CN105523587B - A kind of preparation method of high-quality mangano-manganic oxide and the product for preparing - Google Patents
A kind of preparation method of high-quality mangano-manganic oxide and the product for preparing Download PDFInfo
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Abstract
A kind of preparation method of high-quality mangano-manganic oxide and the product for preparing, wherein：It not to be passivated electrolytic manganese metal piece is raw material that preparation method is, electrolytic manganese metal slurry is prepared using water atomization, and then electrolytic manganese metal slurry suspension oxidation reaction is obtained the preparation method of low selenium, low iron, trace chromium high-quality mangano-manganic oxide.Because the method saves surface passivation technology, the intake of the harmful ions such as chromium ion can be avoided, and appropriate process parameter is set in fusion process, the low boiling harmful elements such as selenium, sulphur, the phosphorus for also containing originally in removable manganese piece, in addition, water atomization slurrying can solve the problems, such as to increase iron, chromium in traditional ball mill crushing technique slurrying serious, and obtained slurry size distribution more concentrates, therefore can prepare low selenium, low iron, the mangano-manganic oxide product of trace chromium high-quality.The present invention also provides the lithium manganate material of the mangano-manganic oxide product and mangano-manganic oxide product synthesis prepared using the above method.
Description
Technical field
It is low the present invention relates to a kind of preparation method of high-quality mangano-manganic oxide and the product for preparing, more particularly to one kind
Selenium, low iron, the preparation method of trace chromium high-quality mangano-manganic oxide and the mangano-manganic oxide product and mangano-manganic oxide product that prepare
The lithium manganate material of synthesis.
Background technology
Mangano-manganic oxide is that a kind of black four directions crystallizes, alias brightness manganese, hausmannite, activity oxidation manganese, through calcination into crystallization,
Belong to spinels, wherein divalence is distributed on two kinds of different lattice positions with Manganic ion, and oxonium ion is cubic close
Pile up, divalent manganesetion accounts for tetrahedron space, and Manganic ion accounts for octahedral interstices.The production of current high-quality mangano-manganic oxide
Technique mainly has following several method：
(1) manganese sulfate solution oxidizing process, the manganese sulfate solution that will be obtained using manganese ore wet-leaching, by impurity and purification,
Plus ammonium salt is alkalized, filtered, obtaining mangano-manganic oxide crystal using air or oxygen oxidation, washing, and mangano-manganic oxide crystal is dried
Do, cool down, packing and to obtain product.Although the method technical maturity, due to manganese sulfate solution purification and impurity removal, potassium sodium calcium is particularly removed
Magnesium addition ion is remained in technological difficulties, therefore, it is difficult that the mangano-manganic oxide of high-purity rank is obtained using the method.
(2) manganese sulfate calcination method：By manganese sulfate crystal heating and calcining, mangano-manganic oxide is directly generated, it is scrubbed to dry
Product.The method it is critical only that high-purity mangano-manganic oxide to be obtained it may first have to ensure the purity of manganese sulfate crystal, because, sulphur
After sour manganese crystal high-temperature is decomposed, impurity may proceed to remain in mangano-manganic oxide, and with the problem of enrichment increase.
(3) electrolytic metal manganese powder suspension oxidizing process：With electrolytic manganese metal piece as raw material, first manganese metal piece is crushed and is made
Manganese powder suspension, recycles air or oxygen to make oxidant, under conditions of uniform temperature and addition ammonium salt, prepares four oxidations three
Manganese.China is Mn3O4 major producing countries, and production technology generally uses electrolytic manganese metal wet oxidation method, its typical process flow
For：Electrolytic manganese metal piece → powder (dry method, wet method) → oxidation → washing → drying → finished product processed.This preparation method has technique
Be simple and convenient to operate, specific yield is big, manganese recovery ratio is high and pollute it is small the advantages of, used by most of manufacturers.Although should
Method technical maturity, simple, small investment, but its shortcoming for protruding is not resolved for many years：1) with low content of technology, production cost is high,
Profit is very low；2) various impurity contents are generally higher, can only produce the product of common grade；3) specific surface area is smaller, typically
It is 5m2/g-10m2/ g, foreign customers are typically required in 10m2/ more than g；4) impure selenium (Se) is higher.
