CN104445423B - A kind of preparation method of high-purity manganese dioxide - Google Patents
A kind of preparation method of high-purity manganese dioxide Download PDFInfo
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- CN104445423B CN104445423B CN201410779249.7A CN201410779249A CN104445423B CN 104445423 B CN104445423 B CN 104445423B CN 201410779249 A CN201410779249 A CN 201410779249A CN 104445423 B CN104445423 B CN 104445423B
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000706 filtrate Substances 0.000 claims abstract description 84
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910052742 iron Inorganic materials 0.000 claims abstract description 34
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 29
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011591 potassium Substances 0.000 claims abstract description 28
- 239000011734 sodium Substances 0.000 claims abstract description 25
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 23
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 22
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 22
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 22
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 22
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 21
- -1 iron ion Chemical class 0.000 claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 239000002817 coal dust Substances 0.000 claims abstract description 4
- 239000013049 sediment Substances 0.000 claims abstract description 3
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract 2
- 238000001914 filtration Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 230000007812 deficiency Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract 1
- 239000003245 coal Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910001813 natrojarosite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- AJAMDKATKXGWKD-UHFFFAOYSA-M sodium manganese(2+) oxygen(2-) hydroxide Chemical compound [OH-].[Na+].[O-2].[Mn+2] AJAMDKATKXGWKD-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of preparation method of high-purity manganese dioxide. Technical scheme of the present invention is: first pyrolusite powder is mixed in proportion to calcining with coal dust; Add again sulfuric acid; Adjust manganese sulfate concentration 215? g/L?-235g/L scope, 10 DEG C-20 DEG C leave standstill; The ratio of adjusting the molal quantity of iron ion and the molal quantity sum of potassium, sodium is 3.01-3.06:1; Adjust manganese sulfate concentration 285? g/L?-300g/L, pH value 4-5.3,10 DEG C-15 DEG C leave standstill, and filter; Reduce deironing with manganese powder; In filtrate, add ammoniacal liquor, adjust pH value in 7.0-7.5 scope, obtain manganous hydroxide precipitation, filter, sediment, in 160 DEG C of roastings, is obtained to manganese dioxide powder. The invention provides a kind of method of utilizing pyrolusite to prepare high-purity manganese dioxide, the method has reduced the application of chemicals, has reduced three waste discharge.
Description
Technical field
The present invention relates to a kind of preparation method of high-purity manganese dioxide. Relate in particular to one pyrolusite and prepare dioxyChange the method for manganese.
Background technology
Manganese dioxide is the positive electrode of lithium battery, and China is populous nation, the consumption of lithium battery occupy the world itFirst. Therefore, battery electrode manganese dioxide has a huge market demand. Commercially available manganese dioxide mainly contains natural twoManganese oxide and artificial synthetic manganese dioxide. Remote because exploiting year, natural manganese dioxide resource is closely exhausted; CitySell that manganese dioxide mainly prepared with electrolysis and chemical method, the manganese dioxide that chemical method is produced is with the production cycleShort, product quality height is more and more subject to liking of people.
LiMn2O4 secondary cell, high to the potassium in manganese dioxide, sodium plasma content requirement. The inventor causesPower, in the manganese dioxide of the low potassium of exploitation, sodium, thinks that lithium battery provides raw material of fine quality.
Chinese patent 201010183376.2 has been introduced the method for preparing low-sodium electrolytic manganese dioxide. The method firstBy electrolytic manganese dioxide fragmentation, and then with the neutralization of lithium hydroxide or lithium carbonate, water is the method for rinsing repeatedly.The potassium of gained manganese dioxide product, sodium amount resultant with approximately 480 micrograms/gram left and right. At present, also do not utilizePyrolusite is produced the method for low potassium, sodium manganese dioxide.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of utilizing pyrolusite to prepare high-purity manganese dioxide.
Technical scheme of the present invention is: a kind of preparation method of high purity manganese sulfate, comprises the following steps:
The first step, mixes pyrolusite powder according to a certain percentage with coal dust, 800 DEG C of-900 DEG C of calcinings.
Second step, adding mass concentration by theoretical acid is 50% sulfuric acid, 75 DEG C-85 DEG C, 1.5 atmospherePress stirring reaction, react complete, be cooled to room temperature, after filtration, obtain the filtrate of containing manganese sulfate.
The 3rd step, concentrated filtrate, to manganese sulfate concentration in filtrate in 215g/L-235g/L scope, 10 DEG C-20 DEG CLeave standstill, after filtration, obtain filtrate; The object of this step is the concentration by adjusting manganese salt, remove calcium in solution,Magnesium ion and heavy metal ion.
The 4th step, measures potassium, sodium, iron content in filtrate, control the molal quantity of iron ion in solution and potassium,The ratio of the molal quantity sum of sodium is 3.01-3.06:1, if do not reached, adds ferrous sulfate and supplements.
