CN1927727A - Method of preparing high-purity manganomanganic oxide by pyrolyzing manganese sulfate at high temperature - Google Patents
Method of preparing high-purity manganomanganic oxide by pyrolyzing manganese sulfate at high temperature Download PDFInfo
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- CN1927727A CN1927727A CN 200610122399 CN200610122399A CN1927727A CN 1927727 A CN1927727 A CN 1927727A CN 200610122399 CN200610122399 CN 200610122399 CN 200610122399 A CN200610122399 A CN 200610122399A CN 1927727 A CN1927727 A CN 1927727A
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Abstract
The present invention provides technological process of producing high purity manganous manganic oxide with industrial manganese sulfate as material. The technological process includes dissolving industrial manganese sulfate, depurating, filtering, the first crystallization, the second crystallization, drying, heating at 400-600 deg.c to eliminate crystal water and pyrolysis at 950-1100 deg.c to obtain high purity manganous manganic oxide. The present invention has simple technological process, low investment, cheap material, low cost, high product purity and great specific surface area of the product.
Description
Technical field:
The present invention relates to a kind of manufacture method of high-purity mangano-manganic oxide, particularly produce the method for trimanganese tetroxide with the manganous sulfate high temperature pyrolysis.
Background technology:
Artificial trimanganese tetroxide causes that as a kind of oxide compound of manganese the extensive interest of people is the thing of recent two decades, and the factor of decision is that the development of electronic industry has driven development of soft magnetic.High-purity mangano-manganic oxide (Mn
3O
4) be the main raw material of producing soft magnetic ferrite of new generation and microwave ferrite material, in industrial sectors such as electronics, electrical equipment, electric power, purposes is widely arranged.Current, soft magnetic materials is functional, low-cost should be manganese, zinc, ferrite, the inductance component made from this soft magnetic materials, transformer winding, reactance coil etc. have obtained at aspects such as communication equipment, broadcast television product, computer product, industrial automation equipment, switch power supply and anti-electromagnetic interference using widely, have particularly replaced heavy silieonized plate in switch power supply and have obtained to put to good use the chance of its excellent specific property.In recent years, along with switch power supply develops to high frequencyization, miniaturization, new high frequency ferrite material is devoted to continually develop in countries in the world.Trimanganese tetroxide is more suitable in this class material of production than artificial high-purity manganese carbonate, and makes product have characteristics such as better high permeability, high resistivity, thereby trimanganese tetroxide is progressively replacing the main ingredient of manganous carbonate as soft magnetic materials.Recent years, soft magnetic ferrite market, the world is with average annual 15% speed sustainable growth.
Mn
3O
4Also can be used as and decompose carbon nitrogen, the catalyzer of oxide compound and the catalyzer of selective reduction oil of mirbane, also can be used as the colorant of some paint or coating, add Mn
3O
4Paint or coating corrosion resistance be significantly improved.Also find high-purity Mn recently
3O
4Be preparation anode material for lithium-ion batteries LiMn
2O
4High quality raw material, its effect is better than Manganse Dioxide (MnO
2).Therefore, Mn
3O
4Product at home or all there are huge demand and boundless application prospect in the world market.
According to reported in literature, make Mn
3O
4Method a lot, as roasting method, reduction method, oxidation style, electrolytic process and manganese powder aqueous solution chlorination method etc.Wherein the high-temperature roasting method of manganese powder aqueous solution chlorination method and high-purity manganese carbonate has been realized suitability for industrialized production.South Africa, the U.S., Japan and China all adopt manganese powder aqueous solution chlorination method to produce, and Belgian Sederma etc. adopt the production of manganous carbonate high-temperature roasting method.
