CN102660756B - High-purity manganese metal and preparation method thereof - Google Patents
High-purity manganese metal and preparation method thereof Download PDFInfo
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- CN102660756B CN102660756B CN201210168223.XA CN201210168223A CN102660756B CN 102660756 B CN102660756 B CN 102660756B CN 201210168223 A CN201210168223 A CN 201210168223A CN 102660756 B CN102660756 B CN 102660756B
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 75
- 239000012065 filter cake Substances 0.000 claims abstract description 42
- 239000000706 filtrate Substances 0.000 claims abstract description 41
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 40
- 238000004073 vulcanization Methods 0.000 claims abstract description 40
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 239000011572 manganese Substances 0.000 claims abstract description 38
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 33
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 33
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 19
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 12
- 230000020477 pH reduction Effects 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000005868 electrolysis reaction Methods 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000779 smoke Substances 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000010009 beating Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 20
- 239000011575 calcium Substances 0.000 abstract description 12
- 239000011777 magnesium Substances 0.000 abstract description 12
- 239000000047 product Substances 0.000 abstract description 12
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052791 calcium Inorganic materials 0.000 abstract description 9
- 150000002500 ions Chemical class 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 69
- 229910052748 manganese Inorganic materials 0.000 description 21
- 238000003756 stirring Methods 0.000 description 15
- 238000001914 filtration Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000002002 slurry Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- 238000003912 environmental pollution Methods 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000004945 emulsification Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- 238000006386 neutralization reaction Methods 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- 229910001316 Ag alloy Inorganic materials 0.000 description 4
- BKOSYCMBHPGYEN-UHFFFAOYSA-H C([O-])([O-])=O.[Ba+2].[C+4].C([O-])([O-])=O.C([O-])([O-])=O Chemical compound C([O-])([O-])=O.[Ba+2].[C+4].C([O-])([O-])=O.C([O-])([O-])=O BKOSYCMBHPGYEN-UHFFFAOYSA-H 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000007792 addition Methods 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- 238000001636 atomic emission spectroscopy Methods 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 206010065042 Immune reconstitution inflammatory syndrome Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to a high-purity manganese metal and a preparation method. The preparation method comprises the following steps of: firstly, carrying out a vulcanization reaction of a manganese sulfate solution with the concentration of 100-350g/L with NH3 gas and H2S gas, wherein the pH value of a reaction solution in the vulcanization reaction is 5.5-6.5; secondly, stopping the vulcanization reaction when Mn<2+> in the reaction solution when is smaller than 200ppm,and separating solid from liquid to obtain a filter cake; thirdly, washing the filter cake, acidifying with a sulfuric acid containing solution and carrying out solid-liquid separation to obtain filtrate; and fourthly, electrolyzing the filtrate to obtain manganese metal. According to the invention, foreign ions such as calcium and magnesium are separated in a vulcanization manner so that the purity of the manganese metal product is higher than 99.99wt%.
Description
Technical field
The present invention relates to a kind of high purity metal manganese and preparation method thereof, concrete, relate to a kind of method that electrolyzing manganese sulfate solution is prepared high purity metal manganese.
Background technology
Current domestic manganese metal annual production has reached more than 100 ten thousand tons, most of manganous carbonate-acidleach-removal of impurities-electrolysis process route that adopts.Manganese carbonate ore grade declines year by year in recent years, contains a large amount of calcium magnesium additions in breeze, therefore causes larger sulfuric acid consumption.Meanwhile, due to the isorrheic restriction of the system that is subject to, cannot carry out washing and recycling to slag, ton metal manganese ore consumption in some areas has reached 12t, contains a large amount of manganous sulfates and ammonium sulfate in slag, has reduced the level of resources utilization and has caused larger environmental pollution.The molten reduction of soaking rate of breeze, adds except the materials consumption of potassium operation, has increased production cost, and in circulation fluid, the decline of product quality is carried and caused to a large amount of calcium magnesium additions of enrichment secretly in addition.