The 5th step, concentrated filtrate, in 285g/L-300g/L scope, uses ammoniacal liquor to manganese sulfate concentration in filtrateAdjust filtrate pH value in 4-5.3 scope, 10 DEG C of-15 DEG C of standing 12-20 hour, obtain filtrate after filtration.
The object of the 4th step and the 5th step is by adjusting the acidity of solution and the concentration of manganese salt, allowing potassium sodium with yellow potassiumThe form precipitation of siderotil, yellow natrojarosite. It is assorted that technical solution of the present invention has reasonably been removed K, the Na etc. in solutionMatter ion, reaction equation is as follows:
3Fe2(SO4)3+12H2O+K2SO4＝K2Fe6(SO4)4(OH)12↓+6H2SO4，
3Fe2(SO4)3+12H2O+Na2SO4＝Na2Fe6(SO4)4(OH)12↓+6H2SO4。
The 6th step, measures the iron content in the 5th step filtrate, reduces deironing with manganese powder, adds theory and needs weightThe manganese powder of 1.05 times, the reaction in 3 hours of 40 DEG C of constant temperature, is cooled to after room temperature, obtains filtrate after filtration.
The 7th step adds ammoniacal liquor in filtrate, is adjusted to pH in 7.0-7.5 scope, obtains hydrogen-oxygenChange manganese precipitation, filter, washing, in 160 DEG C of roastings, obtains manganese dioxide powder by sediment.
The preferred technical scheme of the present invention is that the first step is by the mass ratio of pyrolusite powder and coal dust100:16-20。
The preferred technical scheme of the present invention is that the first step is 100:18 by the mass ratio of pyrolusite powder and coal dust.
The preferred technical scheme of the present invention is, the about 220g/L of manganese sulfate concentration in the 3rd step entire filter liquid, 15 DEG CLeave standstill.
The preferred technical scheme of the present invention is, the molal quantity of the molal quantity of iron ion and potassium, sodium in the 4th step solutionThe ratio of sum is 3.02-3.04:1.
The preferred technical scheme of the present invention is, the molal quantity of the molal quantity of iron ion and potassium, sodium in the 4th step solutionThe ratio of sum is 3.02:1.
The preferred technical scheme of the present invention is, the molal quantity of the molal quantity of iron ion and potassium, sodium in the 4th step solutionThe ratio of sum is 3.03:1.
The preferred technical scheme of the present invention is that the 5th step filtrate is 5,10-15 DEG C with ammoniacal liquor adjustment pH and leaves standstill15 hours.
Beneficial effect: the scheme of the present invention relates to is utilized calcium sulfate, the water-fast feature of magnesium sulfate, by adjustingThe concentration of manganese sulfate solution, has reasonably precipitated calcium salt and the magnesium salts in solution, has avoided the use of sulfide.Same reason, utilizes the way of rationally adjusting pH, allows potassium sodium with autunezite, yellow natrojarositeForm precipitation, has reasonably removed the foreign ion such as K, Na in solution.
Detailed description of the invention
Embodiment 1, pyrolusite, coal were crushed to respectively to 100 mesh sieves, mixed by the mass ratio of 100:18Close, 800 DEG C of calcinings, cooling after, add 50% sulfuric acid by theoretical acid, 80 DEG C of left and right, 1.5 atmospheric pressure stirMix reaction 3 hours, after filtration, obtain filtrate. Concentrated filtrate to manganese sulfate concentration is 215g/L, and 10 DEG C leave standstill 10Hour, after filtration, obtain filtrate. Measure potassium, sodium, iron content in filtrate, control iron ion in solution moleNumber is that 3.02:1 (if do not reached, can add ferrous sulfate and mend with the ratio of the molal quantity sum of potassium, sodiumFill), being concentrated into manganese sulfate concentration is 285g/L, adjusts filtrate pH to 4 with ammoniacal liquor, 10 DEG C leave standstill 15 hours,After filtration, obtain filtrate. Measure iron concentration in filtrate, to adding in filtrate theory to need 1.05 times of weightManganese powder reduced iron ion, 40 DEG C of constant temperature 3 hours, after filtration filtrate. In filtrate, add ammoniacal liquor, adjustPH to 7.0, leaves standstill 1 hour, filters, and washing, filtrate, in 160 DEG C of roastings, obtains manganese dioxide powder.
