CN102765760A - Preparation method of manganous-manganic oxide and manganous-manganic oxide - Google Patents

Preparation method of manganous-manganic oxide and manganous-manganic oxide Download PDF

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CN102765760A
CN102765760A CN2012102915788A CN201210291578A CN102765760A CN 102765760 A CN102765760 A CN 102765760A CN 2012102915788 A CN2012102915788 A CN 2012102915788A CN 201210291578 A CN201210291578 A CN 201210291578A CN 102765760 A CN102765760 A CN 102765760A
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CN102765760B (en
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吴筱菁
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Shenzhen Xinhaoqing Technology Co ltd
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Abstract

The invention provides a preparation method of manganous-manganic oxide and the manganous-manganic oxide. The preparation method comprises the following steps of adjusting the pH value of manganese dioxide powder slurry to be 2.0-2.5, stirring the slurry at the temperature of 60-70 DEG C and conducting solid-liquid separation; adding manganese dioxide after scouring in manganese sulfate solution with the concentration of 100-200g/L; warming the solution at nitrogen atmosphere to the temperature in the scope of 55-60DEG C; leading in NH3 holding solution with the pH value in the scope of 7.5-8.0, and maintaining, stirring and reacting for 0.8-1.2 hours after the pH value of the holding solution is stable; replacing nitrogen atmosphere by using oxygen atmosphere, leading in NH3 holding solution with the pH value in the scope of 7.0-7.5, adding 250-350g/L of MnSO4 solution, reacting until concentration of Mn+ is smaller than 500ppm, stopping the reaction, conducting solid-liquid separation, washing solid phase, and drying to obtain globular Mn3O4 products. The preparation method can use electrolytic manganese dioxide (EMD) tail powder to serve as raw materials, obtained manganous-manganic oxide products are approximately spherical and high in purity, and requirements for lithium-ion secondary battery are met.

Description

METHODS OF MAKING MANGANIC MANGANOUS OXIDE and this trimanganese tetroxide
Technical field
The preparation that to the present invention relates to a kind of lithium-ion secondary cell manganese be base mateiral, concrete, relate to a kind of method for preparing spherical trimanganese tetroxide.
Background technology
Current driving force battery lithium manganate mainly adopts block EMD solid phase synthesis preparation after the powder process operation; Can produce more Manganse Dioxide superfine powder in block EMD powder process operation, this part small-particle Manganse Dioxide tail powder does not require to lose its due using value owing to size-grade distribution reaches.
In the preparation of lithium-ion secondary cell manganese cathode material; Trimanganese tetroxide is owing to its each item physics, the good manganese based material with prospect that becomes of chemical property; Utilize EMD tail powder can improve the level of resources utilization, reduce cost through the special-purpose trimanganese tetroxide of the spherical lithium-ion secondary cell manganese cathode material of each step Processing of Preparation.
Summary of the invention
Technical problem to be solved by this invention is: overcome prior art and adopt Manganse Dioxide to prepare the requirement of trimanganese tetroxide to the Manganse Dioxide particle diameter; A kind of method for preparing trimanganese tetroxide is provided; Even can utilize EMD tail powder as raw material; Gained trimanganese tetroxide product is subsphaeroidal and purity is high, satisfies the lithium-ion secondary cell needs.
The present invention has prepared spherical trimanganese tetroxide product through the second oxidation reduction method, and in addition, the present invention is to manganese dioxide powder, and especially EMD tail powder carries out acid pre-treatment, has reduced MnO 2The content of impurity such as middle K, Na, Ca, Ma, Fe.
