CN107381646A - The method that mangano-manganic oxide is prepared using acid-soluble manganese ore circulated based on sulphur, ammonia - Google Patents

The method that mangano-manganic oxide is prepared using acid-soluble manganese ore circulated based on sulphur, ammonia Download PDF

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CN107381646A
CN107381646A CN201710558865.3A CN201710558865A CN107381646A CN 107381646 A CN107381646 A CN 107381646A CN 201710558865 A CN201710558865 A CN 201710558865A CN 107381646 A CN107381646 A CN 107381646A
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manganese
ammonia
mangano
sulfate
ammonium
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CN107381646B (en
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孙维义
苏仕军
丁桑岚
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Sichuan University
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Sichuan University
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00Compounds of manganese
    • C01G45/02Oxides; Hydroxides

Abstract

The present invention provides the method that mangano-manganic oxide is prepared using acid-soluble manganese ore circulated based on sulphur, ammonia:(1) leach;(2) purification and impurity removal;(3) heavy manganese:Ammoniacal liquor and oxidant are added in gained manganese sulfate solution, manganous hydroxide is converted into mangano-manganic oxide;(4) separation of solid and liquid;(5) evaporative crystallization (6) is dried;(7) ammonium sulfate is pyrolyzed:Gained ammonia sulfate crystal is pyrolyzed, obtains ammonium hydrogen sulfate crystal and ammonia;(8) ammonium hydrogen sulfate circulates:Gained ammonium hydrogen sulfate crystal is soluble in water, ammonium bisulfate solution is obtained, returns it into step (1) as the manganese in leaching agent leaching manganese ore;(9) ammonia recycle:Gained ammonia water is absorbed after being prepared into ammoniacal liquor, return to step (2) and/or step (3) are used as nertralizer.The inventive method can be realized mangano-manganic oxide is prepared to manganese sulphate solution phase oxidation during caused ammonium sulfate recycle, solve ammonium sulfate and be difficult to the problem of recycling.

Description

The method that mangano-manganic oxide is prepared using acid-soluble manganese ore circulated based on sulphur, ammonia
Technical field
It is more particularly to a kind of to utilize acid-soluble manganese ore the invention belongs to the recycling field that manganese ore prepares Mn oxide The method for preparing mangano-manganic oxide.
Background technology
Mangano-manganic oxide is important magnetic material, is the quality raw materials of soft magnetic ferrite and new-energy automobile lithium battery. At present, the production method of mangano-manganic oxide mainly has two kinds:(1) manganese sulfate or manganese carbonate high-temperature decomposition;(2) electrolytic manganese or sulphur Sour manganese solution liquid phase oxidation.Wherein, manganese sulphate solution phase oxidation has that cost is relatively low, the advantage such as easily operated is taken seriously. Preparing mangano-manganic oxide using manganese sulphate solution phase oxidation includes following three steps:(1) leached using the solution containing sulfuric acid Pyrolusite after manganese carbonate ore or roasting reduction, obtain primary manganese sulfate leachate;(2) purification and impurity removal is removed in leachate Impurity element obtain qualified manganese sulfate solution;(3) ammoniacal liquor or sodium hydroxide are added in qualified manganese sulfate solution, is hydrolyzed to hydrogen Manganese oxide, and add oxidant and be allowed to be oxidized to mangano-manganic oxide.Mangano-manganic oxide process is prepared in manganese sulphate solution phase oxidation In, when using ammoniacal liquor as nertralizer, substantial amounts of ammonium sulfate can be produced, due to containing a small amount of in the solution Manganese, such as used as nitrogenous fertilizer, easily cause heavy metal pollution of soil, therefore, it is difficult to later use.And at present due to changing Fertile production capacity surplus causes ammonium sulfate price persistently to reduce, low in economic efficiency, carrys out its exploitation value by later use object of nitrogenous fertilizer Value is little.How in the preparation process of mangano-manganic oxide recycling for ammonium sulfate in system is realized therefore, it is necessary to study.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of base sulphur, the acid-soluble manganese of utilization of ammonia circulation The method that ore deposit prepares mangano-manganic oxide, realize and caused ammonium sulfate during mangano-manganic oxide is prepared to manganese sulphate solution phase oxidation Recycle, solve ammonium sulfate and be difficult to the problem of recycling.