Most producers have used additive SeO in China's electrolytic manganese production process2, thus made electrolytic manganese generally contains
There is the Se of 0.05-0.1%, correspondingly, domestic mangano-manganic oxide usually contains impurity Se higher.To produce four oxidations three of low Se
Manganese, current way is, from low Se electrolytic manganeses but high from low Se manganese piece one side price, on the other hand low Se manganese piece is thick
And it is fine and close, it is difficult to broken, processing cost remains high.Certainly also contemplate for using other without Se raw materials such as MnSO4 etc., but due to
Silicon, calcium, magnesium and other impurities are difficult to purify, and the technological process of production is partially long, and waste is difficult to process and discharge capacity is again big, its industrialization
Still need perfect.Therefore, how the Mn3O4 of low Se into the problem being of practical significance is prepared very much with the piece of manganese containing Se.
Documents 1：CN103178256A discloses a kind of preparation method of mangano-manganic oxide for lithium-manganese battery, and being will be low
After the electrolytic manganese metal piece of S hot water is except Na, Mg, electrolytic manganese metal piece is milled to -200 μm of manganese more than 95% with Vertical Mill and is starched,
Stirred in input reactor, while being passed through air oxidation, and be slowly injected into ammoniacal liquor, reaction obtains average grain diameter in 15-25 hours and is
3-10 μm of mangano-manganic oxide manganese slurry.Secondary response will be carried out in mangano-manganic oxide manganese slurry another reactor of input again, in reactor
Ascorbic acid and formaldehyde, stirring are added, reaction temperature is controlled at 50 DEG C -70 DEG C, and the reaction time is four hours, four oxygen that will be obtained
Change three manganese manganese plasm scourings, after drying, it is 15~20 μm, the heavy mangano-manganic oxide of jolt ramming to obtain average grain diameter.
Documents 2：CN104803419A discloses a kind of preparation method of mangano-manganic oxide, comprises the following steps：(1)
Pretreatment of raw material；(2) slurrying；(3) acidleach：Filter after 98% 40~60min of strong sulfuric acid response to being added in ore pulp, ore pulp with it is dense
The weight ratio of sulfuric acid is 3~4.5:1；(4) removal of impurities；(5) it is electrolysed；(6) it is passivated；(7) clean；(8) dry and peel off；(10) it is dense
Contracting, washing, centrifugation, dehydration, dry mangano-manganic oxide powder.The present invention produces electrolytic manganese metal with low-grade manganese carbonate ore
Powder, then mangano-manganic oxide is prepared with electrolysis manganese powder, the mangano-manganic oxide specific surface area for obtaining is 15~20m2/g, and pine fills close
It is 0.6~0.8g/cm3 to spend, and the mass fraction of mangano-manganic oxide is more than or equal to 71%.
Documents 3：CN103121723A discloses a kind of preparation method of low calcium and magnesium high-purity mangano-manganic oxide, is by electricity
Solution manganese metal piece vertical grinder wet method is milled to 95% can pass through -45 μm of manganese slurry, and air oxidation is passed through in a kettle., stir
Mix, injection ammoniacal liquor makees catalyst, reaction obtains mangano-manganic oxide.
The preparation method of the mangano-manganic oxide disclosed in above documents is all belonging to electrolytic metal manganese powder suspension oxygen
Change method prepares mangano-manganic oxide, and documents 1 and documents 3 all use vertical grinder wet method (ball milling work in its preparation method
Skill) electrolytic manganese metal piece is worn into manganese slurry, the method for slurrying general at present is also using wet method slurrying (ball milling slurrying), wet method
The size distribution of slurry obtained in slurrying is not enough concentrated, and easily increases the heavy metal elements such as iron, chromium in pulping process.Contrast text
Surface passivation is carried out in part 2 to electrolytic manganese piece, passivation technology can raise electrolytic manganese metal piece top layer chromium content, prepared by influence
Mangano-manganic oxide product quality and purity.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of low selenium (content of selenium element is less than 0.0005%), low iron
The high-quality of (content of ferro element be less than 0.015%), trace chromium (content of chromium is hundred a ten thousandths) with complete spinelle
Structure can apply the preparation method and the product for preparing of the mangano-manganic oxide for synthesizing lithium manganate having spinel structure material.