Power cell manganese cathode material is the fast development of CoNiMn tertiary cathode material particularly, to high-purity, containing manganic compound, has proposed strict quality requirements, and as important high-purity base mateiral containing manganic compound, the market requirement of high pure metal manganese also increases year by year.
Summary of the invention
Technical problem to be solved by this invention is: overcome existing manganese metal production technique sulfuric acid consumption large, cannot carry out washing and recycling to slag, in slag, contain a large amount of manganous sulfates and ammonium sulfate, the low while contaminate environment of resource utilization, and the high problem of gained manganese metal product foreign matter content, provides manganese metal more than a kind of purity 99.99wt% and preparation method thereof, adopt vulcanization process, the separated foreign ions such as calcium, magnesium, thereby more than the purity that guarantees metal manganese product reaches 99.99wt%; In addition by vulcanization process, solved that existing manganese metal technique need to consume a large amount of sulfuric acid and the water balance problem that exists, thereby be able to vulcanization reaction filter cake effectively to wash, improve manganese resource utilization, and reduced environmental pollution.
The present invention is by manganese sulfate solution and NH
3, H
2s gas carries out vulcanization reaction, and the separated foreign ions such as calcium, magnesium, have omitted except potassium operation, more than the purity of the manganese metal product of gained reaches 99.99wt%.Because the present invention does not need to consume a large amount of sulfuric acid, be therefore able to vulcanization reaction filter cake effectively to wash, reclaimed manganous sulfate and the ammonium sulfate in filter cake, improve manganese resource utilization, and reduced environmental pollution.
Manganese sulfate solution of the present invention is low-grade MnO in preferably passing through
2ore deposit (being 10-30%(weight percent containing Mn)) react generation with sulfur-containing smoke gas, coordinate the operations such as vulcanization reaction, filter cake washing, improve full manganese recovery ratio, made full manganese recovery ratio be increased to 90～93% from 70% left and right of existing technique, reduced production cost.
In order to solve the problems of the technologies described above, the first technical scheme provided by the invention is, the preparation method of manganese metal more than a kind of purity 99.99wt%, and the method comprises: first step, by the manganese sulfate solution of concentration 100～350g/L and NH
3gas and H
2s gas carries out vulcanization reaction, controls the pH value of reaction soln in vulcanization reaction process in 5.5～6.5 scopes; Second step, [Mn in reaction soln
2+] stop vulcanization reaction during < 200ppm, then solid-liquid separation, obtains filter cake; Third step, washs, by vitriolated solution acidifying, solid-liquid separation, processes described filter cake, obtains filtrate; The 4th step, carries out electrolysis to described filtrate, obtains manganese metal.
The present invention's solid-liquid separation used is conventional solid-liquid separation means, and preferred conventional press filtration is separated.
The present invention is to NH
3gas and H
2s gas does not have particular requirement, conventional chemical reaction NH
3gas and H
2s gas all can be applicable to the present invention.Preferably, the present invention NH used
3gas is commercial liquid NH
3the high-purity N H that vaporization obtains
3gas; The present invention H used
2s gas is the high-purity gas that MnS and sulfuric acid reaction generate.NH
3gas and H
2the usage quantity preferred reaction mole of S gas is made a gesture of measuring, to avoid the waste of unstripped gas.
Preferably, in first step, the concentration of described manganese sulfate solution is 250-300g/L.
Preferably, in first step, low-grade MnO during described manganese sulfate solution adopts
2breeze (being 10-30%(weight percent containing Mn)) react generation with sulfur-containing smoke gas.Main reaction equation is as follows:
MnO
2+SO
2→MnSO
4。
Preferably, in first step, described pH value is controlled in the scope of 5.71-6.24.
