CN116553618A - Preparation method of high-purity manganese dioxide - Google Patents
Preparation method of high-purity manganese dioxide Download PDFInfo
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- CN116553618A CN116553618A CN202310689795.0A CN202310689795A CN116553618A CN 116553618 A CN116553618 A CN 116553618A CN 202310689795 A CN202310689795 A CN 202310689795A CN 116553618 A CN116553618 A CN 116553618A
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 64
- 239000000706 filtrate Substances 0.000 claims abstract description 59
- 238000010438 heat treatment Methods 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 49
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 49
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 49
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000047 product Substances 0.000 claims abstract description 35
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 17
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 17
- 239000012065 filter cake Substances 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- 238000004321 preservation Methods 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000011790 ferrous sulphate Substances 0.000 claims description 12
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 12
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 12
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 abstract description 11
- 238000000227 grinding Methods 0.000 abstract description 9
- 238000001556 precipitation Methods 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 41
- 239000012535 impurity Substances 0.000 description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 description 10
- 229910001437 manganese ion Inorganic materials 0.000 description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 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 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000012086 standard solution Substances 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 239000012286 potassium permanganate Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 3
- 229940039790 sodium oxalate Drugs 0.000 description 3
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 229910052935 jarosite Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DYPHJEMAXTWPFB-UHFFFAOYSA-N [K].[Fe] Chemical compound [K].[Fe] DYPHJEMAXTWPFB-UHFFFAOYSA-N 0.000 description 1
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 1
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 229910001447 ferric ion Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000005048 flame photometry Methods 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- KBMLJKBBKGNETC-UHFFFAOYSA-N magnesium manganese Chemical compound [Mg].[Mn] KBMLJKBBKGNETC-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 229910000314 transition metal oxide 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The application relates to a preparation method of high-purity manganese dioxide, which relates to the field of manganese dioxide preparation technology and comprises the following steps: dissolving manganese sulfate in water to prepare a solution, regulating the pH value of the solution to 3.4-4.1 by using dilute sulfuric acid, heating and stirring for reacting for 2-5 hours, filtering and collecting filtrate after precipitation, concentrating at low temperature, filtering and collecting filtrate after precipitation, regulating the pH value to 7.2-7.8, heating to 50-65 ℃, preserving heat for reacting for 5-6 hours, and filtering and collecting filtrate after precipitation; continuously adjusting the pH value to 9-12, stirring and reacting for 3-5h, then adding an oxidant and heating to 50-85 ℃ and stirring and reacting for 5-8h, filtering out water and collecting a filter cake and drying, washing the product obtained in the step S4 by deionized water, then drying, calcining the product at 300-400 ℃ for 4-5h, washing by water, filtering, drying the water, and grinding to obtain manganese dioxide powder. The manganese dioxide prepared by the technical scheme has high purity and can meet the use requirement of the application field of high purity.
Description
Technical Field
The application relates to the field of manganese dioxide preparation technology, in particular to a preparation method of high-purity manganese dioxide.
Background
Manganese dioxide, also known as oxide of tetravalent manganese, of the formula MnO 2 Manganese dioxide is a stable black or brownish black powdery solid at normal temperature and exists mainly in pyrolusite as an amphoteric transition metal oxide. Manganese dioxide has unique properties and is widely used in a variety of fields. Manganese dioxide is an important electrode material and is widely applied to chemical power sources such as alkaline manganese batteries, zinc manganese batteries, magnesium manganese batteries, lithium manganese batteries and the like. In addition, manganese dioxide is used as a multifunctional fine inorganic reagent, and is prepared from nano material,The new fields of advanced catalysts and the like have wide application prospect.
At present, electrolytic Manganese Dioxide (EMD) is high in cost and unstable in product quality, and the requirements of the rapidly developed battery industry on high-quality manganese dioxide cannot be met. The performance of the chemical manganese dioxide is close to that of electrolytic manganese dioxide, the production cost is low, the coarse product and the high-quality product of the chemical manganese dioxide have good discharge performance, and the discharge performance of the product is enhanced as the purity of the manganese dioxide is higher. However, the chemical manganese dioxide prepared at present cannot reach high purity, which limits the application of the chemical manganese dioxide to a certain extent.
