CN102633306A - High-purity trimanganese tetroxide and preparation method of same - Google Patents
High-purity trimanganese tetroxide and preparation method of same 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 present invention relates to produce the raw material technical field of soft magnetic ferrite, more specifically relate 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, is the important source material of producing soft magnetic ferrite, can be used as magnetic core, the Disk and tape of canned data in the robot calculator; Phone is with X-former and high Q inductor device, the television flyback X-former, and magnetic recording is used magnetic head; Inducer; Transductor amplifier, saturated inductor, aerial rod.The colorant that can be used as some paint or coating in addition, the paint or the paint that contain high-purity mangano-manganic oxide are sprinkled upon on the iron and steel has better corrosion resistance than paint that contains titanium oxide or red stone or coating.The 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; With adopting the manganese ore wet method to leach the manganese sulfate solution that obtains; Through impurity and purification, add ammonium salt alkalization, filter, adopt air or oxygen oxidation, washing to obtain the trimanganese tetroxide crystal, with the trimanganese tetroxide crystal dry, cool off, pack product.Though this method technical maturity because the manganese sulfate solution purification and impurity removal is particularly removed potassium sodium calcium magnesium addition ion and remained in technological difficulties, therefore, adopts this method to be difficult to make high-purity other trimanganese tetroxide of level.(2) electrolytic metal manganese powder suspension-s oxidation style is a raw material with the electrolytic metal Mn sheet, the manganese metal sheet is pulverized processed manganese powder suspension-s earlier, utilizes air or oxygen to make oxygenant again, under the condition of certain temperature and interpolation ammonium salt, and the preparation trimanganese tetroxide.Though this method technical maturity, simple, the raw material electrolytic metal Mn cost that should technology uses is high, and because the current electrolysis manganese metal generally contains selenium, makes the trimanganese tetroxide selenium content exceed standard, and is difficult to reach high-purity rank.(3) manganous sulfate calcination method: with manganous sulfate crystal heating and calcining, directly generate trimanganese tetroxide, get product through washing and drying.The key of this method is to obtain high-purity mangano-manganic oxide, at first must guarantee manganous sulfate crystalline purity, because after the manganous sulfate crystal high-temperature decomposed, impurity can continue to remain in the trimanganese tetroxide, and has the problem that enrichment increases.Chinese patent " a kind of manganous sulfate circulation method prepares the method for trimanganese tetroxide " (application number: 201010537545.8); The method that a kind of manganous sulfate circulation method prepares trimanganese tetroxide is disclosed; The concrete technical scheme of this patented claim is: sulfurous gas and sulphur trioxide mixed gas that the manganous sulfate high-temperature calcination produces is dry through the vitriol oil; And feed in the mixed ore pulp of forming by pyrolusite, manganous carbonate and water with air mixed compression back, extraction temperature be 85 ℃ and constantly stir under leach and got leaching liquid in 7 hours; In leaching liquid, add successively till Sodium Dimethyldithiocarbamate, ammonium sulfate and Neutral ammonium fluoride to the no longer generation deposition, filter and obtain manganese sulfate solution, the manganese sulfate solution evaporation concentration with filtration obtains obtains manganese sulfate monohydrate in 80 ℃-100 ℃; Manganese sulfate monohydrate was made it dehydration in 0.5-2 hour in 350 ℃ of heating; Again in 950 ℃-1050 ℃ calcinings 1-2 hour; The powder that calcining produces is with zero(ppm) water or deionized water rinsing, dry trimanganese tetroxide, and the sulfurous gas that calcining produces and sulphur trioxide mixed gas are through vitriol oil drying; And feed in the mixed ore pulp of forming by pyrolusite, manganous carbonate and water the purpose of realization manganous sulfate cyclic production trimanganese tetroxide with air mixed compression back.The problem that this method exists: (1) undeclared impurity such as iron, aluminium, potassium, sodium of how from the manganese ore leach liquor, removing.(2) specialize incinerating atmosphere (vacuum, antivacuum, nitrogen protection etc.); And think that the gas that calcining produces is sulfurous gas and sulphur trioxide mixed gas; Adopt pyrolusite, manganous carbonate to absorb with the mixed ore pulp that water is formed, day by day under the background of exhaustion, practical value is little in the manganese carbonate ore resource; And the sulfur trioxide gas wet absorption is prone to produce acid mist, causes absorbing not exclusively and the secondary pollution problem.(3) product standard of undeclared trimanganese tetroxide.