For above goal of the invention, the present invention is provided the acid-soluble manganese ore of utilization circulated based on sulphur, ammonia and prepares four oxidations three The method of manganese, is comprised the following steps that:
(1) leach:It is with slurry as leaching agent and acid-soluble manganese ore using ammonium bisulfate solution, it is converted into the manganese in manganese ore solvable Property manganese sulfate, by gained slurries carry out separation of solid and liquid, obtain waste residue and the leachate containing manganese sulfate;
(2) purification and impurity removal:By leachate obtained by step (1) successively neutralized iron removal by oxidation aluminium, vulcanization removing heavy metals, fluorination Manganese sulfate solution is obtained after removing calcium and magnesium;
(3) heavy manganese:Ammoniacal liquor is added in manganese sulfate solution obtained by step (2), manganese sulfate is converted into manganous hydroxide, then add Enter oxidant, manganous hydroxide is converted into mangano-manganic oxide, obtain the slurries of the precipitation containing mangano-manganic oxide;
(4) separation of solid and liquid:Slurries obtained by step (3) are subjected to separation of solid and liquid, mangano-manganic oxide is obtained and contains ammonium sulfate Separating liquid;
(5) evaporative crystallization:By the separating liquid evaporative crystallization containing ammonium sulfate obtained by step (4), ammonia sulfate crystal is obtained;
(6) dry:Mangano-manganic oxide obtained by step (4) is dried, obtains mangano-manganic oxide product;
(7) ammonium sulfate is pyrolyzed:Ammonia sulfate crystal obtained by step (5) is pyrolyzed, obtains ammonium hydrogen sulfate crystal and ammonia;
(8) ammonium hydrogen sulfate circulates:Ammonium hydrogen sulfate crystal obtained by step (7) is soluble in water, ammonium bisulfate solution is obtained, will Its return to step (1) leaches the manganese in manganese ore as leaching agent;
(9) ammonia recycle:Ammonia water obtained by step (8) is absorbed after being prepared into ammoniacal liquor, return to step (2) and/or step Suddenly (3) are used as nertralizer.
In the above-mentioned technical proposal of the present invention, step (1) the acid-soluble manganese ore is manganese carbonate ore (MnCO3), soft manganese The manganese oxide ore (MnO) of ore deposit after carrying out reduction etc. can directly utilize the manganese ore of sulfuric acid leaching, the chemical reaction that leaching process is occurred For:
MnCO3+2NH4HSO4=MnSO4+(NH4)2SO4+H2O+CO2
MnO+2NH4HSO4=MnSO4+(NH4)2SO4+H2O
Fully to leach the manganese in manganese ore, mole of manganese in the ammonium hydrogen sulfate and manganese ore in step (1) ammonium bisulfate solution Than preferably (2~4):1.
In the above-mentioned technical proposal of the present invention, step (2) is described to neutralize iron removal by oxidation aluminium, is by adding into leachate Enter air or hydrogen peroxide, make Fe2+It is oxidized to Fe3+, and it is 5~7 to add ammoniacal liquor regulation pH, makes Fe3+It is converted into Fe (OH)3Precipitation, Make Al in leachate simultaneously3+It is converted into Al (OH)3Precipitate, Fe (OH) is obtained after separation of solid and liquid3、Al(OH)3Precipitation and separating liquid. Further purification, vulcanization removing heavy metals are the heavy-metal ion removals by adding ammonium sulfide into the separating liquid after iron removaling aluminium, Separation of solid and liquid obtains vulcanized slag and separating liquid.Further purify, removing calcium and magnesium is added in the separating liquid after removing heavy metals Ammonium fluoride, deliming, magnesium are removed, precipitated after separation of solid and liquid and manganese sulfate solution.