Disclosure of Invention
Aiming at the technical problems, the application provides a preparation method of high-purity manganese dioxide, which aims to improve the purity of the chemical manganese dioxide and further improve the application of the chemical manganese dioxide in various fields.
A method for preparing high-purity manganese dioxide, comprising the following steps:
s1, dissolving manganese sulfate in water to prepare a solution, regulating the pH value of the solution to 3.4-4.1 by using dilute sulfuric acid, heating to 50-70 ℃, stirring and reacting for 2-5h, filtering out precipitate and collecting filtrate;
s2, collecting the filtrate collected in the step S1, concentrating at low temperature until the manganese sulfate concentration is 135-150g/L, filtering out precipitate, and collecting the filtrate;
s3, adjusting the pH value of the filtrate obtained in the step S2 to 7.2-7.8, heating to 50-65 ℃, preserving heat for reaction for 5-6h, filtering out sediment and collecting filtrate;
s4, adjusting the pH value of the filtrate obtained in the step S3 to 9-12, stirring in a water bath at 50-60 ℃ for 3-5 hours, adding an oxidant, heating to 50-85 ℃ for stirring for 5-8 hours, filtering out water, collecting a filter cake and drying;
s5, washing the product obtained in the step S4 by deionized water, drying, calcining the product at 300-400 ℃ for 4-5 hours, washing with water, filtering, drying the water, and grinding to obtain manganese dioxide powder.
By adopting the technical scheme, manganese sulfate is used as a raw material to prepare manganese dioxide, impurities such as calcium, magnesium and the like contained in the manganese sulfate raw material react with sulfuric acid to generate magnesium sulfate, calcium sulfate and the like which are insoluble in water, and the pH value of a manganese sulfate solution is adjusted by dilute sulfuric acid to precipitate the impurities such as calcium, magnesium and the like, and then the impurities are removed by filtration. Further regulating the pH value to be weak alkaline, further separating out a part of precipitate insoluble in alkaline substances in the range, filtering and removing the precipitate, oxidizing manganese ions to generate manganese hydroxide in the process of continuously regulating the pH value of the solution to 9-12, and calcining to obtain manganese dioxide powder.
Optionally, the concentration of the dilute sulfuric acid in step S1 is 15-25%.
Through adopting above-mentioned technical scheme, through the concentration of dilute sulfuric acid regulation manganese sulfate solution, can filter after making impurity ion precipitation such as calcium, magnesium contained therein get rid of, use dilute sulfuric acid to adjust the pH of solution can avoid introducing new impurity ion, use dilute sulfuric acid simultaneously can avoid the manganese ion to be oxidized in advance and appear precipitating, influence purity and the yield of product.
Optionally, in step S3, the pH adjuster is aqueous ammonia.
By adopting the technical scheme, in the step S3, partial impurity components which are insoluble in the alkaline solution in the solution can be further removed by adjusting the pH value of the solution to be weak, the alkalinity of ammonia water is weaker than that of sodium hydroxide, the generation of manganese hydroxide products in the solution can be reduced in a weak alkaline environment, and the yield of manganese dioxide products is improved. In addition, the introduction of other impurity elements can be reduced by adjusting the pH value through ammonia water, and the purity of the product is improved.
Optionally, in step S4, the pH adjuster is sodium hydroxide.
By adopting the technical scheme, in the step S4, the pH value of the manganese sulfate solution is adjusted to 10-12 to enable manganese sulfate to produce manganese hydroxide, and the manganese hydroxide is insoluble in water and can be separated from the solution and impurity components in the solution through filtration.
Optionally, in step S4, the oxidizing agent includes at least one of hydrogen peroxide, sodium persulfate, and potassium persulfate.
By adopting the technical scheme, in the step S4, the manganese ions are oxidized by the oxidant to oxidize the positive divalent manganese ions into positive tetravalent manganese ions, so that manganese dioxide is generated in the subsequent firing process. The oxidant is selected from strong oxidants such as hydrogen peroxide, sodium persulfate, potassium persulfate and the like, has good oxidation effect, can oxidize divalent manganese ions in the solution as much as possible, reduces the content of low-valence manganese ions in the product, and improves the purity of the manganese dioxide product.
