CN102633306B - Preparation method of high-purity trimanganese tetroxide - Google Patents
Preparation method of high-purity trimanganese tetroxide Download PDFInfo
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Abstract
The invention discloses high-purity trimanganese tetroxide and a preparation method of the same. The high-purity trimanganese tetroxide is spherical, has mass content of manganese being greater than or equal to 71%, apparent density being smaller than or equal to 1.5g/m<3>, specific surface area being smaller than or equal to 1.0m<2>/g, mass contents of potassium, sodium, calcium and magnesium being respectively smaller than or equal to 50ppm, mass content of lead being smaller than or equal to 10ppm, mass content of sulphate being smaller than or equal to 200ppm by taking SO4 as reference, and residue on a test sieve of 45 mu m being smaller than or equal to 25%. The preparation method comprises the steps of adding high-purity manganese sulfate in organic activator for mechanical activation; after mechanical activation, conducting calcination under air or nitrogen atmosphere; allowing sulfur dioxide gas produced in calcination to be subjected to absorption leaching by a compound absorbent prepared from pyrolusite; preparing a high-purity manganese sulfate solution by a purification method of conducting induction in manganese sulfate solution to generate hydroxyl free radical.OH; and heating the high-purity manganese sulfate solution by high-temperature calcining tail gas, concentrating and crystallizing to obtain high-purity manganese sulfate returning-recycling as required.
Description
Technical field:
The raw material technical field that the present invention relates to produce soft magnetic ferrite, more specifically relates to a kind of high-purity mangano-manganic oxide and preparation method thereof.
Background technology:
High-purity mangano-manganic oxide is mainly used in electronic industry, it is the important source material of producing soft magnetic ferrite, can be used as storing in robot calculator magnetic core, the Disk and tape of information, transformer and high Q inductor device for phone, television flyback transformer, magnetic recording magnetic head, inducer, magnetic amplifier, saturated inductor, aerial rod.Can be used as in addition the colorant of some paint or coating, the paint that contains high-purity mangano-manganic oxide or coating are sprayed on iron and steel has better corrosion resistance than paint or coating containing titanium dioxide or ferric oxide.High-purity mangano-manganic oxide technology is an emerging technology at the early-stage in China.
The production technique of current high-purity mangano-manganic oxide mainly contains following several method: (1) manganese sulfate solution oxidation style, by the manganese sulfate solution that adopts manganese ore wet-leaching to obtain, by impurity and purification, add ammonium salt alkalization, filter, adopt air or oxygen oxidation, washing to obtain trimanganese tetroxide crystal, by trimanganese tetroxide crystal dry, cooling, pack to obtain product.Although this method technical maturity, due to manganese sulfate solution purification and impurity removal, particularly removes potassium sodium calcium magnesium addition ion and remain in technological difficulties, therefore, adopt this method to be difficult to make high-purity other trimanganese tetroxide of level.(2) electrolytic metal manganese powder suspension oxidation style, take electrolytic metal Mn sheet as raw material, first manganese metal sheet is pulverized and is made manganese powder suspension, and recycling air or oxygen is made oxygenant, under the condition of certain temperature and interpolation ammonium salt, prepares trimanganese tetroxide.Although this method technical maturity, simple, the raw material electrolytic metal Mn cost of this utilization is high, and because current electrolysis manganese metal is generally containing selenium, trimanganese tetroxide selenium content is exceeded standard, and is difficult to reach high-purity rank.(3) manganous sulfate calcination method: by manganous sulfate crystal heating and calcining, directly generate trimanganese tetroxide, obtain product through washing and drying.The key of this method is to obtain high-purity mangano-manganic oxide, first must guarantee the purity of manganous sulfate crystal, because after manganous sulfate crystal high-temperature decomposes, impurity can continue to remain in trimanganese tetroxide, and has the problem that enrichment increases.Chinese patent " a kind of manganous sulfate circulation method is prepared the method for trimanganese tetroxide " (application number: 201010537545.8), disclose a kind of manganous sulfate circulation method and prepared the method for trimanganese tetroxide, the concrete technical scheme of this patent application is: the sulfurous gas that manganous sulfate high-temperature calcination is produced and sulphur trioxide mixed gas are dry through the vitriol oil, and with air mixed compression after pass in the mixed ore pulp being formed by pyrolusite, manganous carbonate and water, at extraction temperature, be 85 ℃ and constantly leach 7 hours under stirring and obtain leaching liquid; To adding successively in leaching liquid Sodium Dimethyldithiocarbamate, ammonium sulfate and Neutral ammonium fluoride to till no longer producing precipitation, to filter and obtain manganese sulfate solution, the manganese sulfate solution evaporation concentration that filtration is obtained, obtains manganese sulfate monohydrate in 80 ℃-100 ℃; Manganese sulfate monohydrate is made it to dehydration for 0.5-2 hour in 350 ℃ of heating, again in 950 ℃-1050 ℃ calcining 1-2 hour, distilled water or deionized water rinsing for powder that calcining produces, be dried to obtain trimanganese tetroxide, the sulfurous gas that calcining produces and sulphur trioxide mixed gas are dry through the vitriol oil, and pass in the mixed ore pulp being formed by pyrolusite, manganous carbonate and water after compressing with air mixed, realize the object of manganous sulfate cyclic production trimanganese tetroxide.The problem that the method exists: (1) undeclared impurity such as iron, aluminium, potassium, sodium of how removing from Leaching Solution of Manganese Ore.(2) do not specialize the atmosphere (vacuum, antivacuum, nitrogen protection etc.) of calcining; and think that the gas that calcining produces is sulfurous gas and sulphur trioxide mixed gas; adopt the mixed ore pulp that pyrolusite, manganous carbonate and water form to absorb; under the increasingly exhausted background of manganese carbonate ore resource; practical value is little; and sulfur trioxide gas wet absorption easily produces acid mist, cause absorbing not exclusively and secondary pollution problem.(3) product standard of undeclared trimanganese tetroxide.