Preferably, in first step, adopt Multi-stage vulcanization device to carry out vulcanization reaction.Concrete, three grades of vulcanizing plants for example.Every grade of vulcanizing plant is: the mixed gas (NH of reaction mol ratio
3gas and H
2s gas) gas speed control is built in 0.5-4m/sec, average discharge 10000-120000Nm
3/ h, gas-liquid volume ratio example is controlled at 8-10L/m
3.First in the first step of vulcanizing plant, pass into mixed gas, the part that mixed gas is not reacted in first step vulcanizing plant flows into second stage vulcanizing plant, in the vulcanizing plant of the second stage, by reactive moieties, is not flowed into third stage vulcanizing plant, mixed gas and manganese sulfate solution counter current contact in vulcanizing plants at different levels.Adopt conventional pumps feed technique, manganese sulfate solution is pumped to the third stage of vulcanizing plant, and controls it and do countercurrent flow with respect to mixed gas.Three grades of these three grades of vulcanizing plants are carried out separately respectively self-circulation, the first step, the second stage and the third stage, spray manganese sulfate solution downwards respectively, after first step discharging, second stage liquid pumping is to the first step, third stage liquid pumping is to the second stage, and the third stage enters new manganese sulfate solution.The condition of above-mentioned first step discharging is, [Mn in the circulating liquid obtaining in first step vulcanizing plant
2+] after < 200ppm.
In first step, main reaction equation is as follows:
MnSO
4+2NH
3↑+H
2S↑→MnS↓+(NH
4)
2SO
4
MSO
4+ NH
3↑+H
2s ↑ → MS+ (NH
4)
2sO
4wherein (M=Cu, Co, Ni, Pb, As, Cr, Fe etc.)
In first step, control the pH value of reaction soln in vulcanization reaction process in 5.5～6.5 scopes, generated like this MnS precipitation, and the foreign ions such as calcium, magnesium are dissolved in solution, therefore, after solid-liquid separation, reduced foreign matter content.
Preferably, in second step, described solid-liquid separation gained filtrate is produced ammonium sulfate.Concrete, filtrate is multiple-effect evaporation manufacture ammonium sulfate after pre-treatment (such as essence filter, removal of impurities etc.).
Preferably, in third step, described washing is that deionized water is joined in described filter cake, emulsion dispersion at 60-70 ℃, then agitator treating 2.5-3.5 hour (preferably 3 hours), then solid-liquid separation, obtains filter cake.Gained filtrate is low-grade MnO in preferably delivering to
2low-grade MnO in breeze and sulfur-containing smoke gas reactions steps
2breeze making beating step.
Described emulsion dispersion can adopt commercially available conventional emulsification pump to carry out.The add-on of described deionized water to be can fully emulsified washing being as the criterion, the mass ratio that preferably material-water ratio is 1:4.
Because adopting vulcanization reaction, the present invention replaces classical acid soaking technology, do not need to consume a large amount of sulfuric acid, be therefore able to second step gained filter cake fully to wash, the manganous sulfate and the ammonium sulfate that make to remain in filter cake can be recycled, improve manganese resource utilization, reduced environmental pollution.
Preferably, in third step, described acidifying is that the filter cake after carrying out washing treatment is reacted with vitriolated solution, controls the pH value of acidification reaction terminal in 4.0～4.5 scopes.Concrete, due to the water balance requirement in manganese metal production, can not introduce too much water, therefore by the (MnSO obtaining after cake slurry (MnS slurry) and vitriolated solution reaction of small part acidification reaction liquid for the filter cake after carrying out washing treatment
4solution) making beating, dispersed with stirring, obtains cake slurry, then carry out acidification reaction with vitriolated solution (preferably electrolysis mother liquor of the present invention), control the pH value of acidification reaction terminal in 4.0～4.5 scopes, obtain acidification reaction liquid, then acidification reaction solid and liquid is separated, obtain filtrate.Gained filter cake can be for reclaiming valuable metal (Cu, Co, Ni, Pb, As, Cr, Fe etc.).The principal reaction equation of acidification step is as follows:
MnS+H
2SO
4→MnSO
4+H
2S↑
Preferably, in the 4th step, carry out before electrolysis treatment, carry out removal of impurities and solid-liquid separation and process.Described removal of impurities is after acidifying, in gained filtrate, to add a small amount of hydrogen peroxide, be warming up to 75-85 ℃ (preferably 80 ℃) and maintain 25-35 minute (preferably 30 minutes) of stirring, then use a small amount of ammonia neutralization to pH value in 4.0～4.5 scopes, maintain and stir solid-liquid separation after 25-35 minute (preferably 30 minutes), obtain filtrate.