Manganese powder aqueous solution chlorination method is the existing Mn of production
3O
4The most conventional and the method for industrialization, its advantage is the Mn of output
3O
4Quality is higher; But this method will be made raw material with electrolytic manganese, and the production of electrolytic manganese needs complicated technical process and expensive production unit, not only complex process but also production cost height, and only the power consumption of an operation of aqueous electrolysis just needs more than 7000 degree/ton products.And, cause Mn owing in preparation electrolytic metal Mn process, use selenium and potassium bichromate
3O
4Chromium and selenium index are higher in the product.With the high-purity manganese carbonate is raw material production Mn
3O
4Although it is quality product is better, also inadvisable.The price of high-purity manganese carbonate just with high purity Mn
3O
4Approaching, no economic benefit can be sayed.
Because manganous sulfate is cheap, with manganous sulfate as raw material production Mn
3O
4It is the minimum method of present cost.And high-temperature roasting method easily obtains high-quality Mn
3O
4Product, and technology is simpler, therefore becomes the high-purity Mn of present preparation
3O
4One of emphasis of research.Reported some relevant documents as open source literature, we take passages as follows by retrieval:
1. [application (patent) number] CN98112437.2[title] roasting process of preparing very of a kind of high-purity mangano-manganic oxide of roasting process of preparing very and the holy big magnetic material company [summary] in purposes [application (patent right) people] Chenzhou City Ya Shi level ground, Duan Xisheng [address] 423000 Hunan Province of high-purity mangano-manganic oxide, employing manganous sulfate and bicarbonate of ammonia are raw material.Its technological process is such: manganese sulfate solution behind purification and impurity removal and bicarbonate of ammonia reaction obtain manganous carbonate, manganous carbonate after drying under 850～1100 ℃ of aerobic conditions roasting make trimanganese tetroxide.
2. [application (patent) number] CN01106854.X[title] add weak ammonia in a kind of manufacture method [application (patent right) people] manganese sulfate solution of Balin Branch Corp. SINOPEC [address] 414000 Nanhu Avenue, Yueyang City, Hunan Province [summary] behind purification and impurity removal of trimanganese tetroxide, and the control endpoint pH, promptly generate Mn (OH)
2Precipitation with this precipitate and separate, drying, in 1000 ℃ of roastings 2 hours, cooling, washing, again after the drying, promptly obtains the high purity trimanganese tetroxide.Not precipitating completely in the reaction solution, manganese can precipitate MnCO with it with the carbon ammonium
3, the rate of recovery of raising Mn.
Recognize that from above-mentioned result for retrieval the high-temperature roasting manufacture method of the trimanganese tetroxide of open source literature introduction is at first manganous sulfate to be changed into MnCO
3Or Mn (OH)
2, preparation Mn is decomposed in high-temperature roasting then
3O
4Use these two kinds of method roasting process to be easy to control, easily obtain high-purity Mn
3O
4, without harmful gas generation.But 1. document needs to consume a large amount of bicarbonate of ammonia, and 2. document needs to consume a large amount of ammoniacal liquor, and all has the recovery problem of ammonium sulfate in the waste water, makes the whole production process complications, and cost rises.
Summary of the invention:
The present invention relates to a kind of manufacture method of high-purity mangano-manganic oxide.
The present invention adopts following technical scheme to realize: the industrial manganic sulfate first grade is dissolved near state of saturation with clean clear water, makes manganese sulfate solution.The manganese sulfate solution that makes is removed impurity such as heavy metal ion in the solution and calcium, magnesium, silicon by the method for known chemical subtraction.Chemical subtraction mainly is to add various chemical reagent in manganese sulfate solution, makes heavy metal ion and calcium, magnesium, silicon etc. form precipitation.The chemical reagent that diverse ways added, temperature of reaction can be different, but purpose all is in order to remove the undesired impurities in the manganese sulfate solution.The selection of chemical reagent, reaction conditions should belong to known technology at present.
Primary crystallization: the manganese sulfate solution after will purifying concentrates, crystallization, is about 1: 1 o'clock filtered while hot at crystallization content and mother liquor amount (volume ratio), and mother liquor returns cleaning section.
Secondary crystal: the prepared manganous sulfate of primary crystallization is dissolved near state of saturation with soft water again, concentrates once more, crystallization, be about 1: 1 o'clock filtered while hot at crystallization content and mother liquor amount (volume ratio), mother liquor returns the primary crystallization operation.