The present inventor is engaged in manganese ore leaching technique and leach liquor removal of impurities, refining research for a long time, and SEPARATE APPLICATION the Patents of having obtained the authorization are multinomial: Chinese patent 200510021926.X be take method, 200910058061.2 that pyrolusite and pH buffer reagent carry out waste-gas desulfurization as composite absorber and is applicable to SO in the reactor of leaching sulfur dioxide gas out of pyrolusite, method that 200910058062.7 use leaching sulfur dioxide gas out of pyrolusite are prepared manganese sulfate solution, 200910059583.4 pyrolusites leaching solution
2- 4, SO
2- 3, S
2o
2- 6, S
2o
2- 8in synchronized analyzing method, 200910060313.5 process of leaching sulfur dioxide gas out of pyrolusite, suppress the method for manganous dithionate generation, the special purpose reactor of 200920078540.6 leaching sulfur dioxide gas out of pyrolusite extracting sulfuric acid manganese solutions.
Existing research and the present inventor's preliminary experiment research all confirms, the pyrolytic decomposition behavior of manganous sulfate is more complicated, under different atmosphere, decompose resulting product different, therefore, the key issue that adopts manganous sulfate cyclic high-temperature calcination method to prepare trimanganese tetroxide is: how (1) regulates and controls the pyrolytic decomposition condition of manganous sulfate, and making degradation production is trimanganese tetroxide powder and sulfur dioxide gas; (2) how to guarantee the purity of the manganous sulfate that recycles, guarantee the purity of the trimanganese tetroxide that obtains.
Summary of the invention:
Object of the present invention provides a kind of high-purity mangano-manganic oxide of superior performance in order to overcome the shortcoming of above-mentioned prior art just with deficiency, can be used as the raw material of producing soft magnetic ferrite; Two are to provide a kind of method of preparing high-purity mangano-manganic oxide.
High-purity mangano-manganic oxide provided by the invention, its pattern is spherical, manganese mass content>=71%, loose density≤1.5g/m
3, specific surface area≤l.0m
2/ g, potassium, sodium, calcium, magnesium mass content all≤50ppm, plumbous mass content≤10ppm, with SO
4vitriol mass content≤the 200ppm of meter, screenings≤25% sieving with 45um testing sieve.
The present invention also provides the preparation method of this high-purity mangano-manganic oxide, and its processing step mainly comprises:
(1) high purity manganese sulfate and organic activator are inserted grinding plant or the activation of whipping device mixing machinery, and the time is no less than 2 hours;
(2) raw material after mechanical activation is inserted calciner, passes into air or nitrogen and calcines 1～5 hour at 800 ℃～1000 ℃, generates satisfactory trimanganese tetroxide powder;
(3) sulfur dioxide gas that step (2) calcining generates is drawn from calciner, the pyrolusite of take adds water and pH buffer reagent is composite absorber, or take that pyrolusite adds water and gac is composite absorber, or take pyrolusite, to add water, pH buffer reagent and gac be composite absorber, composite absorber, sulfur dioxide gas, oxygen are sent into continuously respectively in the reactor that is provided with the two-stage absorption Leaching reaction chamber of connecting up and down and absorbed successively Leaching reaction, the manganese sulfate solution that generation contains impurity, absorbs Leaching reaction and operates under positive pressure;
(4) manganese sulfate solution that contains impurity that step (3) is produced, employing is induced and is generated the hydroxyl radical free radical OH with strong oxidizing property in manganese sulfate solution, react the Manganse Dioxide or the trimanganese tetroxide that generate nascent state with mn ion in manganese sulfate solution, impurity in absorption manganese sulfate solution forms the purifying method high purity manganese sulfate solution of Mn oxide, the heating of high-purity manganese sulphate soln using calcining high-temperature tail gas, concentrated, crystallization, obtain satisfactory high purity manganese sulfate, return to step (1) circulation.