Contriver of the present invention is engaged in manganese ore extract technology and leach liquor removal of impurities for a long time, makes with extra care research, and the SEPARATE APPLICATION and the related patent U.S. Patent No. of having obtained the authorization are multinomial: Chinese patent 200510021926.X is that the method, 200910058061.2 that composite absorber carries out waste-gas desulfurization is applicable to that the reactor drum of leaching sulfur dioxide gas out of pyrolusite, method, 200910059583.4 pyrolusites that 200910058062.7 usefulness leaching sulfur dioxide gas out of pyrolusite prepare manganese sulfate solution leach SO in the solution with pyrolusite and pH buffer reagent
2- 4, SO
2- 3, S
2O
2- 6, S
2O
2- 8Suppress the method for manganous dithionate generation, the special purpose reactor that 200920078540.6 leaching sulfur dioxide gas out of pyrolusite are produced manganese sulfate solution in synchronized analyzing method, 200910060313.5 process of leaching sulfur dioxide gas out of pyrolusite.
Existing research and contriver's of the present invention preliminary experiment research all confirms; The pyrolytic decomposition behavior of manganous sulfate is complicated; It is different under different atmosphere, to decompose resulting product; Therefore, the key issue that adopts manganous sulfate cyclic high-temperature calcination method to prepare trimanganese tetroxide is: how (1) regulates and control the pyrolytic decomposition condition of manganous sulfate, makes that degradation production is trimanganese tetroxide powder and sulfur dioxide gas; The purity of the manganous sulfate of (2) how guaranteeing to recycle, the purity of the trimanganese tetroxide of guaranteeing to obtain.
Summary of the invention:
The object of the invention provides a kind of high-purity mangano-manganic oxide of superior performance just with deficiency for the shortcoming that overcomes above-mentioned prior art, can be used as the raw material of producing soft magnetic ferrite; Two provide a kind of method for preparing high-purity mangano-manganic oxide.
High-purity mangano-manganic oxide provided by the invention, its pattern are spherical, manganese mass content>=71%, loose density≤1.5g/m
3, specific surface area≤1.0m
2/ g, potassium, sodium, calcium, magnesia amount content all≤50ppm, plumbous mass content≤10ppm is with SO
4Vitriol mass content≤the 200ppm of meter, screenings≤25% that sieves with the 45um testing sieve.
The present invention also provides the preparation method of this high-purity mangano-manganic oxide, and its process 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 behind the mechanical activation is inserted calciner, and bubbling air or nitrogen were calcined 1～5 hour down in 800 ℃～1000 ℃, generated satisfactory trimanganese tetroxide powder;
(3) sulfur dioxide gas of step (2) calcining generation is drawn from calciner; Add water and the pH buffer reagent is a composite absorber with pyrolusite; Or add water and gac is a composite absorber with pyrolusite; Or to add water, pH buffer reagent and gac with pyrolusite be composite absorber; Composite absorber, sulfur dioxide gas, oxygen sent into respectively to be provided with to absorb successively in the reactor drum that the two-stage of connecting up and down absorb to leach reaction chamber continuously leach reaction, generate the manganese sulfate solution that contains impurity, absorb to leach and be reflected at the direct draught operation;
(4) manganese sulfate solution that contains impurity produced of step (3); Be employed in to induce in the manganese sulfate solution and generate hydroxyl radical free radical OH with strong oxidizing property; Manganse Dioxide or trimanganese tetroxide with mn ion reaction generation nascent state in the manganese sulfate solution; Impurity in the absorption manganese sulfate solution forms the purifying method of Mn oxide and produces the high-purity sulphuric acid manganese solution; The heating of high-purity manganese sulphate soln using calcining high-temperature tail gas, concentrated, crystallization obtain satisfactory high purity manganese sulfate, return step (1) circulation.