Embodiment 2, pyrolusite, coal were crushed to respectively to 100 mesh sieves, mixed by the mass ratio of 100:16Close, 800 DEG C of calcinings, cooling after, add 50% sulfuric acid by theoretical acid, 75 DEG C of left and right, 1.5 atmospheric pressure stirMix reaction 3 hours, after filtration, obtain filtrate. Concentrated filtrate to manganese sulfate concentration is 235g/L, and 20 DEG C leave standstill 10Hour, after filtration, obtain filtrate. Measure potassium, sodium, iron content in filtrate, control iron ion in solution moleNumber is that 3.06:1 (if do not reached, can add ferrous sulfate and mend with the ratio of the molal quantity sum of potassium, sodiumFill), being concentrated into manganese sulfate concentration is 300g/L, adjusts filtrate pH5.3 with ammoniacal liquor, 15 DEG C leave standstill 20 hours,After filtration, obtain filtrate. Measure iron concentration in filtrate, to adding in filtrate theory to need 1.05 times of weightManganese powder also has iron ion, 40 DEG C of constant temperature 3 hours, after filtration filtrate. In filtrate, add ammoniacal liquor, adjustPH to 7.5, leaves standstill 1 hour, filters, and washing, filtrate, in 160 DEG C of roastings, obtains manganese dioxide powder.
Embodiment 3, pyrolusite, coal were crushed to respectively to 100 mesh sieves, mixed by the mass ratio of 100:20Close, 800 DEG C of calcinings, cooling after, add 50% sulfuric acid by theoretical acid, 80 DEG C of left and right, 1.5 atmospheric pressure stirMix reaction 3 hours, after filtration, obtain filtrate. Concentrated filtrate to manganese sulfate concentration is 220g/L, and 15 DEG C leave standstill 10Hour, after filtration, obtain filtrate. Measure potassium, sodium, iron content in filtrate, control iron ion in solution moleNumber is that 3.03:1 (if do not reached, can add ferrous sulfate and mend with the ratio of the molal quantity sum of potassium, sodiumFill), being concentrated into manganese sulfate concentration is 295g/L, adjusting filtrate pH value with ammoniacal liquor is 4.5,10 DEG C standing 20Hour, after filtration, obtain filtrate. Measure iron concentration in filtrate, in filtrate, add theory to need weight 1.05Manganese powder doubly also has iron ion, 40 DEG C of constant temperature 3 hours, after filtration filtrate. In filtrate, add ammoniacal liquor, adjustWhole pH to 7.3, leaves standstill 1 hour, filters, and washing, filtrate, in 160 DEG C of roastings, obtains manganese dioxide powder.
Embodiment 4, pyrolusite, coal were crushed to respectively to 100 mesh sieves, mixed by the mass ratio of 100:19Close, 800 DEG C of calcinings, cooling after, add 50% sulfuric acid by theoretical acid, 80 DEG C of left and right, 1.5 atmospheric pressure stirMix reaction 3 hours, after filtration, obtain filtrate. Concentrated filtrate to manganese sulfate concentration is 230g/L, and 10 DEG C leave standstill 12Hour, after filtration, obtain filtrate. Measure potassium, sodium, iron content in filtrate, control iron ion in solution moleNumber is that 3.03:1 (if do not reached, can add ferrous sulfate and mend with the ratio of the molal quantity sum of potassium, sodiumFill), being concentrated into manganese sulfate concentration is 290g/L, adjusting filtrate pH value with ammoniacal liquor is 4.7,10 DEG C standing 15Hour, after filtration, obtain filtrate. Measure iron concentration in filtrate, in filtrate, add theory to need weight 1.05Manganese powder doubly also has iron ion, 40 DEG C of constant temperature 3 hours, after filtration filtrate. In filtrate, add ammoniacal liquor, adjustWhole pH to 7.2, leaves standstill 1 hour, filters, and washing, filtrate, in 160 DEG C of roastings, obtains manganese dioxide powder.
Embodiment 5, pyrolusite, coal were crushed to respectively to 100 mesh sieves, mixed by the mass ratio of 100:19Close, 800 DEG C of calcinings, cooling after, add 50% sulfuric acid by theoretical acid, 80 DEG C of left and right, 1.5 atmospheric pressure stirMix reaction 3 hours, after filtration, obtain filtrate. Concentrated filtrate to manganese sulfate concentration is 230g/L, and 10 DEG C leave standstill 12Hour, after filtration, obtain filtrate. Measure potassium, sodium, iron content in filtrate, control iron ion in solution moleNumber is that 3.04:1 (if do not reached, can add ferrous sulfate and mend with the ratio of the molal quantity sum of potassium, sodiumFill), being concentrated into manganese sulfate concentration is 290g/L, adjusting filtrate pH value with ammoniacal liquor is 5,10 DEG C standing 15Hour, after filtration, obtain filtrate. Measure iron concentration in filtrate, in filtrate, add theory to need weight 1.05Manganese powder doubly also has iron ion, 40 DEG C of constant temperature 3 hours, after filtration filtrate. In filtrate, add ammoniacal liquor, adjustWhole pH to 7.2, leaves standstill 1 hour, filters, and washing, filtrate, in 160 DEG C of roastings, obtains manganese dioxide powder.