Filtrate after removal of impurities is carried out conventional electrolysis, can obtain 99.99% manganese metal product.The principal reaction equation of electrolysis is as follows:
The second technical scheme provided by the invention is, manganese metal more than a kind of purity 99.99wt% is provided, and adopts aforesaid method to make, and by weight percentage, the content that in this manganese metal, the content of Ca is less than or equal to 0.0013%, Mg is less than or equal to 0.0005%.
Preferably, by weight percentage, the content that the content that the content that in this manganese metal, the content of K is less than or equal to 0.0002%, Na is less than or equal to 0.0006%, Fe is less than or equal to 0.0003%, Si is less than or equal to 0.0003%, and the content of P is less than or equal to 0.0001%.
Adopt technical scheme of the present invention, at least there is following beneficial effect: adopt vulcanization process, the separated foreign ions such as calcium, magnesium, have omitted except potassium operation, and more than the purity of manganese metal product reaches 99.99wt%, the impurity ion content such as calcium, magnesium, potassium are low.Solved that existing manganese metal technique need to consume a large amount of sulfuric acid and the water balance problem that exists, thereby be able to vulcanization reaction filter cake effectively to wash, improved manganese resource utilization, and reduced environmental pollution.
Accompanying drawing explanation
The process flow sheet that Fig. 1 the present invention is main.
Embodiment
For fully understanding the present invention's object, feature and effect, by following concrete embodiment, the present invention is elaborated.
The present invention is by the manganese sulfate solution of proper concn and NH
3, H
2s gas carries out vulcanization reaction, and the separated foreign ions such as calcium, magnesium, have omitted except potassium operation, more than the purity of gained manganese metal product reaches 99.99wt%.Because the present invention does not need to consume a large amount of sulfuric acid, and preferably to technological process water circulation use, be therefore able to vulcanization reaction filter cake effectively to wash, reclaimed manganous sulfate and ammonium sulfate in vulcanization reaction filter cake, improve manganese resource utilization, and reduced environmental pollution.
The preparation method who the invention provides manganese metal more than a kind of purity 99.99wt%, the method comprises: first step, by concentration 100～350g/L, manganese sulfate solution and the NH of preferred 250-300g/L
3gas and H
2s gas carries out vulcanization reaction, controls the pH value of reaction soln in vulcanization reaction process at the preferred 5.71-6.24 of 5.5～6.5() in scope; Second step, [Mn in reaction soln
2+] stop vulcanization reaction during < 200ppm, then solid-liquid separation, obtains filter cake; Third step, washs, by vitriolated solution acidifying, solid-liquid separation, processes described filter cake, obtains filtrate; The 4th step, to described filtrate electrolysis, obtains manganese metal.
The invention provides manganese metal more than a kind of purity 99.99wt%, by weight percentage, the content that in this manganese metal, the content of Ca is less than or equal to 0.0013%, Mg is less than or equal to 0.0005%.
Below by specific embodiment, set forth the enforcement of method of the present invention, one skilled in the art will appreciate that this should not be understood to the restriction to the claims in the present invention scope.
Embodiment
When first, manganese metal preparation process in embodiment below and product are analyzed, determinator and measuring method used is described as follows:
Mn
2+detection method: inductively coupled plasma (ICP) atomic emission spectrometry
Product elemental analysis method: inductively coupled plasma (ICP) atomic emission spectrometry
Mn
2+with product Atomic Absorption SpectrophotometerICP: IRIS Intrepid II XSP type inductively coupled plasma atomic emission spectrometer, U.S. power & light company system;
PH value determinator: PHS-3C type precision acidity meter, Shanghai precision instrumentation company system.
