can be oxidized to ultra-fine brown ceramic powder, through X-ray diffraction analysis, ultra-fine brown ceramic powder is mangano-manganic oxide Mn
3O
4, also ultra-fine off-white powder blowing air or oxygen in water can be carried out oxidation.
Carbon manganese alloy is exposed to for a long time also can form ultra-fine brown mangano-manganic oxide Mn in the air
3O
4Powder, but oxidation rate is too slow, and oxidization time is long, is not suitable for industrialized production.
Advantage of the present invention is that technology is simple, easy to operate, reaction process is controlled easily, can be mass-produced, comparing with electrolytic metal manganese powder suspension oxidation style and primary manganese ore chemistry lixiviation process production trimanganese tetroxide is a kind of green production process worthy of the name, and the trimanganese tetroxide product particle of producing is little, particle is spherical and narrow particle size distribution.
Description of drawings
Fig. 1 is the laser particle size size distribution plot of trimanganese tetroxide particle.
Fig. 2 is the scanning electron microscope pattern of trimanganese tetroxide particle.
Embodiment
After now concrete enforcement of the present invention being described in.
Embodiment 1
The first step is used induction furnace melting with the electrolytic manganese of 740 grams and the graphite of 60 grams in air, treat to pour in the ingot mould after furnace charge melts and cool off, and obtains the carbon manganese alloy of fragility, and through X-ray diffraction analysis, principal phase is manganess carbide Mn
5C
2Carbon manganese alloy.
Second step is put into 250ml water (room temperature) with 50 gram particles footpath less than 2 millimeters carbon manganese alloy, at once just there is bubble to occur, and emit with a small amount of reaction heat, through reaction in 25 hours, carbon manganese alloy becomes ultra-fine off-white powder and is deposited in container bottom, through X-ray diffraction analysis, ultra-fine off-white powder is mainly manganous hydroxide Mn (OH)
2, also have a small amount of mangano-manganic oxide Mn
3O
4
The 3rd step was oxidized to ultra-fine brown ceramic powder in 6 hours with the at room temperature oxidation in the air of ultra-fine off-white powder, and through X-ray diffraction analysis, ultra-fine brown ceramic powder is mangano-manganic oxide Mn
3O
4
Fig. 1 is the particle size distribution figure of the trimanganese tetroxide sample of Zetasizer 3000HS laser particle analyzer test, and it is to measure in intensity intensity mode, can see the trimanganese tetroxide particle distribution of sizes in 194.8 nanometers, and mean sizes is in 220 nanometers.Fig. 2 is the pattern that has amplified 30000 times trimanganese tetroxide particle with the JSM-6700F scanning electron microscope, can see the small-particle trimanganese tetroxide of 50～100 nanometers, granular size is more even, particle is spherical and agglomeration is arranged, and it is by due to the agglomeration that the size of 194.8 nanometers of laser particle analyzer test distributes.
Embodiment 2
The first step is used induction furnace melting with the electrolytic manganese of 920 grams and the graphite of 80 grams in air, treat to pour in the ingot mould after furnace charge melts and cool off, and obtains the carbon manganese alloy of fragility, and through X-ray diffraction analysis, principal phase is manganess carbide Mn
5C
2Carbon manganese alloy.
Second step is put into 50ml water (room temperature) with 10 gram particles footpath less than 2 millimeters carbon manganese alloy, at once just there is bubble to occur, and emit with a small amount of reaction heat, through reaction in 20 hours, carbon manganese alloy becomes ultra-fine off-white powder and is deposited in container bottom, through X-ray diffraction analysis, ultra-fine off-white powder is mainly manganous hydroxide Mn (OH)
2, also have a small amount of mangano-manganic oxide Mn
3O
4
The 3rd step was oxidized to ultra-fine brown ceramic powder in 5 hours with the at room temperature oxidation in the air of ultra-fine off-white powder, and through X-ray diffraction analysis, ultra-fine brown ceramic powder is mangano-manganic oxide Mn
3O
4
Claims (3)
1. method of producing trimanganese tetroxide with carbon manganese alloy is characterized in that this method has following process and step:
A) by percentage to the quality, the electrolytic manganese with 91～94.5% and 5.5～9% graphite are used induction furnace melting in air, treat to pour in the ingot mould after furnace charge melts and cool off, and obtaining principal phase is manganess carbide Mn
5C
2The fragility carbon manganese alloy;
B) carbon manganese alloy is broken into pieces, particle diameter is put into the container that fills suitable quantity of water less than 2 millimeters carbon manganese alloy, through reaction in 15～30 hours, obtain manganous hydroxide Mn (OH)
2And a small amount of mangano-manganic oxide Mn
3O
4Ultra-fine off-white powder;
C) with ultra-fine off-white powder at room temperature in the air through oxidation in 4～10 hours, obtain ultra-fine brown mangano-manganic oxide Mn
3O
4Powder.
2. method of producing trimanganese tetroxide with carbon manganese alloy according to claim 1 is characterized in that described being reflected under the agitation condition of step b carry out.
3. method of producing mangano-manganic oxide with carbon manganese alloy according to claim 1 is characterized in that step c is replaced with: ultra-fine off-white powder blowing air or oxygen in water are carried out oxidation, obtain ultra-fine brown mangano-manganic oxide Mn
3O
4Powder.
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| CN2008102039689A CN101428859B (en) | 2008-12-04 | 2008-12-04 | Production process of trimanganese tetroxide with carbon-manganese alloy |
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|---|---|---|---|
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|---|---|
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| CN101428859B true CN101428859B (en) | 2011-01-19 |
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| CN101857259A (en) * | 2010-05-26 | 2010-10-13 | 上海大学 | Method for preparing nanometer La(OH)3 micro powder through hydrolysis of lanthanum carbide |
| CN103717536B (en) * | 2011-06-02 | 2017-02-15 | 康奈尔大学 | Manganese oxide nanoparticles, method and application |
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