The crystallization of secondary manganous sulfate is after about 100 ℃ dry about 2 hours, and heating was dewatered in 1～2 hour under 400～600 ℃, with manganese sulfate monohydrate (MnSO
4.H
2O) water molecules in the lattice is removed.Pyrolysis obtained trimanganese tetroxide after 1～3 hour under 950～1100 ℃ of temperature again.Pyrolytic process need not bubbling air.
The SO that produces in the pyrolytic process
2And SO
3Gas can be used as and produces vitriolic high-quality source of the gas.Through waste heat recovery, dedusting and be cooled to be lower than 50 ℃ after, deliver to before the main air blower of sulfuric acid production plant with after its raw materials for production gas mixes and enter conversion workshop section.So requirement of the present invention and sulfuric acid production plant combine, thereby make the SO that produces in the pyrolytic process
2And SO
3The processing of gas does not need extra investment and working cost, and makes 1t Mn
3O
4Can the about 1.3t of by-product 98% vitriol oil.
The present invention and existing high-temperature roasting prepare Mn
3O
4Technology is compared, and its outstanding substantive distinguishing features and obvious improvement is: need not earlier manganous sulfate to be converted into the compound of other manganese, thereby production cost is significantly descended.Technology is simple, less investment.Mn to this method production
3O
4Analyze, the product that its quality index and manganous carbonate roasting method are produced remains basically stable; Manganous sulfate decomposes fully, and the product sulphur content is lower than 0.005%, far below the German Metox electronic-grade Mn of company
3O
4The desired sulphur content of company standard.And product is difficult for the moisture absorption caking, is difficult for oxidation.
Embodiment:
Embodiment 1
The industrial manganic sulfate first grade is dissolved near state of saturation with clean clear water, makes manganese sulfate solution.The manganese sulfate solution that makes is carried out contained heavy metal ion quantitative analysis, add the 0.5mol/L ammonium sulfide solutions down for 50～80 ℃ in temperature, make Cu with 2 times of contained heavy metal ion total mole number
2+, Ni
2+, Zn
2+, Co
2+Remove etc. heavy metal ion generation sulfide precipitation, left standstill 12～24 hours, filter.Adding in filtrate again and cooperate precipitation agent SDD (diethylamine bamic acid sodium), manganese sulfate solution is further purified, mainly is further to remove heavy metal and trace impurities such as calcium, magnesium.The add-on of SDD is 2 times of last trace impurity theoretical amount, 50～70 ℃ of temperature of reaction, and the reaction times is 1 hour, filters.The Ca that in filtrate, adds filtrate again
2+, Mg
2+2～2.4 times of concentration of ion total mole number are the 1mol/L ammonium fluoride solution, make Ca
2+, Mg
2+Ion generates CaF
2, MgF
2Precipitation is removed, and filters to obtain the purified manganese sulfate solution.
Primary crystallization: the manganese sulfate solution after will making with extra care concentrates, crystallization, is about 1: 1 o'clock filtered while hot at crystallization content and mother liquor amount (volume ratio), and mother liquor returns cleaning section.
Secondary crystal: the prepared manganous sulfate of primary crystallization is dissolved near state of saturation with soft water again, concentrates once more, crystallization, be about 1: 1 o'clock filtered while hot at crystallization content and mother liquor amount (volume ratio), mother liquor returns the primary crystallization operation.
With the prepared pure manganous sulfate of secondary crystal 105 ℃ of dryings 2 hours, 550 ℃ down heating dewatered in 1.5 hours, with manganese sulfate monohydrate (MnSO
4.H
2O) water molecules in the lattice is removed.Pyrolysis obtained trimanganese tetroxide in 2 hours under 1050 ℃ of temperature again.Pyrolytic process need not bubbling air.
The SO that produces in the pyrolytic process
2And SO
3Gas, through waste heat recovery, dedusting and be cooled to be lower than 50 ℃ after, deliver to before the main air blower of sulfuric acid production plant with after its raw materials for production gas mixes and enter conversion workshop section, production sulfuric acid.