In technique scheme, described organic activator can be selected from the organism of alcohol, ketone, aldehydes.The add-on of organic activator is preferably not less than 1% of manganous sulfate crystal mass.
In technique scheme, the amount that calcination process passes into air, nitrogen is passed into the mixed volumetric concentration of gas not higher than 20%(V/V by the sulfur dioxide gas that can make manganous sulfate pyrolysis produce).
In technique scheme, high purity manganese sulfate is that foreign matter content reaches the manganous sulfate crystal that cell-grade requires.Preferably the content of its potassium, sodium, calcium, magnesium addition element is all lower than 50mg/kg, and the content of iron, aluminium, cobalt, nickel, copper, zinc, lead, cadmium, arsenic, sila prime element is all lower than 10mg/kg.
In technique scheme, the amount of oxygen that absorption leaching process passes into preferably can make to absorb the indoor pH value of reaction system of Leaching reaction lower than 3.5; In composite absorber, pyrolusite and quality are than being preferably controlled at the scope of 5:1～1:1; The two-stage of connecting up and down absorbs Leaching reaction chamber and is preferably all furnished with the agitator that every cube of ore pulp is not less than 5kW.
The present invention has also taked some other technical measures.
The present invention compares and has following very outstanding technique effect with existing manganous sulfate Cyclic Calcination technique:
(1) the present invention adopts high purity manganese sulfate as manganese based raw material, has overcome traditional calcination method raw material manganic compound foreign matter content high, and particularly Na, K ion are difficult to remove the problem that the product bringing is difficult to stably reaching standard.
(2) the present invention, to high purity manganese sulfate crystal by adopting organic activator mechanical activation before calcining, can reduce manganous sulfate decomposition temperature, saving heat energy.
(3) the present invention adopts organic activator to carry out mechanical activation to high purity manganese sulfate crystal, and it is inner that organic activator penetrates into manganous sulfate crystal lattices, and the micro-decomposition gas producing in high-temperature calcination decomposition course can significantly improve the specific surface area of trimanganese tetroxide.
(4) organic activator coordinates air or nitrogen atmosphere calcining, can make manganous sulfate decompose the gas producing is sulfurous gas, do not produce sulphur trioxide, not only can efficiently utilize pyrolusite, and avoid sulfur trioxide gas wet absorption easily to produce the secondary pollution problem of acid mist.
(5) the supporting pyrolusite pulp that adopts the present patent application people to obtain patent absorbs, manganese sulfate solution deep purifying impurity removing technology, the high purity manganese sulfate of one of synthesis material be can obtain again, thereby closed cycle, energy-saving and emission-reduction, the eco-friendly operational path of manganese based raw material formed.
Accompanying drawing explanation
Accompanying drawing 1 is the process flow diagram of one embodiment of the invention.
Embodiment:
Below by embodiment, the present invention is specifically described; but be necessary to be pointed out that at this; embodiment is only for the present invention is further illustrated; can not be interpreted as limiting the scope of the invention; person skilled in art can content according to the present invention makes some nonessential improvement and adjustment is specifically implemented, but so concrete enforcement should still belong to protection scope of the present invention.
In each of the embodiments described below, involved component concentration, except special instruction, is mass percent or mass fraction.
Embodiment 1
It is organic activator that the high purity manganese sulfate that meets quality standard is added to the acetone of its quality 2%, then admixture activation 3 hours in ball mill.Raw material after mechanical activation is sent into calciner, control temperature at 900 ℃, under air atmosphere, calcine 3 hours, the sulfur dioxide gas that air intake can produce according to manganous sulfate pyrolysis is 15%(V/V by the mixed volumetric concentration of passing into gas) control, generate satisfactory trimanganese tetroxide powder, the sulfur dioxide gas synchronously calcining being generated is drawn and is adopted the authorized Chinese patent 200510021926.X of patent applicant of the present invention to take the method that pyrolusite and pH buffer reagent carry out waste-gas desulfurization as composite absorber, 200910058061.2 be applicable to the reactor of leaching sulfur dioxide gas out of pyrolusite, 200910058062.7 prepare the method for manganese sulfate solution with leaching sulfur dioxide gas out of pyrolusite, 200910060313.5 suppress the method that manganous dithionate generates in process of leaching sulfur dioxide gas out of pyrolusite, with pyrolusite pulp, absorb and generate the manganese sulfate solution that contains impurity.Adopt a kind of " method of high purity manganese sulfate solution " that the present patent application people is examining in first to file to purify the highly purified manganese sulfate solution of acquisition the above-mentioned manganese sulfate solution that contains impurity, by the high-purity manganese sulphate soln using calcining high-temperature tail gas heating obtaining, concentrated, crystallization, acquisition meets the high purity manganese sulfate that present method requires, again Returning utilization.