Optionally, in step S4, the temperature is raised after adding the oxidizing agent in the following manner: heating to 50-55 ℃ at a heating rate of 8-10 ℃/min, performing heat preservation reaction for 1-2h, heating to 65-70 ℃ at a heating rate of 3-5 ℃/min, performing heat preservation reaction for 2-3h, and finally heating to 80-85 ℃ at a heating rate of 1-3 ℃/min, performing heat preservation reaction for 2-3h.
By adopting the technical scheme, in the oxidation reaction process, the reaction byproducts such as manganese hydroxide and the like are firstly heated to 50-55 ℃ at a relatively fast heating rate, the basic reaction temperature is quickly reached, and the reaction byproducts such as manganese hydroxide and the like are avoided in a low-temperature environment. The temperature reaches the basic reaction speed and then is changed into a slower heating speed to carry out oxidation reaction, so that incomplete reaction and larger change of the valence of manganese ions caused by too fast change of the reaction temperature are avoided, and excessive high-valence manganese ion byproducts are generated. And the higher the temperature is in the heating process, the lower the heating speed is adopted, so that the temperature is ensured to be slowly and stably increased, and the stability of the oxidation reaction process is improved.
Optionally, between S2 and S3, the method further comprises the following steps:
adding ferrous sulfate into the filtrate, stirring and reacting for 1-2h at 45-60 ℃ in water bath, cooling to room temperature, and filtering out precipitate.
By adopting the technical scheme, the impurity elements contained in the manganese sulfate solution comprise elements such as sodium, potassium and the like besides calcium and magnesium, sulfate of the sodium and potassium elements cannot be precipitated and cannot be removed in a filtering mode, and the added ferrous sulfate can be separated out in a form of jarosite and jarosite precipitation with the potassium and sodium elements in the manganese sulfate solution, so that potassium ions and sodium ions in the manganese sulfate solution are removed, the content of impurity components in a product is further reduced, and the purity of the product is improved.
Optionally, the ferrous sulfate accounts for 6.8-11.2% of the manganese sulfate by mass.
By adopting the technical scheme, potassium ions and sodium ions in the manganese sulfate solution cannot be completely precipitated out when the addition amount of the ferrous sulfate is too small, so that the purity of the product does not reach the standard; and excessive ferrous sulfate can introduce excessive ferrous ions, and the ferrous ions can be oxidized into ferric ions in the subsequent oxidation reaction process so as to form ferric hydroxide and other precipitates, so that the purity of the product is reduced.
Optionally, the manganese sulfate is feed-grade manganese sulfate.
By adopting the technical scheme, the feed-grade manganese sulfate has less impurity content and higher purity, and is more beneficial to the preparation of high-purity manganese dioxide.
In summary, the present application includes at least one of the following beneficial technical effects:
1. in the technical scheme, the high-purity manganese dioxide is prepared by taking manganese sulfate as a raw material, the solution is firstly adjusted to be weakly acidic by adding dilute sulfuric acid into the manganese sulfate solution, in the process, impurity components such as magnesium, calcium and the like in the manganese sulfate solution are separated out in the form of magnesium sulfate and calcium sulfate precipitation, part of impurities in the manganese sulfate solution are removed, the impurity content in the prepared manganese dioxide product is reduced, and the product purity is improved.
2. In the process of preparing manganese dioxide, positive divalent manganese ions are oxidized into positive tetravalent ions through an oxidant, in the process, oxidation reaction is promoted through regular water bath temperature rising reaction, and the generation of reaction byproducts can be effectively reduced through controlling the temperature change in the reaction process, so that the purity of the prepared manganese dioxide is further improved.
3. The addition of a certain amount of ferrous sulfate into the manganese sulfate solution can separate out impurity components such as sodium, potassium and the like in the manganese sulfate solution in the form of potassium-iron alum and sodium-iron alum precipitation, so that potassium ions and sodium ions in the manganese sulfate solution are removed, the content of the impurity components in the product is further reduced, and the purity of the product is improved.