Embodiment 1
Flue gas adopts technical grade barium carbonate carbon reduction rotary kiln tail gas, average tolerance 25000Nm
3/ h, average SO
2content 13400mg/m
3, 170 ℃ of left and right of cyclone dust removal temperature out.In low-grade MnO
2breeze (being 15%(weight percent containing Mn)) adopt the rear filtrate of vulcanization reaction thing washing to pull an oar, obtain slurry, then pass into sulfur-containing smoke gas and react, generate manganese sulfate solution, then its concentration is adjusted to 250g/L.
The manganese sulfate solution of concentration 250g/L is joined in the third stage of three grades of vulcanizing plants.In the first step of three grades of vulcanizing plants, pass into NH
3gas and H
2the mixed gas of S gas, NH
3gas and H
2the molar ratio of S gas is 2:1.In every grade of vulcanizing plant, the gas speed control of mixed gas is built in 2m/sec, average discharge 10000Nm
3/ h, gas-liquid volume ratio example is controlled at 9L/m
3, manganese sulfate solution contacts with mixed gas is reverse in every grade, carries out vulcanization reaction, controls the pH value of reaction soln 5.71 in reaction process.The circulating liquid obtaining in first step vulcanizing plant is measured to [Mn
2+] after < 200ppm, the circulating liquid obtaining in first step vulcanizing plant is discharged.
The liquid of above-mentioned discharge is carried out to press filtration separation, obtain filter cake.The mass ratio that deionized water is 1:4 according to material-water ratio joins in described filter cake, adopts emulsification pump to carry out emulsion dispersion at 63 ℃, and then agitator treating is 3 hours, and then press filtration is separated, obtains filter cake.Filtrate is back to MnO
2breeze is prepared manganese sulfate solution step.
By the small part acidification reaction liquid making beating looping back for the filter cake after carrying out washing treatment, dispersed with stirring, obtains cake slurry, then react with electrolysis mother liquor, control the pH value of acidification reaction terminal 4.2, obtain acidification reaction liquid, then the filter of acidification reaction hydraulic pressure is separated, obtain filtrate.
After acidifying, in gained filtrate, add a small amount of hydrogen peroxide, be warming up to 80 ℃ and maintain and stir 30 minutes, then use a small amount of ammonia neutralization to pH value 4.2, maintain that to stir after 30 minutes press filtration separated, obtain filtrate.
It is 105g/L that this filtrate is diluted to manganous sulfate concentration.Diluent is delivered in electrolyzer, and stainless steel plate is as negative electrode, and plumbous zinc-silver alloy is as anode, and metal refining manganese on negative electrode, obtains sample 1#.
Embodiment 2
Flue gas adopts technical grade barium carbonate carbon reduction rotary kiln tail gas, average tolerance 25000Nm
3/ h, average SO
2content 13400mg/m
3, 170 ℃ of left and right of cyclone dust removal temperature out.In low-grade MnO
2breeze (being 20%(weight percent containing Mn)) adopt the rear filtrate of vulcanization reaction thing washing to pull an oar, obtain slurry, then pass into sulfur-containing smoke gas and react, generate manganese sulfate solution, then its concentration is adjusted to 300g/L.
The manganese sulfate solution of concentration 300g/L is joined in the third stage of three grades of vulcanizing plants.In the first step of three grades of vulcanizing plants, pass into NH
3gas and H
2the mixed gas of S gas, NH
3gas and H
2the molar ratio of S gas is 2:1.In every grade of vulcanizing plant, the gas speed control of mixed gas is built in 2m/sec, average discharge 10000Nm
3/ h, gas-liquid volume ratio example is controlled at 9L/m
3, manganese sulfate solution contacts with mixed gas is reverse in every grade, carries out vulcanization reaction, controls the pH value of reaction soln 6.24 in reaction process.The circulating liquid obtaining in first step vulcanizing plant is measured to [Mn
2+] after < 200ppm, the circulating liquid obtaining in first step vulcanizing plant is discharged.
The liquid of above-mentioned discharge is carried out to press filtration separation, obtain filter cake.The mass ratio that deionized water is 1:4 according to material-water ratio joins in described filter cake, adopts emulsification pump to carry out emulsion dispersion at 68 ℃, and then agitator treating is 3 hours, and then press filtration is separated, obtains filter cake.Filtrate is back to MnO
2breeze is prepared manganese sulfate solution step.