In the above-mentioned technical proposal of the present invention, the addition of ammoniacal liquor should meet to make solution ph maintain 8 in step (3) ~10, so that the manganese sulfate in solution is fully converted into manganous hydroxide.Oxidant may be selected from air, oxygen, hydrogen peroxide, ozone One or more.Chemical reaction in step (3) is:
In the above-mentioned technical proposal of the present invention, the pyrolysis temperature range of step (8) described ammonium sulfate is preferably 253~ 350 DEG C, the chemical reaction occurred in the pyrolytic process of ammonium sulfate is:
In the above-mentioned technical proposal of the present invention, preferably by after caused water vapor condensation in crystallization process in step (5) Obtain condensed water and be used for mangano-manganic oxide precipitation obtained by washing step (4), pure mangano-manganic oxide and washings are obtained, by gained Washings are used for dissolving ammonium hydrogen sulfate crystal in step (8), realize recycling for water.
Compared with prior art, the present invention has following very prominent advantageous effects:
1st, process of the present invention, it is that the ammonium bisulfate solution leaching acid prepared using self-produced ammonium sulfate pyrolysis is molten Property manganese ore in manganese, by the use of ammonium sulfate pyrolysis prepare ammonia as nertralizer precipitation leachate in manganese sulfate, constitute sulphur, The close circulation technology of ammonia, in the case where not consuming sulfuric acid (ammonium hydrogen sulfate) and ammonia, realize the recycling of manganese in manganese ore Utilize, while realize ammonium sulfate recycling, solve manganese sulphate solution phase oxidation and prepare sulphur during mangano-manganic oxide Sour ammonium is difficult to the problem of recycling, avoids the outer row of byproduct of ammonium sulfate, reduces the environmental hazard of producing ammonium sulfate byproduct, simultaneously Purchasing for manganese ore leaching agent sulfuric acid and nertralizer ammoniacal liquor is reduced, there is environmental protection and economic double dominant.
2nd, the pyrolysis of ammonium sulfate is controlled and carried out in a low temperature of 253~350 DEG C by technique of the present invention, is pyrolyzed reducing While energy consumption, the loss of sulphur, ammonia during high temperature pyrolysis is avoided, has operating cost, sulphur and ammonia comprehensive utilization ratio high Advantage.
Brief description of the drawings
Fig. 1 is the process chart of the present invention.
Embodiment
With reference to process chart and by embodiment, the present invention is described in further detail, it is necessary to points out It is that following embodiment is served only for that the present invention is described further, it is impossible to limiting the scope of the invention is interpreted as, Art is skillful at personnel according to foregoing invention content, and some nonessential modifications and adaptations are made to the present invention and are had Body is implemented, and should still fall within protection scope of the present invention.
Embodiment 1
Mangano-manganic oxide is prepared using manganese carbonate ore, concrete technology step is as follows:
(1) leach:It is with slurry with manganese carbonate ore by the use of ammonium bisulfate solution as leaching agent, in ammonium hydrogen sulfate and manganese carbonate ore The mol ratio of manganese is 3:1, make manganese ore manganese be converted into solubility manganese sulfate, by gained slurries carry out press filtration, obtain waste residue with Separating liquid containing manganese sulfate;
(2) purification and impurity removal:Air is passed through in separating liquid obtained by step (1), make the Fe in leachate2+It is oxidized to Fe3+, And it is 5.5 to add ammoniacal liquor regulation pH, is allowed to be converted into Fe (OH)3Precipitation, while Al in leachate3+It is converted into Al (OH)3Precipitation, Fe (OH) is obtained after separation of solid and liquid3、Al(OH)3Precipitation and separating liquid;Ammonium sulfide is added in gained separating liquid, removes removing heavy metals Ion, separation of solid and liquid obtain vulcanized slag and separating liquid;Ammonium fluoride is added in gained separating liquid, removes removing calcium and magnesium, after separation of solid and liquid Obtain precipitation and qualified manganese sulfate solution.