In technique scheme, said organic activator can be selected from the organism of alcohol, ketone, aldehydes.The add-on of organic activator preferably is not less than 1% of manganous sulfate crystal mass.
In technique scheme, the amount of calcination process bubbling air, nitrogen is fed the mixed volumetric concentration of gas by the sulfur dioxide gas that the manganous sulfate pyrolysis is produced and is not higher than 20% (V/V).
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 all is lower than 50mg/kg, and the content of iron, aluminium, cobalt, nickel, copper, zinc, lead, cadmium, arsenic, sila prime element all is lower than 10mg/kg.
In technique scheme, the amount of oxygen that absorbs the leaching process feeding preferably can make the pH value of reaction system that absorbs in the leaching reaction chamber be lower than 3.5; Pyrolusite and quality are than the scope that preferably is controlled at 5: 1～1: 1 in the composite absorber; The two-stage of connecting up and down absorbs the leaching reaction chamber and preferably all is furnished with the whisking appliance 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 with existing manganous sulfate circulation calcining process has the outstanding technique effect of following ten minutes:
(1) the present invention adopts high purity manganese sulfate as the manganese based raw material, and it is high to have overcome traditional calcination method raw material manganic compound foreign matter content, and particularly Na, K ion are difficult to remove the problem that the product that brings is difficult to stably reaching standard.
(2) the present invention to high purity manganese sulfate crystal by adopting organic activator mechanical activation, can reduce the manganous sulfate decomposition temperature before calcining, practices thrift heat energy.
(3) the present invention adopts organic activator that the high purity manganese sulfate crystal is carried out mechanical activation, and it is inner that organic activator penetrates into the manganous sulfate crystal lattices, and the micro-dissolving gas that in the high-temperature calcination decomposition course, produces can significantly improve the specific surface area of trimanganese tetroxide.
(4) organic activator cooperates air or nitrogen atmosphere calcining; Can make manganous sulfate decompose the gas that produces is sulfurous gas; Do not produce sulphur trioxide, not only can efficiently utilize pyrolusite, and avoid the sulfur trioxide gas wet absorption to be prone to produce the secondary pollution problem of acid mist.
(5) the supporting pyrolusite pulp that adopts applicant of the present invention 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 constituted.
Description of drawings
Accompanying drawing 1 is the process flow diagram of one embodiment of the invention.
Embodiment:
Through embodiment the present invention is carried out concrete description below; But be necessary to be pointed out that at this; Embodiment only is used for the present invention is further described; Can not be interpreted as the restriction to protection domain of the present invention, the technician in this field can content according to the present invention makes some nonessential improvement and practical implementation is carried out in adjustment, but such practical implementation should still belong to protection scope of the present invention.
In following each embodiment, involved component concentration except that specifying, is mass percent or mass fraction.
Embodiment 1
The acetone that the high purity manganese sulfate that will meet quality standard adds its quality 2% is organic activator, then admixture activation 3 hours in ball mill.Raw material behind the mechanical activation is sent into calciner; Controlled temperature is at 900 ℃; Calcining is 3 hours under air atmosphere; Air feeding amount is that 15% (V/V) controls according to the sulfur dioxide gas that the manganous sulfate pyrolysis can produce by the mixed volumetric concentration of feeding gas; Generate satisfactory trimanganese tetroxide powder; To calcine the sulfur dioxide gas that generates synchronously and draw and adopt the authorized Chinese patent 200510021926.X of patent applicant of the present invention, absorb the manganese sulfate solution that generation contains impurity with pyrolusite pulp to suppress the method that manganous dithionate generates in pyrolusite and pH buffer reagent are method, 200910058061.2 that composite absorber the carries out waste-gas desulfurization reactor drum that is applicable to leaching sulfur dioxide gas out of pyrolusite, 200910058062.7 usefulness leaching sulfur dioxide gas out of pyrolusite prepare manganese sulfate solution method, 200910060313.5 process of leaching sulfur dioxide gas out of pyrolusite." a kind of method of producing the high-purity sulphuric acid manganese solution " that adopt applicant of the present invention examining in first to file the above-mentioned manganese sulfate solution that contains impurity purifies the highly purified manganese sulfate solution of acquisition; With the high-purity manganese sulphate soln using calcining high-temperature tail gas heating that obtains, concentrated, crystallization; Acquisition meets the high purity manganese sulfate that present method requires, Returning utilization once more.