In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：
The present invention provides a kind of preparation method of high-quality mangano-manganic oxide, specially：
One kind is raw material not to be passivated electrolytic manganese metal piece, and electrolytic manganese metal slurry is prepared using water atomization, then will
Electrolytic manganese metal slurry suspension oxidation reaction is obtained low selenium, low iron, the preparation method of trace chromium high-quality mangano-manganic oxide.
Further, the preparation method specifically includes following steps：
A, the surface treatment for not being passivated electrolytic manganese metal piece：
Directly the fresh electrolytic manganese metal piece that is not passivated is cleaned, is dried；
B, electrolytic manganese metal slurry is prepared using water atomization, comprised the following steps：
B1, smelting technology：To be carried out by not being passivated in electrolytic manganese metal piece input intermediate frequency furnace after step A surface treatments
Melting, a length of 35-40 minutes during its melting, smelting temperature is 1250-1350 DEG C；
B2, water smoke chemical conversion slurry：Enter water-filling by water atomization plant is poured into by the manganese metal piece turndown after melting in intermediate frequency furnace
Atomization process, regulation water atomization pressure is 300-400 kilograms, a length of 10-12min during turndown；
B3, size mixing：The need for the suspension oxidation reaction solution concentration of rear end, regulation slurry concentration to solid-liquid ratio is 1.6-
2.0；
C, suspension oxidation reaction：
Obtained electrolytic manganese metal slurry in step B is placed in carries out suspension oxidation reaction in reactor, injection ammoniacal liquor does
Catalyst, is passed through air, and reaction temperature is 50-70 DEG C；Mixing speed is 220-260r/min；The blow rate required is 1.8-2.2L/
min；Reaction time is 20-24h；
D, centrifugal drying：Mangano-manganic oxide is obtained after the completion of suspension oxidation reaction, through over cleaning, using centrifugal drying technique
After being dehydrated, get product.
Further,
Step B2 reclaimed waters are atomized into the electrolytic manganese metal slurry that slurry is formed more widely than to pass through equal to 95% -150 mesh.
Further,
Reactor described in step C is ceramic pipeline reactor.
Preferably, the reactor of the ceramic pipeline is the reactor on aluminum oxide abrasion resistant ceramic tube road.
Further,
Slag making also including melting and operation of skimming in the step B1 smelting technologies, use slag hitting in the operation of skimming
Agent carries out slag hitting treatment, improves melting purity.
Also known as slag former, slagging agent has suction-operated and melting ability to slag body to slagging agent, can sufficiently cleaned up metal bath,
Slag is reduced to metallic pollution, valuable effective metal is fully reclaimed, product direct yield is improved, reduces cost reduces slag rate.This programme
Described in slagging agent can using industrial melting conventional slagging agent, for example：Ice crystal.
Further,
Electrolytic manganese metal piece is protected using inert gas shielding air ring in the step B1 smelting technologies, it is prevented
Oxidation；
The inert gas preferably uses nitrogen or argon gas.
Preferably,
The intermediate frequency furnace is 500KG grades of intermediate frequency furnace.
Further,
In the not passive metal manganese piece：Mn >=99.9%；C≤0.02%；S≤0.04%；P≤0.002%；Si≤
0.004%；Se≤0.001%；Fe≤0.01%.
It is preferred that DJMnB not passive metal manganese pieces.
The present invention also provides a kind of using mangano-manganic oxide obtained in above-mentioned preparation method, and the mangano-manganic oxide has had
Whole spinel structure, in the mangano-manganic oxide：
Content≤0.0005% of Se elements；Content≤0.015% of Fe elements；The content of chromium is trace, i.e. chromium
Content be less than hundred a ten thousandths；
The content of S elements is 8-12ppm, the content ＜ 5ppm of P element, the content ＜ 15ppm of C element.