(3) heavy manganese:Ammoniacal liquor is added in qualified manganese sulfate solution is contained obtained by step (2), regulation pH is 8.5, makes sulfuric acid Manganese is converted into manganous hydroxide, and is passed through air, manganous hydroxide is converted into mangano-manganic oxide, obtains precipitating containing mangano-manganic oxide Slurries.
(4) separation of solid and liquid:By slurries obtained by step (3) and centrifuged, obtain mangano-manganic oxide precipitation and ammonium sulfate point Chaotropic.
(5) evaporative crystallization:By the evaporative crystallization at 95 DEG C of the separating liquid containing ammonium sulfate ammonium obtained by step (4), sulphur is obtained Sour ammonium crystal, condensed water is obtained after water vapor condensation.
(6) wash:By mangano-manganic oxide precipitation obtained by condensation water wash step (4) obtained by step (5), pure four oxygen is obtained Change three manganese and washings.
(7) dry:Mangano-manganic oxide obtained by step (6) is dried into 2h at 105 DEG C, obtains mangano-manganic oxide product.
(8) ammonium sulfate is pyrolyzed:Ammonia sulfate crystal obtained by step (5) is pyrolyzed at 300 DEG C, obtain ammonium hydrogen sulfate solid and Ammonia.
(9) ammonium hydrogen sulfate circulates:By step (8) ammonium hydrogen sulfate solid be dissolved in washings obtained by step (6), obtain Ammonium bisulfate solution, step (1) is returned it into as the manganese in leaching agent leaching manganese ore.
(10) ammonia recycle:Ammonia obtained by step (8) is absorbed with water, the ammoniacal liquor that concentration is 30% is obtained, by gained ammonia Water return to step (2) and (3) are used as nertralizer, and precipitation is removed in the iron aluminium and sulfate precipitate manganese solution in manganese sulfate solution respectively Manganese.
Embodiment 2
Manganese oxide ore after sharp pyrolusite reduction prepares mangano-manganic oxide, and its operating procedure is as follows:
(1) leach:With slurry, ammonium hydrogen sulfate and manganese ore by the use of ammonium bisulfate solution as leaching agent and the manganese oxide ore after original The mol ratio of middle manganese is 2.5:1, the manganese of manganese ore is converted into the manganese sulfate of solubility, and gained slurries are centrifuged, obtain Waste residue and the separating liquid containing manganese sulfate.
(2) purification and impurity removal:Hydrogen peroxide is added in separating liquid obtained by step (1), make the Fe in leachate2+It is oxidized to Fe3+, and it is 6.0 to add ammoniacal liquor regulation pH, is allowed to be converted into Fe (OH)3Precipitation, while Al in leachate3+It is converted into Al (OH)3 Precipitate, Fe (OH) is obtained after separation of solid and liquid3、Al(OH)3Precipitation and separating liquid;Ammonium sulfide is added in gained separating liquid, removes weight Metal ion, it is centrifugally separating to obtain vulcanized slag and separating liquid;Ammonium fluoride is added in gained separating liquid, removing calcium and magnesium is removed, after filtering Obtain precipitation and qualified manganese sulfate solution.
(3) heavy manganese:Ammoniacal liquor is added in qualified manganese sulfate solution is contained obtained by step (2), manganese sulfate is converted into hydrogen-oxygen Change manganese, and add hydrogen peroxide, be allowed to be converted into mangano-manganic oxide, obtain the slurries containing mangano-manganic oxide precipitation.
(4) separation of solid and liquid:Slurry obtained by step (3) is centrifuged, mangano-manganic oxide precipitation is obtained and contains sulfuric acid The separating liquid of ammonium.