Embodiment 2
The USP Kosher that will meet its quality 4% of high purity manganese sulfate adding of quality standard is an organic activator, then stirrer for mixing activation 4 hours.Raw material behind the mechanical activation is sent into calciner; Controlled temperature is at 950 ℃; Calcining is 3.5 hours under the feeding nitrogen atmosphere; Nitrogen feeding amount is that 10% (V/V) controls according to the sulfur dioxide gas that the manganous sulfate pyrolysis can produce by the mixed volumetric concentration of feeding gas; Generate satisfactory trimanganese tetroxide powder; To calcine the sulfur dioxide gas that generates synchronously and draw and adopt the authorized Chinese patent 200510021926.X of patent applicant of the present invention, absorb the manganese sulfate solution that generation contains impurity with pyrolusite pulp to suppress the method that manganous dithionate generates in pyrolusite and pH buffer reagent are method, 200910058061.2 that composite absorber the carries out waste-gas desulfurization reactor drum that is applicable to leaching sulfur dioxide gas out of pyrolusite, 200910058062.7 usefulness leaching sulfur dioxide gas out of pyrolusite prepare manganese sulfate solution method, 200910060313.5 process of leaching sulfur dioxide gas out of pyrolusite." a kind of method of producing the high-purity sulphuric acid manganese solution " that adopt applicant of the present invention examining in first to file the above-mentioned manganese sulfate solution that contains impurity purifies the highly purified manganese sulfate solution of acquisition; With 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, Returning utilization once more.
Embodiment 3
The acetaldehyde that the high purity manganese sulfate that will meet quality standard adds its quality 3% is organic activator, then airtight admixture activation 2.5 hours in ball mill.Raw material behind the mechanical activation is sent into calciner; Controlled temperature is at 1000 ℃; Calcining is 3.5 hours under the atmosphere of bubbling air and nitrogen mixture; Gas mixture feeding amount is that 5% (V/V) controls according to the sulfur dioxide gas that the manganous sulfate pyrolysis can produce by the mixed volumetric concentration of feeding gas; Generate satisfactory trimanganese tetroxide powder; To calcine the sulfur dioxide gas that generates synchronously and draw and adopt the authorized Chinese patent 200510021926.X of patent applicant of the present invention, absorb the manganese sulfate solution that generation contains impurity with pyrolusite pulp to suppress the method that manganous dithionate generates in pyrolusite and pH buffer reagent are method, 200910058061.2 that composite absorber the carries out waste-gas desulfurization reactor drum that is applicable to leaching sulfur dioxide gas out of pyrolusite, 200910058062.7 usefulness leaching sulfur dioxide gas out of pyrolusite prepare manganese sulfate solution method, 200910060313.5 process of leaching sulfur dioxide gas out of pyrolusite." a kind of method of producing the high-purity sulphuric acid manganese solution " that adopt applicant of the present invention examining in first to file the above-mentioned manganese sulfate solution that contains impurity purifies the highly purified manganese sulfate solution of acquisition; With 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, Returning utilization once more.
Claims (10)
1. high-purity mangano-manganic oxide, it is characterized in that: pattern is spherical, manganese mass content>=71%, loose density≤1.5g/m
3, specific surface area≤1.0m
2/ g, potassium, sodium, calcium, magnesia amount content all≤50ppm, plumbous mass content≤10ppm is with SO
4Vitriol mass content≤the 200ppm of meter, screenings≤25% that sieves with the 45um testing sieve.