The present invention also provides a kind of lithium manganate material using mangano-manganic oxide synthesis obtained in above-mentioned preparation method, described
Lithium manganate material is lithium manganate having spinel structure (LiMn2O4) material.
Due to Mn3O4And LiMn2O4All it is spinel structure, uses Mn3O4Synthesis LiMn2O4In the absence of violent structure change,
With use general electrolytic MnO2It is manganese source, the LiMn prepared using same process2O4Compare, LiMn2O4Formation it is relatively easy,
Therefore with Mn3O4Synthesis LiMn2O4Gradually it is taken seriously.With Mn3O4It is manganese source, LiMn is prepared using solid reaction process2O4Technique
Flow is as follows：
With Mn3O4、Li2O3Be raw material, absolute ethyl alcohol is dispersant ground and mixed, after 600 DEG C of pre-burning 6h, as crucible in,
Then crucible is placed in Muffle furnace calcination reaction 30h at 750 DEG C, afterwards, 600 DEG C of annealing 6h can obtain after furnace cooling
LiMn2O4Material.
Beneficial effects of the present invention：
1st, in the conventional method for preparing mangano-manganic oxide, to ensure the appearance luster and performance of electrolytic manganese metal piece,
Need to generally chromating treatment be carried out to the manganese metal piece being electrolysed out, and after passivation technology before processing, electrolytic manganese metal piece
Top layer chromium content can increase to 80ppm or so by 20ppm.The method of the present invention cancels surface blunt after the preparation of electrolytic manganese metal piece
Chemical industry skill, is directly applied to using unpassivated electrolytic manganese metal piece and prepares mangano-manganic oxide product, can be prevented effectively from chromium from
The intake of the harmful ions such as son, can avoid the increasing chromium problem in passivating process.
2nd, in the metal smelting process of the water atomization technique of the inventive method, smelting temperature is arranged on 1250-1350 DEG C, leads to
Technological parameter is overregulated, the low boiling harmful element such as original selenium, sulphur, phosphorus for containing in electrolytic manganese metal piece can be removed, make to be obtained
Mangano-manganic oxide in：The content of selenium element is less than 5ppm, and in 10ppm or so, the content of P elements is less than the content of element sulphur
5ppm, the content of carbon is less than 15ppm.The physical function parameter of part low boiling harmful element is as follows：
Physical function parameter index table
| Mn | Se | S | P | Fe | Cr | |
| Fusing point DEG C | 1244 | 217 | 112.8 | 44.1 | 1535 | 1857 |
| Boiling point DEG C | 1962 | 684.9 | 444.674 | 280 | 2750 | 2672 |
3rd, melting, and the slag making using melting and work of skimming are carried out to manganese metal piece using intermediate frequency furnace in the inventive method
Sequence, slag hitting treatment is carried out using slagging agent, improves melting purity, also can further remove the wherein harmful element such as selenium, sulphur, phosphorus.
4th, in traditional handicraft, electrolytic manganese metal slurry is often obtained using ball mill crushing technique, increases the heavy metals such as iron, chromium unit
The phenomenon of element is serious, has a strong impact on the quality of product, and the method in the present invention prepares electrolytic manganese metal slurry, makes by atomization
The slurry size distribution that must be prepared more is concentrated, and can avoid increasing the content of the heavy metal elements such as iron, chromium, is improved and is produced
The quality of product.
5th, the harmful elements such as iron, chromium, selenium can be avoided using ceramic pipeline in the suspension oxidation technique in the inventive method
Intake, low selenium, low iron, the mangano-manganic oxide product of trace chromium high-quality are prepared, in mangano-manganic oxide obtained in this method：Selenium
The content of element is the content of trace, i.e. chromium less than the content of 0.015%, chromium less than the content of 0.0005%, ferro element
It is hundred a ten thousandths.