In order to solve the problems of the technologies described above, first technical scheme provided by the invention is, a kind of METHODS OF MAKING MANGANIC MANGANOUS OXIDE, and this method comprises the steps:
1) pickling
Regulate the manganese dioxide powder slurry pH value to 2.0-2.5, stir said slurry under the 60-70 ℃ of temperature, solid-liquid separation, the solid phase Manganse Dioxide that obtains gets into next-step operation through the washing back;
2) the first step redox
Manganse Dioxide after the pickling is joined in the manganese sulfate solution, and wherein the concentration of manganese sulfate solution is 100-200g/L; Under the nitrogen atmosphere, solution is warming up in the 55-60 ℃ of scope; Then, feed NH 3Keep the pH value of solution value in the 7.5-8.0 scope, treat the pH value of solution value stabilization after, kept stirring reaction 0.8-1.2 hour;
3) the second step redox
Replace nitrogen atmosphere with oxygen atmosphere, feed NH 3Keep the pH value of solution value in the 7.0-7.5 scope, add the MnSO of 250-350g/L 4Solution reacts Mn to the solution 2+Stopped reaction behind weight concentration＜500ppm, solid-liquid separation obtains spherical Mn with the washing of gained solid phase, drying 3O 4Product.
Aforesaid METHODS OF MAKING MANGANIC MANGANOUS OXIDE, step 2) in the first step redox, the concentration of said manganese sulfate solution is 150-170g/L.
Aforesaid METHODS OF MAKING MANGANIC MANGANOUS OXIDE, step 2) in the first step redox, presses MnO 2: MnSO 4The molar ratio of=1:1.5 joins the Manganse Dioxide after the pickling in the manganese sulfate solution.
Aforesaid METHODS OF MAKING MANGANIC MANGANOUS OXIDE, in the step 3) second step redox, oxygen atmosphere pressure is 0.01～0.1MPa.
Aforesaid METHODS OF MAKING MANGANIC MANGANOUS OXIDE in the step 3) second step redox, adds the MnSO of 250-350g/L 4Solution is until Mn 3O 4Granularity Distribution meets targeted particle size distribution D 50Scope for 5-10 μ m.
Adopt the trimanganese tetroxide of method for preparing.
Aforesaid trimanganese tetroxide, this trimanganese tetroxide are spherical, 5.670 μ m≤D 50≤9.142 μ m.
Aforesaid trimanganese tetroxide, Mn wt%>=71wt% in this trimanganese tetroxide; K content≤40ppm; Na content≤12.5ppm.
Aforesaid trimanganese tetroxide, Ca content is less than 100ppm in this trimanganese tetroxide; Mg is less than 50ppm; Fe content≤4.7ppm.
Adopt technical scheme of the present invention, have following beneficial effect at least:
1. the present invention has prepared spherical trimanganese tetroxide product through the second oxidation reduction method.
2. the present invention can utilize EMD tail powder to be raw material, and EMD tail powder is carried out acid pre-treatment, has reduced MnO 2In the content of impurity such as K, Na, Ca, Ma, Fe, make K content≤40ppm in the product, Na content≤12.5ppm, Ca content be less than 100ppm, Mg is less than 50ppm, Fe content≤4.7ppm has satisfied the index request of lithium ion battery material.
3. the present invention has improved MnSO through second oxidation reduction operation 4Efficient, and improved MnO 2The pattern of powder helps improving the tap density of material.
Description of drawings
The process flow sheet that Fig. 1 the present invention is main;
Fig. 2 is by the XRD figure of the sample 1# of the embodiment of the invention 1 preparation.
Embodiment
For fully understanding the present invention's purpose, characteristic and effect,, the present invention is elaborated by following concrete embodiment.
The present invention has prepared spherical trimanganese tetroxide product through the second oxidation reduction method.The present invention is to manganese dioxide powder, and especially EMD tail powder carries out acid pre-treatment, has reduced MnO 2In the content of impurity such as K, Na, Ca, Ma, Fe, satisfied the index request of lithium ion battery material.The present invention has improved MnSO through second oxidation reduction operation 4Efficient, and improved MnO 2The pattern of powder helps improving the tap density of material.
Specifying the present invention below adopts manganese dioxide powder to prepare the method for trimanganese tetroxide.
1) pickling
Regulate under manganese dioxide powder slurry pH value to 2.0～2.5,60～70 ℃ of temperature and stir said slurry, solid-liquid separation, the solid phase that obtains (Manganse Dioxide) gets into next-step operation through the washing back.