With potassium, the sodium content of flame spectrophotometric determination embodiment 1-4 product, measure real with aas determinationExecute the tenors such as the calcium, magnesium, nickel of routine 1-5 product, outcome record is in table 1.
The testing result of table 1 embodiment 1-3 product
Table 1 data declaration, technical solution of the present invention has obtained the extremely low titanium dioxide of the metal ion content such as potassium, sodiumManganese, for lithium battery provides high-quality raw material.
Claims (7)
1. a preparation method for high-purity manganese dioxide, is characterized in that, comprises the following steps:
The first step, is that 100:16-20 mixes by pyrolusite powder and the mass ratio of coal dust, in 800 DEG C of-900 DEG C of calcinings;
Second step, adding mass concentration by theoretical acid is 50% sulfuric acid, 75 DEG C-85 DEG C, 1.5 atmospheric pressure stirring reactions 4 hours, are cooled to room temperature, obtain filtrate after filtration;
The 3rd step, concentrated filtrate, to manganese sulfate concentration in filtrate, in 215g/L-235g/L scope, 10 DEG C-20 DEG C leave standstill, obtain filtrate after filtration;
The 4th step, measures potassium, sodium, iron content in filtrate, and in control solution, the ratio of the molal quantity of iron ion and the molal quantity sum of potassium, sodium is 3.01-3.06:1, if iron ion deficiency adds ferrous sulfate and supplements;
The 5th step, concentrated filtrate, in 285g/L-300g/L scope, adjusts filtrate pH value in 4.0-5.3 scope with ammoniacal liquor to manganese sulfate concentration in filtrate, and 10 DEG C of-15 DEG C of standing 12-20 hour, obtain filtrate after filtration;
The 6th step, measures the iron content in the 5th step filtrate, reduces deironing with manganese powder, adds the manganese powder that theory needs 1.05 times of weight, and the reaction in 3 hours of 40 DEG C of constant temperature, is cooled to after room temperature, obtains filtrate after filtration;
The 7th step adds ammoniacal liquor in the 6th step filtrate, is adjusted to pH in 7.0-7.5 scope, obtains manganous hydroxide precipitation, filters, and washing, in 160 DEG C of roastings, obtains manganese dioxide powder by sediment.
2. a kind of preparation method of high-purity manganese dioxide according to claim 1, is characterized in that: the 3rd step concentrated filtrate is 220g/L to manganese sulfate concentration in filtrate, and 15 DEG C leave standstill.
3. a kind of preparation method of high-purity manganese dioxide according to claim 1, is characterized in that: the 5th step concentrated filtrate, and, adjust pH with ammoniacal liquor and be 5,10-15 DEG C and leave standstill 15 hours in 285g/L-300g/L scope to manganese sulfate concentration in filtrate.
4. a kind of preparation method of high-purity manganese dioxide according to claim 1, is characterized in that: in described the 4th step, needing to control the ratio of the molal quantity of iron ion and the molal quantity sum of potassium, sodium in solution is 3.02-3.04:1.
5. a kind of preparation method of high-purity manganese dioxide according to claim 1, is characterized in that: in described the 4th step, needing to control the ratio of the molal quantity of iron ion and the molal quantity sum of potassium, sodium in solution is 3.02:1.
6. a kind of preparation method of high-purity manganese dioxide according to claim 1, is characterized in that: in described the 4th step, needing to control the ratio of the molal quantity of iron ion and the molal quantity sum of potassium, sodium in solution is 3.04:1.
7. a kind of preparation method of high-purity manganese dioxide according to claim 1, is characterized in that: in described the 4th step, needing to control the ratio of the molal quantity of iron ion and the molal quantity sum of potassium, sodium in solution is 3.03:1.
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| JPS59223236A (en) * | 1983-06-02 | 1984-12-15 | Chuo Denki Kogyo Kk | Production of high purity manganese compound |
| CN1023694C (en) * | 1990-11-21 | 1994-02-09 | 重庆干电池总厂 | Prepn. of manganese dioxide |
| US5277890A (en) * | 1992-09-28 | 1994-01-11 | Duracell Inc. | Process for producing manganese dioxide |
| CN100500577C (en) * | 2006-05-15 | 2009-06-17 | 北京科技大学 | Method for preparing hybrid oxide of manganese by manganese sulfate solution |
| CN1919741A (en) * | 2006-09-19 | 2007-02-28 | 北京科技大学 | Method for preparing high apparent density manganese dioxide using manganese sulfate solution |
| CN101786666B (en) * | 2010-02-10 | 2012-02-22 | 彭天剑 | lithium manganate anode material and preparation method thereof |
| CN103011297B (en) * | 2012-12-07 | 2014-12-10 | 中信大锰矿业有限责任公司 | Method for production of high purity manganese sulfate by using pyrolusite as raw material |
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