6th, the mangano-manganic oxide that the method for the present invention is prepared has purity and complete spinel structure very high, can
Application well is synthetic spinel type LiMn2O4.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the process chart of preparation method of the invention；
Fig. 2 is the X-ray diffraction of the LiMn2O4 product that the mangano-manganic oxide prepared using the method for the present invention is used for production
Collection of illustrative plates；
Fig. 3 is that the spinel structure of the LiMn2O4 synthesized using mangano-manganic oxide obtained in the methods described of embodiment 1 is illustrated
Figure.
Specific embodiment
Below in conjunction with the accompanying drawings and embodiment is further illustrated to invention, but it is not limited to the scope of the present invention.
Embodiment 1
As shown in figure 1, a kind of preparation method of the high-quality mangano-manganic oxide in the present embodiment, specifically includes following step
Suddenly：
A, the surface treatment for not being passivated electrolytic manganese metal piece：
Directly the fresh electrolytic manganese metal piece that is not passivated is cleaned, is dried；
B, electrolytic manganese metal slurry is prepared using water atomization, comprised the following steps：
B1, smelting technology：500KG grades of intermediate frequency will be put into by the electrolytic manganese metal piece that is not passivated after step A surface treatments
Stove carries out melting, and a length of 35 minutes during its melting, smelting temperature is 1250 DEG C；
Slag making and operation of skimming are used in fusion process, is carried out at slag hitting using slagging agent ice crystal in the operation of skimming
Reason, improves melting purity；
Electrolytic manganese metal piece is protected using nitrogen protection air ring also in fusion process, prevents it from aoxidizing；
B2, water smoke chemical conversion slurry：Enter water-filling by water atomization plant is poured into by the manganese metal piece turndown after melting in intermediate frequency furnace
Atomization process, regulation water atomization pressure is 300 kilograms, is formed more widely than to pass through equal to 95% the electrolytic manganese metal slurry of -150 mesh
Material, a length of 10min during turndown；
B3, size mixing：The need for the suspension oxidation reaction solution concentration of rear end, regulation slurry concentration to solid-liquid ratio is 1.6；
C, suspension oxidation reaction：
Obtained electrolytic manganese metal slurry in step B is placed in the reactor on aluminum oxide abrasion resistant ceramic tube road and is suspended
Oxidation reaction, reaction temperature is 50 DEG C；Mixing speed is 220r/min；The blow rate required is 1.8L/min；Reaction time is 20h；
D, centrifugal drying：Mangano-manganic oxide is obtained after the completion of suspension oxidation reaction, through over cleaning, using centrifugal drying technique
After being dehydrated, get product, finished product is tested packaging.
Not passive metal manganese piece in the present embodiment uses DJMnB not passive metal manganese pieces, and DJMnB is electrolytic manganese metal piece
One kind in professional standard, the constituent content requirement in its raw material is as follows：
The DJMnB of table 1.1 not in passive metal manganese piece each element content requirement
After measured, selenium, iron, the content of chromium and common prior art method in mangano-manganic oxide obtained in the present embodiment method
The content balance situation such as following table of selenium, iron, chromium in obtained mangano-manganic oxide：
The content balance situation table of selenium, iron, chromium in mangano-manganic oxide product obtained in the embodiment 1 of table 1.2
| Sequence number | Element type | Ordinary skill is prepared (unit/%) | It is prepared by new technology |
| 1 | Selenium | 0.0015 | 0.0005 |
| 2 | Iron | 0.5 | 0.015 |
| 3 | Chromium | 0.001 | Trace |
After measured, sulphur in mangano-manganic oxide obtained in the present embodiment method, phosphorus, carbon content it is as follows：
Sulphur, phosphorus, the content of carbon in mangano-manganic oxide product obtained in the embodiment 1 of table 1.3