By the small part acidification reaction liquid making beating looping back for the filter cake after carrying out washing treatment, dispersed with stirring, obtains cake slurry, then react with electrolysis mother liquor, control the pH value of acidification reaction terminal 4.4, obtain acidification reaction liquid, then the filter of acidification reaction hydraulic pressure is separated, obtain filtrate.
After acidifying, in gained filtrate, add a small amount of hydrogen peroxide, be warming up to 80 ℃ and maintain and stir 30 minutes, then use a small amount of ammonia neutralization to pH value 4.4, maintain that to stir after 30 minutes press filtration separated, obtain filtrate.
It is 105g/L that this filtrate is diluted to manganous sulfate concentration.Diluent is delivered in electrolyzer, and stainless steel plate is as negative electrode, and plumbous zinc-silver alloy is as anode, and metal refining manganese on negative electrode, obtains sample 2#.
Embodiment 3
Flue gas adopts technical grade barium carbonate carbon reduction rotary kiln tail gas, average tolerance 25000Nm
3/ h, average SO
2content 13400mg/m
3, 170 ℃ of left and right of cyclone dust removal temperature out.In low-grade MnO
2breeze (being 30%(weight percent containing Mn)) adopt the rear filtrate of vulcanization reaction thing washing to pull an oar, obtain slurry, then pass into sulfur-containing smoke gas and react, generate manganese sulfate solution, then its concentration is adjusted to 100g/L.
The manganese sulfate solution of concentration 100g/L is joined in the third stage of three grades of vulcanizing plants.In the first step of three grades of vulcanizing plants, pass into NH
3gas and H
2the mixed gas of S gas, NH
3gas and H
2the molar ratio of S gas is 2:1.In every grade of vulcanizing plant, the gas speed control of mixed gas is built in 2m/sec, average discharge 10000Nm
3/ h, gas-liquid volume ratio example is controlled at 9L/m
3, manganese sulfate solution contacts with mixed gas is reverse in every grade, carries out vulcanization reaction, controls the pH value of reaction soln 5.5 in reaction process.The circulating liquid obtaining in first step vulcanizing plant is measured to [Mn
2+] after < 200ppm, the circulating liquid obtaining in first step vulcanizing plant is discharged.
The liquid of above-mentioned discharge is carried out to press filtration separation, obtain filter cake.The mass ratio that deionized water is 1:4 according to material-water ratio joins in described filter cake, adopts emulsification pump to carry out emulsion dispersion at 60 ℃, and then agitator treating is 2.5 hours, and then press filtration is separated, obtains filter cake.Filtrate is back to MnO
2breeze is prepared manganese sulfate solution step.
By the small part acidification reaction liquid making beating looping back for the filter cake after carrying out washing treatment, dispersed with stirring, obtains cake slurry, then react with electrolysis mother liquor, control the pH value of acidification reaction terminal 4.0, obtain acidification reaction liquid, then the filter of acidification reaction hydraulic pressure is separated, obtain filtrate.
After acidifying, in gained filtrate, add a small amount of hydrogen peroxide, be warming up to 75 ℃ and maintain and stir 30 minutes, then use a small amount of ammonia neutralization to pH value 4.0, maintain that to stir after 30 minutes press filtration separated, obtain filtrate.
It is 105g/L that this filtrate is diluted to manganous sulfate concentration.Diluent is delivered in electrolyzer, and stainless steel plate is as negative electrode, and plumbous zinc-silver alloy is as anode, and metal refining manganese on negative electrode, obtains sample 3#.
Embodiment 4
Flue gas adopts technical grade barium carbonate carbon reduction rotary kiln tail gas, average tolerance 25000Nm
3/ h, average SO
2content 13400mg/m
3, 170 ℃ of left and right of cyclone dust removal temperature out.In low-grade MnO
2breeze (being 10%(weight percent containing Mn)) adopt the rear filtrate of vulcanization reaction thing washing to pull an oar, obtain slurry, then pass into sulfur-containing smoke gas and react, generate manganese sulfate solution, then its concentration is adjusted to 350g/L.