Embodiment 2
It is organic activator that the high purity manganese sulfate that meets quality standard is added to the glycerol of its quality 4%, then stirrer for mixing activation 4 hours.Raw material after mechanical activation is sent into calciner, control temperature at 950 ℃, calcine 3.5 hours passing under nitrogen atmosphere, the sulfur dioxide gas that nitrogen intake can produce according to manganous sulfate pyrolysis is 10%(V/V by the mixed volumetric concentration of passing into gas) control, generate satisfactory trimanganese tetroxide powder, the sulfur dioxide gas synchronously calcining being generated is drawn and is adopted the authorized Chinese patent 200510021926.X of patent applicant of the present invention to take the method that pyrolusite and pH buffer reagent carry out waste-gas desulfurization as composite absorber, 200910058061.2 be applicable to the reactor of leaching sulfur dioxide gas out of pyrolusite, 200910058062.7 prepare the method for manganese sulfate solution with leaching sulfur dioxide gas out of pyrolusite, 200910060313.5 suppress the method that manganous dithionate generates in process of leaching sulfur dioxide gas out of pyrolusite, with pyrolusite pulp, absorb and generate the manganese sulfate solution that contains impurity.Adopt a kind of " method of high purity manganese sulfate solution " that the present patent application people is examining in first to file to purify the highly purified manganese sulfate solution of acquisition the above-mentioned manganese sulfate solution that contains impurity, by the heating of high-purity manganese sulphate soln using calcining high-temperature tail gas, concentrated, crystallization, acquisition meets the high purity manganese sulfate that present method requires, again Returning utilization.
Embodiment 3
It is organic activator that the high purity manganese sulfate that meets quality standard is added to the acetaldehyde of its quality 3%, then airtight admixture activation 2.5 hours in ball mill.Raw material after mechanical activation is sent into calciner, control temperature at 1000 ℃, under the atmosphere that passes into air and nitrogen mixture, calcine 3.5 hours, the sulfur dioxide gas that gas mixture intake can produce according to manganous sulfate pyrolysis is 5%(V/V by the mixed volumetric concentration of passing into gas) control, generate satisfactory trimanganese tetroxide powder, the sulfur dioxide gas synchronously calcining being generated is drawn and is adopted the authorized Chinese patent 200510021926.X of patent applicant of the present invention to take the method that pyrolusite and pH buffer reagent carry out waste-gas desulfurization as composite absorber, 200910058061.2 be applicable to the reactor of leaching sulfur dioxide gas out of pyrolusite, 200910058062.7 prepare the method for manganese sulfate solution with leaching sulfur dioxide gas out of pyrolusite, 200910060313.5 suppress the method that manganous dithionate generates in process of leaching sulfur dioxide gas out of pyrolusite, with pyrolusite pulp, absorb and generate the manganese sulfate solution that contains impurity.Adopt a kind of " method of high purity manganese sulfate solution " that the present patent application people is examining in first to file to purify the highly purified manganese sulfate solution of acquisition the above-mentioned manganese sulfate solution that contains impurity, by the heating of high-purity manganese sulphate soln using calcining high-temperature tail gas, concentrated, crystallization, acquisition meets the high purity manganese sulfate that present method requires, again Returning utilization.