2. the preparation method of the said high-purity mangano-manganic oxide of claim 1, its spy is to comprise following process step:
(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 behind the mechanical activation is inserted calciner, and bubbling air or nitrogen were calcined 1～5 hour down in 800 ℃～1000 ℃, generated satisfactory trimanganese tetroxide powder;
(3) sulfur dioxide gas of step (2) calcining generation is drawn from calciner; Add water and the pH buffer reagent is a composite absorber with pyrolusite; Or add water and gac is a composite absorber with pyrolusite; Or to add water, pH buffer reagent and gac with pyrolusite be composite absorber; Composite absorber, sulfur dioxide gas, oxygen sent into respectively to be provided with to absorb successively in the reactor drum that the two-stage of connecting up and down absorb to leach reaction chamber continuously leach reaction, generate the manganese sulfate solution that contains impurity, absorb to leach and be reflected at the direct draught operation;
(4) manganese sulfate solution that contains impurity produced of step (3); Be employed in to induce in the manganese sulfate solution and generate hydroxyl radical free radical OH with strong oxidizing property; Manganse Dioxide or trimanganese tetroxide with mn ion reaction generation nascent state in the manganese sulfate solution; Impurity in the absorption manganese sulfate solution forms the purifying method of Mn oxide and produces the high-purity sulphuric acid manganese solution; The heating of high-purity manganese sulphate soln using calcining high-temperature tail gas, concentrated, crystallization obtain satisfactory high purity manganese sulfate, return step (1) circulation.
3. the preparation method of high-purity mangano-manganic oxide according to claim 2 is characterized in that said organic activator is selected from the organism of alcohol, ketone, aldehydes.
4. the preparation method of high-purity mangano-manganic oxide according to claim 3 is characterized in that the add-on of said organic activator is not less than 1% of manganous sulfate crystal mass.
5. according to the preparation method of claim 2 or 3 or 4 described high-purity mangano-manganic oxides, it is characterized in that air or nitrogen amount that said calcining feeds are not higher than 20% for the sulfur dioxide gas that can make manganous sulfate pyrolysis generation feeds the mixed volumetric concentration of gas.
6. according to the preparation method of claim 2 or 3 or 4 described high-purity mangano-manganic oxides, it is characterized in that said high purity manganese sulfate is that foreign matter content reaches the manganous sulfate crystal that cell-grade requires.
7. the preparation method of high-purity mangano-manganic oxide according to claim 6; It is characterized in that said high purity manganese sulfate is that the content of potassium, sodium, calcium, magnesium addition element all is lower than 50mg/kg, the content of iron, aluminium, cobalt, nickel, copper, zinc, lead, cadmium, arsenic, sila prime element all is lower than 10mg/kg.
8. according to the preparation method of claim 2 or 3 or 4 described high-purity mangano-manganic oxides, it is characterized in that the amount of oxygen that absorbs the leaching process feeding is lower than 3.5 for making the pH value of reaction system that absorbs in the leaching reaction chamber.
9. according to the preparation method of claim 2 or 3 or 4 described high-purity mangano-manganic oxides, it is characterized in that the mass ratio of pyrolusite and water is 5: 1～1: 1 in the composite absorber.
10. according to the preparation method of claim 2 or 3 or 4 described high-purity mangano-manganic oxides, the two-stage that it is characterized in that connecting up and down absorbs the leaching reaction chamber and all is furnished with the whisking appliance that every cube of ore pulp is not less than 5kW.
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| CN104362327A (en) * | 2014-11-10 | 2015-02-18 | 常开军 | High-purity battery-level manganese source and preparation method thereof |
| CN109336184A (en) * | 2018-10-31 | 2019-02-15 | 胡义华 | A method of mangano-manganic oxide is prepared using two sections of dry method roastings of manganese sulfate |
| CN111620377A (en) * | 2020-06-12 | 2020-09-04 | 福建常青新能源科技有限公司 | Process and device for removing oil and impurities from 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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| 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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| CN102633306B (en) | 2014-01-22 |
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