The present invention does not have particular requirement to the particle diameter of used manganese dioxide powder, and the manganese dioxide powder that can form slurry is all within protection domain of the present invention.Particularly; The present invention can adopt industry to go up depleted Manganse Dioxide superfine powder; For example the present invention can adopt electrolytic manganese dioxide (EMD) tail powder, and electrolytic manganese dioxide (EMD) tail powder is meant the Manganse Dioxide superfine powder that block electrolytic manganese dioxide produces, its MnO usually in the powder process operation 2Content is about 91wt%, D 50Particle diameter is in the 0.5-1.8 micrometer range, and the mass content of Fe is in the 80-150ppm scope, and tap density is at 1.40-1.45g/cm 3In the scope.
Preferably, adopt deionized water that manganese dioxide powder is prepared slurry, the consumption of deionized water does not have particular requirement, and an amount of water yield that can process slurry all in protection domain of the present invention, preferably adds deionized water according to material-water ratio (mass ratio) for 1:5.
Preferably, the present invention adopts conventional mineral acid to regulate the manganese dioxide powder pH value of slurry, for example sulfuric acid, hydrochloric acid or phosphoric acid, preferably sulfuric acid.
Preferably, the manganese dioxide powder slurry stirs 1.5-2.5 hour (preferred 2 hours) under 60～70 ℃ of temperature.
Preferably, said solid-liquid separation adopts press filtration to separate.
Preferably, the said solid phase that obtains is washed with small amount of deionized water, merges washing lotion, and this washing lotion is with among the CaO and back qualified discharge.
This acid pickling step has reduced the content of impurity such as the K in the Manganse Dioxide, Na, Ca, Ma, Fe.
2) the first step redox
The main chemical reaction of this step is following:
MnO 2+2MnSO 4+4NH 3+2H 2O→Mn 3O 4+2(NH 4) 2SO 4
Manganse Dioxide after the pickling is joined in the manganese sulfate solution, and wherein the concentration of manganese sulfate solution is 100～200g/L (preferred 150-170g/L); Under the nitrogen atmosphere, stirring down, solution is warming up in 55～60 ℃ of scopes; Then, feed NH 3Keep the pH value of solution value in 7.5～8.0 scopes, treat the pH value of solution value stabilization after, keep stirring reaction 0.8-1.2 hour (preferred 1 hour).Here " after treating the pH value of solution value stabilization " is meant and stops to feed NH 3, the pH value of solution value still is stabilized in 7.5～8.0 scopes.
Preferably, press MnO 2: MnSO 4The molar ratio of=1:1.5 joins the Manganse Dioxide after the pickling in the manganese sulfate solution.
3) the second step redox
The main chemical reaction of this step is following:
6MnSO 4+6H 2O+O 2+12NH 3→2Mn 3O 4+6(NH 4) 2SO 4
Replace nitrogen atmosphere with oxygen atmosphere, feed NH 3Keep the pH value of solution value in 7.0～7.5 scopes, add the MnSO of 250-350g/L 4Solution is to Mn 2+Stopped reaction behind the＜500ppm, solid-liquid separation obtains spherical Mn with the washing of gained solid phase, drying 3O 4Product.
Preferably, oxygen atmosphere pressure is 0.01～0.1MPa.
Preferably, the MnSO that adds 250-350g/L (preferred 300g/L) 4Solution is until Mn 3O 4Granularity Distribution meets targeted particle size and distributes.Said targeted particle size distributes and is meant the Mn according to the downstream customer demand 3O 4The particle diameter of product, preferred Mn 3O 4The particle diameter of product reaches D 50Scope for 5-10 μ m.
MnSO 4The addition manner of solution, interpolation speed are to final Mn 3O 4The particle diameter of product is influence not.In addition, because the tail powder can be crystal seed in reaction, MnSO 4Add-on decision Mn 3O 4The product final size distributes.
Preferably, after the solid-liquid separation gained solid phase with the ratio of de-ionized according to material-water ratio 1:5,60～70 ℃ of following washed twice, each 1-2 hour (preferred 1.5 hours), filtrating reclaim(ed) sulfuric acid ammonium, the solid phase airflow drying obtains spherical Mn 3O 4Product.