Detailed Description
The present application is described in further detail below in connection with specific examples. In the following examples, no specific details are set forth, and the examples were conducted under conventional conditions or conditions recommended by the manufacturer; the raw materials used in the following examples were all commercially available from ordinary sources except for the specific descriptions.
Example 1
A method for preparing high-purity manganese dioxide, comprising the following steps:
s1, dissolving feed-grade manganese sulfate in deionized water, adding 15% dilute sulfuric acid to adjust the pH value of the solution to 3.4, heating to 50 ℃, preserving heat, stirring and reacting for 2 hours, filtering, and collecting filtrate for later use;
s2, collecting the filtrate obtained in the step S1, concentrating at low temperature until the concentration of manganese sulfate is 135g/L, filtering at the concentration temperature of 55 ℃, and collecting the filtrate for later use;
s3, adding ammonia water into the filtrate obtained by filtering in the step S2 to adjust the pH value to 7.2, heating to 65 ℃ for heat preservation reaction 5, and filtering and collecting the filtrate for later use;
s4, adding sodium hydroxide into the filtrate collected in the step S3 to adjust the pH value to 12, heating to 55 ℃ in a water bath, preserving heat, stirring and reacting for 4.5 hours, adding hydrogen peroxide, heating to 85 ℃ at a speed of 5 ℃/min, preserving heat, stirring and reacting for 5 hours, filtering, and drying a filter cake;
and S5, washing the filter cake dried in the step S4 by using deionized water until the solution is neutral, putting the dried product into a muffle furnace, calcining for 5 hours at 350 ℃, washing with water, filtering, drying, and grinding to obtain the high-purity manganese dioxide powder.
Example 2
A method for preparing high-purity manganese dioxide, comprising the following steps:
s1, dissolving feed-grade manganese sulfate in deionized water, adding 25% dilute sulfuric acid to adjust the pH value of the solution to 4.1, heating to 50 ℃, preserving heat, stirring and reacting for 2 hours, filtering, and collecting filtrate for later use;
s2, collecting the filtrate obtained in the step S1, concentrating at low temperature until the concentration of manganese sulfate is 150g/L, filtering at the concentration temperature of 55 ℃, and collecting the filtrate for later use;
s3, adding ammonia water into the filtrate obtained by filtering in the step S2 to adjust the pH value to 7.8, heating to 65 ℃ for heat preservation reaction 5, and filtering and collecting the filtrate for later use;
s4, adding sodium hydroxide into the filtrate collected in the step S3 to adjust the pH value to 9, heating to 55 ℃ in a water bath, preserving heat, stirring and reacting for 4.5 hours, adding hydrogen peroxide, heating to 85 ℃ at a speed of 5 ℃/min, preserving heat, stirring and reacting for 5 hours, filtering, and drying a filter cake;
and S5, washing the filter cake dried in the step S4 by using deionized water until the solution is neutral, putting the dried product into a muffle furnace, calcining for 5 hours at 350 ℃, washing with water, filtering, drying, and grinding to obtain the high-purity manganese dioxide powder.
Example 3
A method for preparing high-purity manganese dioxide, comprising the following steps:
s1, dissolving feed-grade manganese sulfate in deionized water, adding 18% dilute sulfuric acid to adjust the pH value of the solution to 3.8, heating to 50 ℃, preserving heat, stirring and reacting for 2 hours, filtering, and collecting filtrate for later use;
s2, collecting the filtrate obtained in the step S1, concentrating at low temperature until the concentration of manganese sulfate is 145g/L, filtering at the concentration temperature of 55 ℃, and collecting the filtrate for later use;
s3, adding ammonia water into the filtrate obtained by filtering in the step S2 to adjust the pH value to 7.5, heating to 65 ℃ for heat preservation reaction 5, and filtering and collecting the filtrate for later use;
s4, adding sodium hydroxide into the filtrate collected in the step S3 to adjust the pH value to 11, heating to 55 ℃ in a water bath, preserving heat, stirring and reacting for 4.5 hours, adding sodium peroxide, heating to 85 ℃ at a speed of 5 ℃/min, preserving heat, stirring and reacting for 5 hours, filtering, and drying a filter cake;
and S5, washing the filter cake dried in the step S4 by using deionized water until the solution is neutral, putting the dried product into a muffle furnace, calcining for 5 hours at 350 ℃, washing with water, filtering, drying, and grinding to obtain the high-purity manganese dioxide powder.