(5) evaporative crystallization:By the evaporative crystallization at 98 DEG C of the separating liquid containing ammonium sulfate obtained by step (4), sulfuric acid is obtained Ammonium crystal, condensed water is obtained after water vapor condensation;
(6) wash:By mangano-manganic oxide precipitation obtained by condensation water wash step (4) obtained by step (5), pure four oxygen is obtained Change three manganese and washings;
(7) dry:By mangano-manganic oxide obtained by step (6) in 110 DEG C of dry 2h, mangano-manganic oxide product is obtained.
(8) ammonium sulfate is pyrolyzed:Ammonia sulfate crystal obtained by step (5) is pyrolyzed 3h at 280 DEG C, obtains ammonium hydrogen sulfate solid And ammonia.
(9) ammonium hydrogen sulfate circulates:By step (8) ammonium hydrogen sulfate solid be dissolved in washings obtained by step (6), obtain Ammonium bisulfate solution, step (1) is returned it into as the manganese in leaching agent leaching manganese ore.
(10) ammonia recycle:Ammonia obtained by step (8) is absorbed with water, the ammoniacal liquor that concentration is 25% is obtained, gained is returned Return step (2) and (3) are used as nertralizer, precipitation removes the manganese in the iron and sulfate precipitate manganese solution in manganese sulfate solution respectively.

Claims (10)

1. the method that mangano-manganic oxide is prepared using acid-soluble manganese ore circulated based on sulphur, ammonia, it is characterised in that including following work Skill step:
(1) leach:It is with slurry as leaching agent and acid-soluble manganese ore using ammonium bisulfate solution, the manganese in manganese ore is converted into solubility Manganese sulfate, gained slurries are subjected to separation of solid and liquid, obtain waste residue and the leachate containing manganese sulfate;
(2) purification and impurity removal:By leachate obtained by step (1) successively neutralized iron removal by oxidation aluminium, vulcanization removing heavy metals, fluorination deliming Manganese sulfate solution is obtained after magnesium;
(3) heavy manganese:Ammoniacal liquor is added in manganese sulfate solution obtained by step (2), manganese sulfate is converted into manganous hydroxide, adds oxygen Agent, manganous hydroxide is converted into mangano-manganic oxide, obtain the slurries of the precipitation containing mangano-manganic oxide;
(4) separation of solid and liquid:Slurries obtained by step (3) are subjected to separation of solid and liquid, obtain mangano-manganic oxide and point containing ammonium sulfate Chaotropic;
(5) evaporative crystallization:By the separating liquid evaporative crystallization containing ammonium sulfate obtained by step (4), ammonia sulfate crystal is obtained;
(6) dry:Mangano-manganic oxide obtained by step (4) is dried, obtains mangano-manganic oxide product;
(7) ammonium sulfate is pyrolyzed:Ammonia sulfate crystal obtained by step (5) is pyrolyzed, obtains ammonium hydrogen sulfate crystal and ammonia;
(8) ammonium hydrogen sulfate circulates:Ammonium hydrogen sulfate crystal obtained by step (7) is soluble in water, ammonium bisulfate solution is obtained, is returned Step (1) is returned as the manganese in leaching agent leaching manganese ore;
(9) ammonia recycle:Ammonia water obtained by step (8) is absorbed after being prepared into ammoniacal liquor, return to step (2) and/or step (3) As nertralizer.
2. the method that mangano-manganic oxide is prepared using acid-soluble manganese ore circulated according to claim 1 based on sulphur, ammonia, it is special Sign is that step (1) the acid-soluble manganese ore is the manganese oxide ore of manganese carbonate ore or pyrolusite after carrying out reduction.
3. the method that mangano-manganic oxide is prepared using acid-soluble manganese ore circulated according to claim 1 based on sulphur, ammonia, it is special Sign is that the mol ratio of manganese in ammonium hydrogen sulfate and manganese ore in step (1) ammonium bisulfate solution is (2~4):1.