The manganese sulfate solution of concentration 350g/L is joined in the third stage of three grades of vulcanizing plants.In the first step of vulcanizing plant, pass into NH
3gas and H
2the mixed gas of S gas, NH
3gas and H
2the molar ratio of S gas is 2:1.In every grade of vulcanizing plant, the gas speed control of mixed gas is built in 2m/sec, average discharge 10000Nm
3/ h, gas-liquid volume ratio example is controlled at 9L/m
3, manganese sulfate solution contacts with mixed gas is reverse in every grade, carries out vulcanization reaction, controls the pH value of reaction soln 6.5 in reaction process.The circulating liquid obtaining in first step vulcanizing plant is measured to [Mn
2+] after < 200ppm, the circulating liquid obtaining in first step vulcanizing plant is discharged.
The liquid of above-mentioned discharge is carried out to press filtration separation, obtain filter cake.The mass ratio that deionized water is 1:4 according to material-water ratio joins in described filter cake, adopts emulsification pump to carry out emulsion dispersion at 70 ℃, and then agitator treating is 3.5 hours, and then press filtration is separated, obtains filter cake.Filtrate is back to MnO
2breeze is prepared manganese sulfate solution step.
By the small part acidification reaction liquid making beating looping back for the filter cake after carrying out washing treatment, dispersed with stirring, obtains cake slurry, then react with electrolysis mother liquor, control the pH value of acidification reaction terminal 4.5, obtain acidification reaction liquid, then the filter of acidification reaction hydraulic pressure is separated, obtain filtrate.
After acidifying, in gained filtrate, add a small amount of hydrogen peroxide, be warming up to 85 ℃ and maintain and stir 30 minutes, then use a small amount of ammonia neutralization to pH value 4.5, maintain that to stir after 30 minutes press filtration separated, obtain filtrate.
It is 105g/L that this filtrate is diluted to manganous sulfate concentration.Diluent is delivered in electrolyzer, and stainless steel plate is as negative electrode, and plumbous zinc-silver alloy is as anode, and metal refining manganese on negative electrode, obtains sample 4#.
Through ultimate analysis, the results are shown in Table 1.
Table 1
| Project | 1 # | 2 # | 3 # | 4 # |
| K (quality %) | 0.0001 | 0.0001 | 0.0002 | 0.0002 |
| Na (quality %) | 0.0003 | 0.0005 | 0.0006 | 0.0006 |
| Ca (quality %) | 0.0007 | 0.0010 | 0.0011 | 0.0013 |
| Mg (quality %) | 0.0003 | 0.0003 | 0.0004 | 0.0005 |
| Fe (quality %) | 0.0003 | 0.0003 | 0.0003 | 0.0003 |
| Si (quality %) | 0.0003 | 0.0003 | 0.0003 | 0.0003 |
| P (quality %) | 0.0001 | 0.0001 | 0.0001 | 0.0001 |
| Cu | ND | ND | ND | ND |
| Co | ND | ND | ND | ND |
| Ni | ND | ND | ND | ND |
| Pb | ND | ND | ND | ND |
| Zn | ND | ND | ND | ND |
| Cr | ND | ND | ND | ND |
| As | ND | ND | ND | ND |
| Se | ND | ND | ND | ND |
Wherein, ND refers to not detect.
From the results shown in Table 1, the present invention is by manganese sulfate solution and NH
3, H
2s gas carries out vulcanization reaction, the separated foreign ions such as calcium, magnesium, thereby more than the purity of gained manganese metal product reaches 99.99wt%, and the impurity ion content such as calcium, magnesium, potassium is low.Because the present invention does not need to consume a large amount of sulfuric acid, be therefore able to vulcanization reaction filter cake effectively to wash, improve manganese resource utilization, and reduced environmental pollution.The full manganese recovery ratio of dioxide ore for manganese of the present invention is increased to 90～93%, has reduced production cost, has improved the level of resources utilization.