Example 4
A method for preparing high-purity manganese dioxide, comprising the following steps:
s1, dissolving feed-grade manganese sulfate in deionized water, adding 18% dilute sulfuric acid to adjust the pH value of the solution to 3.8, heating to 50 ℃, preserving heat, stirring and reacting for 2 hours, filtering, and collecting filtrate for later use;
s2, collecting the filtrate obtained in the step S1, concentrating at low temperature until the concentration of manganese sulfate is 145g/L, filtering at the concentration temperature of 55 ℃, and collecting the filtrate for later use;
s3, adding ammonia water into the filtrate obtained by filtering in the step S2 to adjust the pH value to 7.5, heating to 65 ℃ for heat preservation reaction 5, and filtering and collecting the filtrate for later use;
s4, adding sodium hydroxide into the filtrate collected in the step S3 to adjust the pH value to 11, heating to 55 ℃ for water bath heat preservation and stirring reaction for 4.5 hours, then adding sodium peroxide, heating to 55 ℃ for heat preservation reaction for 2 hours at the heating rate of 10 ℃/min, heating to 70 ℃ for heat preservation reaction for 3 hours at the heating rate of 4 ℃/min, heating to 85 ℃ for heat preservation reaction for 2 hours at the heating rate of 2 ℃/min, filtering, and drying a filter cake;
and S5, washing the filter cake dried in the step S4 by using deionized water until the solution is neutral, putting the dried product into a muffle furnace, calcining for 5 hours at 350 ℃, washing with water, filtering, drying, and grinding to obtain the high-purity manganese dioxide powder.
Example 5
A method for preparing high-purity manganese dioxide, comprising the following steps:
s1, dissolving feed-grade manganese sulfate in deionized water, adding 18% dilute sulfuric acid to adjust the pH value of the solution to 3.8, heating to 50 ℃, preserving heat, stirring and reacting for 2 hours, filtering, and collecting filtrate for later use;
s2, collecting the filtrate obtained in the step S1, concentrating at low temperature until the concentration of manganese sulfate is 145g/L, filtering at the concentration temperature of 55 ℃, and collecting the filtrate for later use;
s3, adding ferrous sulfate to the filtrate collected in the step S2, wherein the addition amount of the ferrous sulfate accounts for 8.7wt% of the manganese sulfate, stirring and reacting for 1-2h at the temperature of 45-60 ℃ in a water bath, cooling to room temperature, filtering out precipitate, and collecting filtrate for later use.
S4, adding ammonia water into the filtrate obtained by filtering in the step S3 to adjust the pH value to 7.5, heating to 65 ℃ for heat preservation reaction 5, and filtering and collecting the filtrate for later use;
s5, adding sodium hydroxide into the filtrate collected in the step S4 to adjust the pH value to 11, heating to 55 ℃ in a water bath, preserving heat, stirring and reacting for 4.5 hours, then adding sodium peroxide, heating to 85 ℃ at a speed of 5 ℃/min, preserving heat, stirring and reacting for 5 hours, filtering, and drying a filter cake;
and S6, washing the filter cake dried in the step S5 by using deionized water until the solution is neutral, putting the dried product into a muffle furnace, calcining for 5 hours at 350 ℃, washing with water, filtering, drying, and grinding to obtain the high-purity manganese dioxide powder.
Example 6
This example differs from example 5 in that the amount of ferrous sulfate added is 15wt% of manganese sulfate, the remainder remaining consistent with example 5.