| Sequence number | Element type | Content (unit/ppm) |
| 1 | Sulphur | 10 |
| 2 | Phosphorus | 5 |
| 3 | Carbon | 15 |
Embodiment 2
The present embodiment is with the difference of embodiment 1：
A length of 40 minutes during its melting, smelting temperature is 1350 DEG C；
Electrolytic manganese metal piece is protected using argon gas protection air ring also in fusion process, prevents it from aoxidizing；
Regulation water atomization pressure is 400 kilograms；A length of 12min during turndown；
Regulation slurry concentration to solid-liquid ratio is 2.0；
The reaction temperature of suspension oxidation reaction is 70 DEG C；Mixing speed is 260r/min；The blow rate required is 2.2L/min；Reaction
Time is 24h；
After measured, selenium, iron, the content of chromium and common prior art method in mangano-manganic oxide obtained in the present embodiment method
The content balance situation such as following table of selenium, iron, chromium in obtained mangano-manganic oxide：
The content balance situation table of selenium, iron, chromium in the mangano-manganic oxide product of 2.1 embodiment of table 2
| Sequence number | Element type | Ordinary skill is prepared (unit/%) | It is prepared by new technology |
| 1 | Selenium | 0.0015 | 0.0004 |
| 2 | Iron | 0.5 | 0.015 |
| 3 | Chromium | 0.001 | Trace |
After measured, sulphur in mangano-manganic oxide obtained in the present embodiment method, phosphorus, carbon content it is as follows：
Sulphur, phosphorus, the content of carbon in mangano-manganic oxide product obtained in the embodiment 2 of table 2.2
| Sequence number | Element type | Content (unit/ppm) |
| 1 | Sulphur | 9 |
| 2 | Phosphorus | 4 |
| 3 | Carbon | 15 |
Embodiment 3
The present embodiment is with the difference of embodiment 1：
A length of 38 minutes during its melting, smelting temperature is 1300 DEG C；
Regulation water atomization pressure is 350 kilograms；A length of 11min during turndown；
Regulation slurry concentration to solid-liquid ratio is 1.8；
The reaction temperature of suspension oxidation reaction is 60 DEG C；Mixing speed is 240r/min；The blow rate required is 2.0L/min；Reaction
Time is 22h；
The content balance situation table of selenium, iron, chromium in the mangano-manganic oxide product of 3.1 embodiment of table 3
| Sequence number | Element type | Ordinary skill is prepared (unit/%) | It is prepared by new technology |
| 1 | Selenium | 0.0015 | 0.0003 |
| 2 | Iron | 0.5 | 0.012 |
| 3 | Chromium | 0.001 | Trace |
After measured, sulphur in mangano-manganic oxide obtained in the present embodiment method, phosphorus, carbon content it is as follows：
Sulphur, phosphorus, the content of carbon in mangano-manganic oxide product obtained in the embodiment 3 of table 3.2
| Sequence number | Element type | Content (unit/ppm) |
| 1 | Sulphur | 8 |
| 2 | Phosphorus | 4 |
| 3 | Carbon | 12 |
Embodiment 4
The present embodiment is using Mn obtained in the methods described of embodiment 13O4It is manganese source, is prepared using solid reaction process
LiMn2O4Material, technological process is as follows：
With obtained Mn in above-described embodiment 13O4、Li2O3It is raw material, is dispersant ground and mixed, 600 with absolute ethyl alcohol
After DEG C pre-burning 6h, as crucible in, crucible is then placed in Muffle furnace calcination reaction 30h at 750 DEG C, afterwards, 600 DEG C of annealing
6h, LiM is can obtain after furnace coolingn2O4Material.
After measured：Obtained LiMn2O4Material, its D50 is 4.80 μm, and specific surface area is 1.0 ㎡/g, and its crystal grain is regular
Octahedron and size uniformity, 2.1 μm or so are concentrated on, with the LiMn prepared with electrolytic manganese dioxide2O4Compare, its crystal grain compared with
It is small but size is more homogeneous.
Gained LiMn2O4 initial discharge specific capacity at 25 DEG C and 50 DEG C is 135mAh/g and 136mAh/g, is followed for 10 times
Capability retention is 97.8%, 94.9% after ring.
As shown in Fig. 2 the lithium manganate having spinel structure material synthesized using mangano-manganic oxide obtained in the methods described of embodiment 1
Characteristic peak it is consistent with the standard diagram JCPDS35-0782 of LiMn2O4, without display any impurity peak.