Claims (9)
1. a preparation method for manganese metal more than purity 99.99wt%, the method comprises:
First step, by the manganese sulfate solution of concentration 100～350g/L and NH
3gas and H
2s gas carries out vulcanization reaction, controls the pH value of reaction soln in vulcanization reaction process 5.5～6.5;
Second step, [Mn in reaction soln
2+] stop vulcanization reaction during < 200ppm, then solid-liquid separation, obtains filter cake;
Third step, washs, by vitriolated solution acidifying, solid-liquid separation, processes described filter cake, obtains filtrate;
The 4th step, to described filtrate electrolysis, obtains manganese metal;
Wherein, in third step, described acidifying is that the filter cake after carrying out washing treatment is reacted with vitriolated solution, controls the pH value of acidification reaction terminal in 4.0～4.5 scopes;
Wherein, in first step, adopt Multi-stage vulcanization device to carry out vulcanization reaction.
2. the preparation method of manganese metal more than purity 99.99wt% according to claim 1, is characterized in that, the concentration of described manganese sulfate solution is 250-300g/L.
3. the preparation method of manganese metal more than purity 99.99wt% according to claim 1 and 2, is characterized in that, described manganese sulfate solution adopts MnO
2breeze reacts generation with sulfur-containing smoke gas.
4. the preparation method of manganese metal more than purity 99.99wt% according to claim 1, is characterized in that, in the value of pH described in first step, is controlled in the scope of 5.71-6.24.
5. the preparation method of manganese metal more than purity 99.99wt% according to claim 1, is characterized in that, in second step, described solid-liquid separation gained filtrate is for the production of ammonium sulfate.
6. the preparation method of manganese metal more than purity 99.99wt% according to claim 1, it is characterized in that, in third step, described washing is that deionized water is joined in described filter cake, emulsion dispersion at 60-70 ℃, follow agitator treating 2.5-3.5 hour, then solid-liquid separation, obtains filter cake.
7. the preparation method of manganese metal more than purity 99.99wt% according to claim 1, is characterized in that, in third step, described washing step gained filtrate cycle is back to MnO
2the MnO of breeze and sulfur-containing smoke gas reactions steps
2breeze making beating step.
8. manganese metal more than the purity 99.99wt% that prepared by the method for employing as described in claim 1-7 any one, is characterized in that, by weight percentage, in this manganese metal, Ca content is less than or equal to 0.0013%, Mg content and is less than or equal to 0.0005%.
9. manganese metal more than purity 99.99wt% according to claim 9, it is characterized in that, by weight percentage, in this manganese metal, the content of K is less than or equal to 0.0002%, the content of Na is less than or equal to 0.0006%, the content that the content of Fe is less than or equal to 0.0003%, Si is less than or equal to 0.0003%, and the content of P is less than or equal to 0.0001%.
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| CN113957482B (en) * | 2021-10-20 | 2023-04-21 | 宁波创致超纯新材料有限公司 | Method for preparing high-purity manganese by using anolyte |
| CN115571919A (en) * | 2022-09-29 | 2023-01-06 | 广西汇元锰业有限责任公司 | Method for removing calcium and magnesium ions in production of high-purity manganese sulfate |
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| GB740837A (en) * | 1952-06-03 | 1955-11-23 | Electric Furnace Prod Co | Improvements in the production of manganese solutions and the electrowinning of metallic manganese therefrom |
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| CN101798119A (en) * | 2010-03-29 | 2010-08-11 | 贵州红星发展股份有限公司 | Method for preparing manganese sulfate monohydrate |
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| AU776180B2 (en) * | 2000-04-04 | 2004-09-02 | Tosoh Corporation | Treated manganese ore, process for producing the same, and use thereof |
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| CN1772345A (en) * | 2005-10-25 | 2006-05-17 | 四川大学 | Waste gas desulfurizing method with composite absorbant comprising pyrolusite and pH buffering agent |
| CN101732956A (en) * | 2008-11-21 | 2010-06-16 | 胡海清 | Process for producing manganese salt by using sulfur-containing smoke gas |
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