Comparative example 1
A method for preparing high-purity manganese dioxide, comprising the following steps:
s1, dissolving feed-grade manganese sulfate in deionized water, heating to 50 ℃, preserving heat, stirring, reacting for 2 hours, filtering, and collecting filtrate for later use;
s2, collecting the filtrate obtained in the step S1, concentrating at low temperature until the concentration of manganese sulfate is 135g/L, filtering at the concentration temperature of 55 ℃, and collecting the filtrate for later use;
s3, adding ammonia water into the filtrate obtained by filtering in the step S2 to adjust the pH value to 7.2, heating to 65 ℃ for heat preservation reaction 5, and filtering and collecting the filtrate for later use;
s4, adding sodium hydroxide into the filtrate collected in the step S3 to adjust the pH value to 12, heating to 55 ℃ in a water bath, preserving heat, stirring and reacting for 4.5 hours, adding hydrogen peroxide, heating to 85 ℃ at a speed of 5 ℃/min, preserving heat, stirring and reacting for 5 hours, filtering, and drying a filter cake;
and S5, washing the filter cake dried in the step S4 by using deionized water until the solution is neutral, putting the dried product into a muffle furnace, calcining for 5 hours at 350 ℃, washing with water, filtering, drying, and grinding to obtain the high-purity manganese dioxide powder.
Comparative example 2
A method for preparing high-purity manganese dioxide, comprising the following steps:
s1, dissolving feed-grade manganese sulfate in deionized water, heating to 50 ℃, preserving heat, stirring, reacting for 2 hours, filtering, and collecting filtrate for later use;
s2, collecting the filtrate obtained in the step S1, concentrating at low temperature until the concentration of manganese sulfate is 135g/L, filtering at the concentration temperature of 55 ℃, and collecting the filtrate for later use;
s3, adding sodium hydroxide into the filtrate collected in the step S2 to adjust the pH value to 12, heating to 55 ℃ in a water bath, preserving heat, stirring and reacting for 4.5 hours, adding hydrogen peroxide, mixing and dissolving, heating to 85 ℃ at a speed of 5 ℃/min, preserving heat, stirring and reacting for 5 hours, filtering, and drying a filter cake;
and S4, washing the filter cake dried in the step S3 by using deionized water until the solution is neutral, putting the dried product into a muffle furnace, calcining for 5 hours at 350 ℃, washing with water, filtering, drying, and grinding to obtain the high-purity manganese dioxide powder.
Comparative example 3
This comparative example differs from example 1 in that the pH of the solution was adjusted in step S1 using sulfuric acid having a concentration of 50%, the remainder remaining in accordance with example 1.
Performance detection
The purity of the manganese dioxide powder prepared in each example and comparative example was measured by potassium permanganate titration, and the purity of manganese dioxide was represented by N, and the specific measurement method was as follows:
0.2500g of a sample having a particle size of less than 0.097mm and air-dried under laboratory conditions was weighed and subjected to a blank test along with the sample in a 300mL Erlenmeyer flask. 75mL of sulfuric acid was added, 35.00L of oxalic acid standard solution was accurately added with a burette, covered with a porcelain crucible cover, and heated in a hot water bath at 80℃until the black particles disappeared to completely dissolve. During the heating process, the test solution in the conical flask is often shaken, and the water lost by evaporation is supplemented. After the sample is completely dissolved (sometimes because the sample contains a large amount of other elements, the sample cannot be completely decomposed and heated to 90 minutes, mn0 can be completely decomposed by sodium acid by reduction), taking off the sample and titrating the sample by using a potassium permanganate standard solution while the sample is hot, slowly titrating the sample when the sample approaches to the end point, and keeping the titration temperature between 75 ℃ until the last drop of the potassium permanganate standard solution changes the sample into reddish color to the end point (V).
Wherein C is sodium oxalate standard solutionConcentration, mol/L; v1 is the volume of the excessive sodium oxalate standard solution added when the sample is dissolved, and mL; v2 is the volume of the potassium permanganate standard solution consumed during back drop and mL; k is the proportionality coefficient of 1mL of potassium permanganate standard solution corresponding to the mL of sodium oxalate standard solution; 43.47 is the molar mass, g/mol, of 1/2 manganese dioxide; m is the mass of the sample and g.
In addition, the content of potassium and sodium in the sample is detected by flame photometry, and the content of metal elements such as calcium, magnesium and the like in the sample is detected by atomic absorption method.