4. the method that mangano-manganic oxide is prepared using acid-soluble manganese ore circulated according to claim 1 based on sulphur, ammonia, it is special Sign is that step (2) the iron removal by oxidation aluminium that neutralizes is by adding air or hydrogen peroxide into leachate, making Fe2+It is oxidized to Fe3+, and it is 5~7 to add ammoniacal liquor regulation pH, makes Fe3+It is converted into Fe (OH)3Precipitation, while make Al in leachate3+It is converted into Al (OH)3Precipitate, Fe (OH) is obtained after separation of solid and liquid3、Al(OH)3Precipitation and separating liquid.
5. the method that mangano-manganic oxide is prepared using acid-soluble manganese ore circulated according to claim 4 based on sulphur, ammonia, it is special Sign is that step (2) the vulcanization removing heavy metals are that ammonium sulfide is added into the separating liquid after iron removaling aluminium, heavy-metal ion removal, Separation of solid and liquid obtains vulcanized slag and separating liquid.
6. the method that mangano-manganic oxide is prepared using acid-soluble manganese ore circulated according to claim 5 based on sulphur, ammonia, it is special Sign is that step (2) described removing calcium and magnesium is to add ammonium fluoride in the separating liquid after removing heavy metals, goes deliming, magnesium, separation of solid and liquid After precipitated and manganese sulfate solution.
7. four oxygen are prepared based on the acid-soluble manganese ore of utilization that sulphur, ammonia circulate according to any claim in claim 1~6 Change the method for three manganese, it is characterised in that in step (3) addition of ammoniacal liquor be can make manganous hydroxide generate after pH value of solution 8~ 10 scopes.
8. four oxygen are prepared based on the acid-soluble manganese ore of utilization that sulphur, ammonia circulate according to any claim in claim 1~6 Change the method for three manganese, it is characterised in that the oxidant in step (3) is selected from air, oxygen, hydrogen peroxide and ozone.
9. four oxygen are prepared based on the acid-soluble manganese ore of utilization that sulphur, ammonia circulate according to any claim in claim 1~6 Change the method for three manganese, it is characterised in that the pyrolysis temperature range of step (7) described ammonium sulfate is 253~350 DEG C.
10. prepare four based on the acid-soluble manganese ore of utilization that sulphur, ammonia circulate according to any claim in claim 1~6 The method of Mn 3 O, it is characterised in that by caused water vapor condensation in crystallization process in step (5), obtained condensed water is used In mangano-manganic oxide precipitation obtained by washing step (4), pure mangano-manganic oxide and washings are obtained, gained washings are used to walk Suddenly dissolving ammonium hydrogen sulfate crystal in (8), realizes recycling for water.
CN201710558865.3A 2017-07-11 2017-07-11 The method for preparing mangano-manganic oxide using acid-soluble manganese ore recycled based on sulphur, ammonia Active CN107381646B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1644513A (en) * 2004-12-28 2005-07-27 北京科技大学 Direct production of electron grade high purity trimangnese tetraoxide from ores
CN102134101A (en) * 2011-04-29 2011-07-27 金瑞新材料科技股份有限公司 Method for preparing trimanganese tetroxide by using rhodochrosite
CN104528786A (en) * 2014-12-15 2015-04-22 沈阳工业大学 Method for producing aluminum oxide by treating low-grade bauxite with ammonia-alkali combination method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1644513A (en) * 2004-12-28 2005-07-27 北京科技大学 Direct production of electron grade high purity trimangnese tetraoxide from ores
CN102134101A (en) * 2011-04-29 2011-07-27 金瑞新材料科技股份有限公司 Method for preparing trimanganese tetroxide by using rhodochrosite
CN104528786A (en) * 2014-12-15 2015-04-22 沈阳工业大学 Method for producing aluminum oxide by treating low-grade bauxite with ammonia-alkali combination method

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