In an embodiment, the method that adopts manganese dioxide powder to prepare trimanganese tetroxide comprises the steps:
1) pickling
In electrolytic manganese dioxide (EMD) tail powder, add deionized water according to material-water ratio 1:5, process the Manganse Dioxide slurry.Regulate slurry pH value to 2.0-2.5 with sulfuric acid, stirred said slurry 2 hours under the 60-70 ℃ of temperature, press filtration separates, and the solid phase that obtains (Manganse Dioxide) gets into next-step operation through the washing back.
2) the first step redox
Press MnO 2: MnSO 4The molar ratio of=1:1.5 joins the Manganse Dioxide after the pickling in the manganese sulfate solution of concentration 100-200g/L (preferred 150-170g/L), adopts nitrogen replacement and encloses container, and stirring down, solution is warming up to 55-60 ℃; Then, feed NH 3Keep the pH value of solution value at 7.5-8.0, treat the pH value of solution value stabilization after, kept stirring reaction 1 hour.
3) the second step redox
Replace nitrogen atmosphere with oxygen atmosphere, and to keep oxygen atmosphere pressure be 0.01-0.1MPa.Feed NH 3Keep the pH value of solution value in the 7.0-7.5 scope, add the MnSO of concentration 300g/L 4Solution reacts to Mn 2+Stopped reaction behind the＜500ppm, press filtration separate, and the gained solid phase is with the ratio of de-ionized according to material-water ratio 1:5,60～70 ℃ of following washed twice, and each 1.5 hours, the filtrating recovery, the solid phase airflow drying obtains spherical Mn 3O 4Product
Adopt the trimanganese tetroxide of method for preparing.
Preferably, this trimanganese tetroxide is spherical, 5.670 μ m≤D 50≤9.142 μ m.
Preferably, Mn wt%>=71wt% in this trimanganese tetroxide; K content≤40ppm; Na content≤12.5ppm.
Preferably, in this trimanganese tetroxide Ca content less than 100ppm; Mg is less than 50ppm; Fe content≤4.7ppm.
Set forth the enforcement of method of the present invention below through concrete embodiment, one skilled in the art will appreciate that this should not be understood that the restriction to claim scope of the present invention.
Embodiment
The purity of used relevant chemical reagent and the measuring method that relates to are described below in the embodiments of the invention.
Sulfuric acid: H 2SO 4Content 98%; Nitrogen: analytical pure nitrogen; Oxygen: analytical pure oxygen; Ammonia: analytical pure nitrogen.
Mn, K, Na, Ca, Mg and Fe content elemental analysis method: inductively coupled plasma (ICP) atomic emission spectrometry
Mn 2+Detection method: inductively coupled plasma (ICP) atomic emission spectrometry
Atomic Absorption SpectrophotometerICP: IRIS Intrepid II XSP type inductively coupled plasma atomic emission spectrometer, U.S. power & light company system;
PH value determinator: PHS-3C type precision acidity meter, Shanghai precision instrumentation corporate system;
Particle size analysis method: the particle diameter of the volume reference that records with the wet type laser method;
Particle size analysis device: 2000MU type particle diameter appearance, Britain Ma Erda corporate system;
XRD determining device: Rigaku D/max-IIIC type, Japanese corporate system of science.
Embodiment 1
1) pickling
In 200 kilograms of electrolytic manganese dioxides (EMD) tail powder, add deionized water according to material-water ratio 1:5, process the Manganse Dioxide slurry.The MnO of electrolytic manganese dioxide (EMD) tail powder wherein 2Content is about 91wt%, D 50Particle diameter is 1.0 microns, and Fe content is 100ppm.Regulate slurry pH value to 2.3 with sulfuric acid, stirred said slurry 2 hours under 65 ℃ of temperature, press filtration separates, and the solid phase that obtains (Manganse Dioxide) gets into next-step operation through the washing back.
2) the first step redox
Press MnO 2: MnSO 4=1: 1.5 molar ratio is about to adopt nitrogen replacement and encloses container in the manganese sulfate solution of concentration 150g/L that Manganse Dioxide after the pickling joins 3120L, and stirring down, solution is warming up to 58 ℃; Then, feed NH 3Keep the pH value of solution value 7.7, treat the pH value of solution value stabilization after, kept stirring reaction 1 hour.