The high-purity mangano-manganic oxide product quality indicator that makes is:
Mn 71.57%, and Ca 0.004%, and Mg 0.002%, and Si 0.001%, and Pb 0.0005%, and S 0.005%, specific surface area 16.1m
2/ g.
Embodiment 2
The prepared pure manganous sulfate of secondary crystal, is heated under 400 ℃ and dewatered in 2 hours after 2 hours 100 ℃ of dryings.Pyrolysis 1 hour under 1100 ℃ of temperature then obtains total manganese content and reaches 71.51% trimanganese tetroxide, and other quality index and embodiment one are approaching.
Embodiment 3
With the prepared pure manganous sulfate of secondary crystal 105 ℃ of dryings 2 hours, 600 ℃ down heating dewatered in 1 hour.Pyrolysis obtained total manganese content in 3 hours and reaches 71.40% trimanganese tetroxide under 950 ℃ of temperature then, and other quality index and embodiment one are approaching.
Claims (3)
1, the manganous sulfate high temperature pyrolysis is produced the method for high-purity mangano-manganic oxide, it is characterized in that: with industrial manganic sulfate dissolving, removal of impurities, filtration, primary crystallization, secondary crystal, drying, heating take off crystal water, high temperature pyrolysis makes high-purity mangano-manganic oxide.
2, the preparation method of high-purity mangano-manganic oxide according to claim 1 is characterized in that crystal water was taken off in manganous sulfate heating under 400～600 ℃ in 1～2 hour.
3, the preparation method of high-purity mangano-manganic oxide according to claim 1 is characterized in that anhydrous manganous sulfate pyrolysis under 950～1100 ℃ of temperature was obtained trimanganese tetroxide in 1～3 hour.
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|---|---|---|---|
| CN 200610122399 CN1927727A (en) | 2006-09-21 | 2006-09-21 | Method of preparing high-purity manganomanganic oxide by pyrolyzing manganese sulfate at high temperature |
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|---|---|---|---|
| CN 200610122399 CN1927727A (en) | 2006-09-21 | 2006-09-21 | Method of preparing high-purity manganomanganic oxide by pyrolyzing manganese sulfate at high temperature |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633306A (en) * | 2012-04-10 | 2012-08-15 | 四川大学 | High-purity trimanganese tetroxide and preparation method of same |
| CN105948130A (en) * | 2016-07-05 | 2016-09-21 | 湖南蒙达新能源材料有限公司 | Trimanganese tetraoxide, as well as preparation method and application 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 |
| CN111139516A (en) * | 2019-12-31 | 2020-05-12 | 无锡晶石新型能源股份有限公司 | Preparation method of single crystal type lithium manganate material and precursor thereof |
| 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 |
| CN115448369A (en) * | 2022-08-26 | 2022-12-09 | 广西大学 | Preparation method and application of precipitator for removing calcium ions from manganese sulfate solution |
-
2006
- 2006-09-21 CN CN 200610122399 patent/CN1927727A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102633306A (en) * | 2012-04-10 | 2012-08-15 | 四川大学 | High-purity trimanganese tetroxide and preparation method of same |
| CN102633306B (en) * | 2012-04-10 | 2014-01-22 | 四川大学 | Preparation method of high-purity trimanganese tetroxide |
| CN105948130A (en) * | 2016-07-05 | 2016-09-21 | 湖南蒙达新能源材料有限公司 | Trimanganese tetraoxide, as well as preparation method and application thereof |
| CN105948130B (en) * | 2016-07-05 | 2017-06-09 | 湖南蒙达新能源材料有限公司 | A kind of mangano-manganic oxide, preparation method and applications |
| 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 |
| CN111139516A (en) * | 2019-12-31 | 2020-05-12 | 无锡晶石新型能源股份有限公司 | Preparation method of single crystal type lithium manganate material and precursor thereof |
| 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 |
| CN115448369A (en) * | 2022-08-26 | 2022-12-09 | 广西大学 | Preparation method and application of precipitator for removing calcium ions from manganese sulfate solution |
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