As shown in figure 3, there is rule using the lithium manganate material that mangano-manganic oxide obtained in the methods described of embodiment 1 synthesizes
Spinel structure.
Above-described embodiment is further illustrated to of the invention, rather than limitation the scope of the present invention.The present invention is not departed from
Whole technical scope, various modifications and changes can be carried out.
Claims (3)
1. a kind of preparation method of high-quality mangano-manganic oxide, it is characterised in that
Not to be passivated electrolytic manganese metal piece it is raw material for one kind, electrolytic manganese metal slurry is prepared using water atomization, then by electricity
Solution manganese metal slurry suspension oxidation reaction is obtained low selenium, low iron, the preparation method of trace chromium high-quality mangano-manganic oxide；
The preparation method specifically includes following steps：
A, the surface treatment for not being passivated electrolytic manganese metal piece：
Directly the fresh electrolytic manganese metal piece that is not passivated is cleaned, is dried；
B, electrolytic manganese metal slurry is prepared using water atomization, comprised the following steps：
B1, smelting technology：To be put into 500KG grades of intermediate frequency furnace by the electrolytic manganese metal piece that is not passivated after step A surface treatments
Melting is carried out, a length of 35-40 minutes during its melting, smelting temperature is 1250-1350 DEG C；
B2, water smoke chemical conversion slurry：Carried out water atomization plant is poured into by the manganese metal piece turndown after melting in 500KG grades of intermediate frequency furnace
Water atomization is processed, and regulation water atomization pressure is 300-400 kilograms, a length of 10-12min during turndown, using inert gas shielding gas
Circle is protected to electrolytic manganese metal piece, prevents it from aoxidizing；The inert gas uses nitrogen or argon gas；
Water smoke chemical conversion slurry is formed more widely than to pass through equal to 95% the electrolytic manganese metal slurry of -150 mesh；
B3, size mixing：The need for the suspension oxidation reaction solution concentration of rear end, regulation slurry concentration to solid-liquid ratio is 1.6-2.0；
C, suspension oxidation reaction：
Obtained electrolytic manganese metal slurry in step B is placed in carries out suspension oxidation reaction in ceramic pipeline reactor, inject ammonia
Water makees catalyst, is passed through air, and reaction temperature is 50-70 DEG C；Mixing speed is 220-260r/min；The blow rate required is 1.8-
2.2L/min；Reaction time is 20-24h；
D, centrifugal drying：Mangano-manganic oxide is obtained after the completion of suspension oxidation reaction, through over cleaning, is carried out using centrifugal drying technique
After dehydrating, get product；
In the not passive metal manganese piece：Mn >=99.9%；C≤0.02%；S≤0.04%；P≤0.002%；Si≤
0.004%；Se≤0.001%；Fe≤0.01%；
The slag making also including melting and operation of skimming, are entered in the operation of skimming using slagging agent in the step B1 smelting technologies
Row slag hitting is processed, and improves melting purity；
The finished product mangano-manganic oxide has a complete spinel structure, and Se elements content≤0.0005%；Fe elements
Content≤0.015%；The content of chromium is trace；The content of S elements is 8-12ppm, the content ＜ 5ppm of P element, C element
Content ＜ 15ppm.
2. a kind of using mangano-manganic oxide obtained in preparation method described in claim 1, it is characterised in that
The mangano-manganic oxide product has complete spinel structure, in the mangano-manganic oxide：
Content≤0.0005% of Se elements；Content≤0.015% of Fe elements；The content of chromium is trace；
The content of S elements is 8-12ppm, the content ＜ 5ppm of P element, the content ＜ 15ppm of C element.
3. the lithium manganate material that mangano-manganic oxide obtained in preparation method described in a kind of use claim 1 synthesizes, its feature exists
In specific preparation method is as follows：
With Mn3O4、Li2O3It is raw material, absolute ethyl alcohol is dispersant ground and mixed, after 600 DEG C of pre-burning 6h, is placed in crucible, then
Crucible is placed in Muffle furnace calcination reaction 30h at 750 DEG C, afterwards, 600 DEG C of annealing 6h can obtain after furnace cooling
LiMn2O4Material.
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