3) the second step redox
Replace nitrogen atmosphere with oxygen atmosphere, and to keep oxygen atmosphere pressure be 0.05MPa.Feed NH 3Keep the pH value of solution value in 7.2 scopes, add the MnSO of the concentration 300g/L of 2000L 4Solution reacts to Mn 2+Stopped reaction behind the＜500ppm, press filtration separate, and the gained solid phase is with the ratio of de-ionized according to material-water ratio 1:5,60～70 ℃ of following washed twice, and each 1.5 hours, the filtrating recovery, the solid phase airflow drying obtains spherical Mn 3O 4Product 1#.
Fig. 2 is Mn 3O 4The X ray diffractive crystal structure collection of illustrative plates of product 1#.Can find out Mn by Fig. 2 3O 4Product 1# does not have dephasign, and the peak is narrow, peak shape is sharp-pointed and intensity is high, shows this Mn 3O 4Crystalline structure complete, do not contain the dephasign Mn oxide basically.
Embodiment 2
1) pickling
In 200 kilograms of electrolytic manganese dioxides (EMD) tail powder, add deionized water according to material-water ratio 1:5, process the Manganse Dioxide slurry.The MnO of electrolytic manganese dioxide (EMD) tail powder wherein 2Content is about 91wt%, D 50Particle diameter is 0.5 micron, and the mass content of Fe is 80ppm.Regulate slurry pH value to 2.2 with sulfuric acid, stirred said slurry 2 hours under 62 ℃ of temperature, press filtration separates, and the solid phase that obtains (Manganse Dioxide) gets into next-step operation through the washing back.
2) the first step redox
Press MnO 2: MnSO 4=1: 1.5 molar ratio joins the Manganse Dioxide after the pickling in the manganese sulfate solution of concentration 150g/L of 3120L, adopts nitrogen replacement and encloses container, and stirring down, solution is warming up to 56 ℃; Then, feed NH 3Keep the pH value of solution value 7.6, treat the pH value of solution value stabilization after, kept stirring reaction 1 hour.
3) the second step redox
Replace nitrogen atmosphere with oxygen atmosphere, and to keep oxygen atmosphere pressure be 0.03MPa.Feed NH 3Keep the pH value of solution value in 7.1 scopes, add the MnSO of the concentration 300g/L of 4500L 4Solution reacts to Mn 2+Stopped reaction behind the＜500ppm, press filtration separate, and the gained solid phase is with the ratio of de-ionized according to material-water ratio 1:5,60～70 ℃ of following washed twice, and each 1.5 hours, the filtrating recovery, the solid phase airflow drying obtains spherical Mn 3O 4Product 2#.
Embodiment 3
1) pickling
In 200 kilograms of electrolytic manganese dioxides (EMD) tail powder, add deionized water according to material-water ratio 1:5, process the Manganse Dioxide slurry.The MnO of electrolytic manganese dioxide (EMD) tail powder wherein 2Content is about 91wt%, D 50Particle diameter is 1.8 microns, and the mass content of Fe is 150ppm.Regulate slurry pH value to 2.4 with sulfuric acid, stirred said slurry 2 hours under 68 ℃ of temperature, press filtration separates, and the solid phase that obtains (Manganse Dioxide) gets into next-step operation through the washing back.
2) the first step redox
Press MnO 2: MnSO 4The molar ratio of=1:1.5 joins the Manganse Dioxide after the pickling in the manganese sulfate solution of concentration 170g/L of 2790L, adopts nitrogen replacement and encloses container, and stirring down, solution is warming up to 58 ℃; Then, feed NH 3Keep the pH value of solution value 7.8, treat the pH value of solution value stabilization after, kept stirring reaction 1 hour.