Claims (10)
1. a preparation method for high-purity mangano-manganic oxide, its spy is to comprise following processing step:
(1) high purity manganese sulfate and organic activator are inserted grinding plant or the activation of whipping device mixing machinery, time is no less than 2 hours, the add-on of described organic activator is not less than 1% of manganous sulfate crystal mass, and described organic activator is selected from the organism of alcohol, ketone, aldehydes;
(2) raw material after mechanical activation is inserted calciner, passes into air or nitrogen and calcines 1～5 hour at 800 ℃～1000 ℃, and it is spherical generating pattern, manganese mass content>=71%, loose density≤1.5g/m
3, specific surface area≤l.0m
2/ g, potassium, sodium, calcium, magnesium mass content all≤50ppm, plumbous mass content≤10ppm, with SO
4vitriol mass content≤the 200ppm of meter, the trimanganese tetroxide powder of screenings≤25% sieving with 45um testing sieve;
(3) sulfur dioxide gas that step (2) calcining generates is drawn from calciner, the pyrolusite of take adds water and pH buffer reagent is composite absorber, or take that pyrolusite adds water and gac is composite absorber, or take pyrolusite, to add water, pH buffer reagent and gac be composite absorber, composite absorber, sulfur dioxide gas, oxygen are sent into continuously respectively in the reactor that is provided with the two-stage absorption Leaching reaction chamber of connecting up and down and absorbed successively Leaching reaction, the manganese sulfate solution that generation contains impurity, absorbs Leaching reaction and operates under positive pressure;
(4) manganese sulfate solution that contains impurity that step (3) is produced, employing is induced and is generated the hydroxyl radical free radical OH with strong oxidizing property in manganese sulfate solution, react the Manganse Dioxide or the trimanganese tetroxide that generate nascent state with mn ion in manganese sulfate solution, impurity in absorption manganese sulfate solution forms the purifying method high purity manganese sulfate solution of Mn oxide, the heating of high-purity manganese sulphate soln using calcining high-temperature tail gas, concentrated, crystallization, obtain satisfactory high purity manganese sulfate, return to step (1) circulation, described high purity manganese sulfate is that foreign matter content reaches the manganous sulfate crystal that cell-grade requires.
2. the preparation method of high-purity mangano-manganic oxide according to claim 1, is characterized in that air or nitrogen amount that described calcining passes into are passed into the mixed volumetric concentration of gas not higher than 20% by the sulfur dioxide gas that can make manganous sulfate pyrolysis produce.
3. the preparation method of high-purity mangano-manganic oxide according to claim 1, it is characterized in that described high purity manganese sulfate be the content of potassium, sodium, calcium, magnesium addition element all lower than 50mg/Kg, the content of iron, aluminium, cobalt, nickel, copper, zinc, lead, cadmium, arsenic, sila prime element is all lower than 10mg/Kg.
4. according to the preparation method of the high-purity mangano-manganic oxide described in claim 1 or 2 or 3, it is characterized in that absorbing amount of oxygen that leaching process passes into for can make to absorb the indoor pH value of reaction system of Leaching reaction lower than 3.5.
5. according to the preparation method of the high-purity mangano-manganic oxide described in claim 1 or 2 or 3, it is characterized in that in composite absorber, the mass ratio of pyrolusite and water is 5:1～1:1.
6. the preparation method of high-purity mangano-manganic oxide according to claim 4, is characterized in that in composite absorber, the mass ratio of pyrolusite and water is 5:1～1:1.
7. according to the preparation method of the high-purity mangano-manganic oxide described in claim 1 or 2 or 3, the two-stage that it is characterized in that connecting up and down absorbs Leaching reaction chamber and is all furnished with the agitator that every cube of ore pulp is not less than 5KW.
8. the preparation method of high-purity mangano-manganic oxide according to claim 4, the two-stage that it is characterized in that connecting up and down absorbs Leaching reaction chamber and is all furnished with the agitator that every cube of ore pulp is not less than 5KW.
9. the preparation method of high-purity mangano-manganic oxide according to claim 5, the two-stage that it is characterized in that connecting up and down absorbs Leaching reaction chamber and is all furnished with the agitator that every cube of ore pulp is not less than 5KW.
10. the preparation method of high-purity mangano-manganic oxide according to claim 6, the two-stage that it is characterized in that connecting up and down absorbs Leaching reaction chamber and is all furnished with the agitator that every cube of ore pulp is not less than 5KW.
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| CN104362327B (en) * | 2014-11-10 | 2016-06-15 | 湖北高博科技有限公司 | A kind of high purity battery level manganese source and preparation method thereof |
| CN109336184B (en) * | 2018-10-31 | 2021-01-19 | 胡义华 | Method for preparing manganous-manganic oxide by utilizing two-stage dry roasting of manganese sulfate |
| CN111620377B (en) * | 2020-06-12 | 2023-06-30 | 福建常青新能源科技有限公司 | Oil removal and impurity removal process and device for manganese sulfate solution |
| CN112357964A (en) * | 2020-10-30 | 2021-02-12 | 杜长福 | Preparation method of battery-grade trimanganese tetroxide |
| CN112795985A (en) * | 2020-12-29 | 2021-05-14 | 无锡晶石新型能源股份有限公司 | Preparation method of doped single crystal manganous-manganic oxide |
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