The results of the performance measurements for examples 1-3 and comparative examples 1-3 are shown in Table 1 below.
Table 1: examples 1-3 and comparative examples 1-3 were tested for performance.
As can be seen from the data in the table 1, the impurity metal elements such as calcium and magnesium in the solution can be effectively removed in the process of adjusting the concentration of the manganese sulfate solution by using the dilute sulfuric acid, the content of the calcium and magnesium elements in the product is reduced, and the purity of the product is improved. Further, ammonia water is used for adjusting the pH value of the manganese sulfate solution to be slightly alkaline, and the product purity can be further improved after the filtration, so that the high-purity manganese dioxide is obtained.
As can be seen from the detection data of the embodiment 4 and the embodiment 5, the addition of ferrous sulfate can further precipitate metal elements such as sodium, potassium and the like in the precipitation solution, and the precipitated impurities are removed by a filtering mode, so that the method is simple and efficient, and no impurity element is introduced.
The foregoing are all preferred embodiments of the present application, and are not intended to limit the scope of the present application in any way, therefore: all equivalent changes in structure, shape and principle of this application should be covered in the protection scope of this application.
Claims (9)
1. A method for preparing high-purity manganese dioxide, which is characterized by comprising the following steps:
s1, dissolving manganese sulfate in water to prepare a solution, regulating the pH value of the solution to 3.4-4.1 by using dilute sulfuric acid, heating to 50-70 ℃, stirring and reacting for 2-5h, filtering out precipitate and collecting filtrate;
s2, collecting the filtrate collected in the step S1, concentrating at low temperature until the manganese sulfate concentration is 135-150g/L, filtering out precipitate, and collecting the filtrate;
s3, adjusting the pH value of the filtrate obtained in the step S2 to 7.2-7.8, heating to 50-65 ℃, preserving heat for reaction for 5-6h, filtering out sediment and collecting filtrate;
s4, adjusting the pH value of the filtrate obtained in the step S3 to 9-12, stirring in a water bath at 50-60 ℃ for 3-5 hours, adding an oxidant, heating to 50-85 ℃ for stirring for 5-8 hours, filtering out water, collecting a filter cake and drying;
s5, washing the product obtained in the step S4 with deionized water, drying, calcining the product at 300-400 ℃ for 4-5 hours, washing with water, filtering, and drying to obtain a manganese dioxide product.
2. The method for producing high purity manganese dioxide according to claim 1, wherein the concentration of dilute sulfuric acid in step S1 is 15 to 25%.
3. The method for producing high purity manganese dioxide according to claim 1, wherein in step S3, the pH adjuster is aqueous ammonia.
4. The method of producing high purity manganese dioxide according to claim 1, wherein in step S4, the pH adjuster is sodium hydroxide.
5. The method for producing high purity manganese dioxide according to claim 1, wherein in step S4, the oxidizing agent comprises at least one of hydrogen peroxide, sodium persulfate, and potassium persulfate.
6. The method for producing high purity manganese dioxide according to claim 1, wherein in step S4, the temperature is raised by adding an oxidizing agent as follows: heating to 50-55 ℃ at a heating rate of 8-10 ℃/min, performing heat preservation reaction for 1-2h, heating to 65-70 ℃ at a heating rate of 3-5 ℃/min, performing heat preservation reaction for 2-3h, and finally heating to 80-85 ℃ at a heating rate of 1-3 ℃/min, performing heat preservation reaction for 2-3h.
7. The method for producing high purity manganese dioxide according to claim 1, further comprising the steps of, between steps S2 and S3: adding ferrous sulfate into the filtrate, stirring and reacting for 1-2h at 45-60 ℃ in water bath, cooling to room temperature, and filtering out precipitate.
8. The method for preparing high-purity manganese dioxide according to claim 7, wherein the ferrous sulfate accounts for 6.8-11.2% of the manganese sulfate by mass.
9. The method for preparing high-purity manganese dioxide according to claim 1, wherein the manganese sulfate is any one of feed-grade manganese sulfate, high-purity manganese sulfate and industrial-grade manganese sulfate.
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