3) the second step redox
Replace nitrogen atmosphere with oxygen atmosphere, and to keep oxygen atmosphere pressure be 0.07MPa.Feed NH 3Keep the pH value of solution value in 7.4 scopes, add the MnSO of the concentration 300g/L of 7000L 4Solution is to Mn 2+Stopped reaction behind the＜500ppm, press filtration separate, and the gained solid phase is with the ratio of de-ionized according to material-water ratio 1:5,60～70 ℃ of following washed twice, and each 1.5 hours, the filtrating recovery, the solid phase airflow drying obtains spherical Mn 3O 4Product 3#.
Embodiment 4
1) pickling
In 200 kilograms of electrolytic manganese dioxides (EMD) tail powder, add deionized water according to material-water ratio 1:5, process the Manganse Dioxide slurry.The MnO of electrolytic manganese dioxide (EMD) tail powder wherein 2Content is about 91wt%, D 50Particle diameter is 1.0 microns, and the mass content of Fe is 100ppm.Regulate slurry pH value to 2.0 with sulfuric acid, stirred said slurry 1.5 hours under 60 ℃ of temperature, press filtration separates, and the solid phase that obtains (Manganse Dioxide) gets into next-step operation through the washing back.
2) the first step redox
Press MnO 2: MnSO 4The molar ratio of=1:1.5 joins the Manganse Dioxide after the pickling in the manganese sulfate solution of concentration 100g/L of 4680L, adopts nitrogen replacement and encloses container, and stirring down, solution is warming up to 55 ℃; Then, feed NH 3Keep the pH value of solution value 7.5, treat the pH value of solution value stabilization after, kept stirring reaction 0.8 hour.
3) the second step redox
Replace nitrogen atmosphere with oxygen atmosphere, and to keep oxygen atmosphere pressure be 0.01MPa.Feed NH 3Keep the pH value of solution value in 7.0 scopes, add the MnSO of the concentration 300g/L of 3000L 4Solution is to Mn 2+Stopped reaction behind the＜500ppm, press filtration separate, and the gained solid phase is with the ratio of de-ionized according to material-water ratio 1:5,60～70 ℃ of following washed twice, and each 1 hour, the filtrating recovery, the solid phase airflow drying obtains spherical Mn 3O 4Product 4#.
Embodiment 5
1) pickling
In 200 kilograms of electrolytic manganese dioxides (EMD) tail powder, add deionized water according to material-water ratio 1:5, process the Manganse Dioxide slurry.The MnO of electrolytic manganese dioxide (EMD) tail powder wherein 2Content is about 91wt%, D 50Particle diameter is 1.0 microns, and the mass content of Fe is 100ppm.Regulate slurry pH value to 2.5 with sulfuric acid, stirred said slurry 2.5 hours under 70 ℃ of temperature, press filtration separates, and the solid phase that obtains (Manganse Dioxide) gets into next-step operation through the washing back.
2) the first step redox
Press MnO 2: MnSO 4=1: 1.5 molar ratio joins the Manganse Dioxide after the pickling in the manganese sulfate solution of concentration 200g/L of 2340L, adopts nitrogen replacement and encloses container, and stirring down, solution is warming up to 60 ℃; Then, feed NH 3Keep the pH value of solution value 8.0, treat the pH value of solution value stabilization after, kept stirring reaction 1.2 hours.
3) the second step redox
Replace nitrogen atmosphere with oxygen atmosphere, and to keep oxygen atmosphere pressure be 1MPa.Feed NH 3Keep the pH value of solution value in 7.5 scopes, add the MnSO of the concentration 300g/L of 3500L 4Solution is to Mn 2+Stopped reaction behind the＜500ppm, press filtration separate, and the gained solid phase is with the ratio of de-ionized according to material-water ratio 1:5,60～70 ℃ of following washed twice, and each 2 hours, the filtrating recovery, the solid phase airflow drying obtains spherical Mn 3O 4Product 5#.
Mn for the foregoing description 1-5 gained 3O 4Sample 1 #～5 #, carried out constituent content analysis, particle size determination, pattern mensuration, will measure the result and be shown in as in the following table 1.
Table 1
Figure BDA00002020270000101
By the prepared Mn of embodiment in the above-mentioned table 11 ~ 5 3O 4, 71.44%>=Mn wt%>=71% that is to say, uses method of the present invention to adopt EMD tail powder to be raw material, can prepare to meet lithium-ion secondary cell manganese based material and use Mn 3O 4
The Mn that embodiment 1～5 obtains 3O 4Particle diameter D 50Scope is 5.670 μ m≤D 50≤9.142 μ m meet targeted particle size distribution requirement.
The Mn that embodiment 1～5 obtains 3O 4Product, its 17.0ppm≤K content≤40ppm; 8.1ppm≤Na content≤12.5ppm; Ca content is less than 100ppm; Mg content is less than 50ppm; 3.7ppm≤Fe content≤4.7ppm.Explanation thus, the present invention adopts the method for pickling, has reduced the content of impurity such as the K in the Manganse Dioxide, Na, Ca, Ma, Fe, has satisfied the index request of lithium ion battery material.
Generally speaking, the foregoing description 1～5 shows, through the Mn of method preparation of the present invention 3O 4Product, each index such as its particle diameter, pattern, purity all meets the requirement for preparing lithium-ion secondary cell.

Claims (9)

1. METHODS OF MAKING MANGANIC MANGANOUS OXIDE, this method comprises the steps:
1) pickling
Regulate the manganese dioxide powder slurry pH value to 2.0-2.5, stir said slurry under the 60-70 ℃ of temperature, solid-liquid separation, the solid phase Manganse Dioxide that obtains gets into next-step operation through the washing back;
2) the first step redox
Manganse Dioxide after the pickling is joined in the manganese sulfate solution, and wherein the concentration of manganese sulfate solution is 100-200g/L; Under the nitrogen atmosphere, solution is warming up in the 55-60 ℃ of scope; Then, feed NH 3Keep the pH value of solution value in the 7.5-8.0 scope, treat the pH value of solution value stabilization after, kept stirring reaction 0.8-1.2 hour;
3) the second step redox
Replace nitrogen atmosphere with oxygen atmosphere, feed NH 3Keep the pH value of solution value in the 7.0-7.5 scope, add the MnSO of 250-350g/L 4Solution reacts Mn to the solution 2+Stopped reaction behind weight concentration＜500ppm, solid-liquid separation obtains spherical Mn with the washing of gained solid phase, drying 3O 4Product.
2. METHODS OF MAKING MANGANIC MANGANOUS OXIDE according to claim 1 is characterized in that, in the step 1) pickling, said Manganse Dioxide is electrolytic manganese dioxide tail powder; Step 2) in the first step redox, the concentration of said manganese sulfate solution is 150-170g/L.
3. METHODS OF MAKING MANGANIC MANGANOUS OXIDE according to claim 1 and 2 is characterized in that step 2) in the first step redox, press MnO 2: MnSO 4The molar ratio of=1:1.5 joins the Manganse Dioxide after the pickling in the manganese sulfate solution.
4. according to each described METHODS OF MAKING MANGANIC MANGANOUS OXIDE of claim 1-3, it is characterized in that in the step 3) second step redox, oxygen atmosphere pressure is 0.01～0.1MPa.
5. according to each described METHODS OF MAKING MANGANIC MANGANOUS OXIDE of claim 1-4, it is characterized in that, in the step 3) second step redox, add the MnSO of 250-350g/L 4Solution is until Mn 3O 4Granularity Distribution meets targeted particle size distribution D 50Scope for 5-10 μ m.
6. the trimanganese tetroxide for preparing like each method of claim 1-5.
7. trimanganese tetroxide according to claim 6 is characterized in that, this trimanganese tetroxide is spherical, and 5.670 μ m≤D 50≤9.142 μ m.
8. according to claim 6 or 7 described trimanganese tetroxides, it is characterized in that Mn wt%>=71wt% in this trimanganese tetroxide; K content≤40ppm; Na content≤12.5ppm.
9. according to each described trimanganese tetroxide of claim 6-8, it is characterized in that Ca content is less than 100ppm in this trimanganese tetroxide; Mg content is less than 50ppm; Fe content≤4.7ppm.
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CN108975408A (en) * 2018-10-10 2018-12-11 北京科技大学 A method of preparing mangano-manganic oxide

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