CN115744995A - Method for preparing flaky manganese dioxide by continuous flow microwave method and prepared flaky manganese dioxide - Google Patents
Method for preparing flaky manganese dioxide by continuous flow microwave method and prepared flaky manganese dioxide Download PDFInfo
- Publication number
- CN115744995A CN115744995A CN202211443253.7A CN202211443253A CN115744995A CN 115744995 A CN115744995 A CN 115744995A CN 202211443253 A CN202211443253 A CN 202211443253A CN 115744995 A CN115744995 A CN 115744995A
- Authority
- CN
- China
- Prior art keywords
- manganese dioxide
- manganese
- solution
- microwave
- chemical reactor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 238000000034 method Methods 0.000 title claims abstract description 61
- 239000000126 substance Substances 0.000 claims abstract description 59
- 239000011259 mixed solution Substances 0.000 claims abstract description 36
- 150000002696 manganese Chemical class 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000002585 base Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 238000002347 injection Methods 0.000 claims abstract description 3
- 239000007924 injection Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 239000012286 potassium permanganate Substances 0.000 claims description 62
- 239000007864 aqueous solution Substances 0.000 claims description 26
- 229940099596 manganese sulfate Drugs 0.000 claims description 23
- 239000011702 manganese sulphate Substances 0.000 claims description 23
- 235000007079 manganese sulphate Nutrition 0.000 claims description 23
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- JYLNVJYYQQXNEK-UHFFFAOYSA-N 3-amino-2-(4-chlorophenyl)-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(CN)C1=CC=C(Cl)C=C1 JYLNVJYYQQXNEK-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 5
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 5
- 239000011565 manganese chloride Substances 0.000 claims description 5
- 235000002867 manganese chloride Nutrition 0.000 claims description 5
- 229940099607 manganese chloride Drugs 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 239000000920 calcium hydroxide Substances 0.000 claims description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims 1
- 230000035484 reaction time Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 66
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 40
- 238000005303 weighing Methods 0.000 description 29
- 230000002572 peristaltic effect Effects 0.000 description 24
- 239000011521 glass Substances 0.000 description 17
- 239000013078 crystal Substances 0.000 description 13
- 239000007787 solid Substances 0.000 description 12
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical class ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
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
- 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
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing flaky manganese dioxide by a continuous flow microwave method and the flaky manganese dioxide prepared by the method, wherein the method comprises the following steps: mixing divalent manganese salt, heptavalent manganese salt, alkali and water to obtain a mixed solution; wherein the molar ratio of the base to the heptavalent manganese salt is > 1; injecting the mixed solution into a microwave chemical reactor to carry out continuous flow microwave reaction, flowing out of the microwave chemical reactor, filtering and drying to obtain the flaky manganese dioxide; wherein the power of the microwave chemical reactor is more than or equal to 300W, and the injection speed of the mixed liquid is less than or equal to 10mL/min. The method has the characteristics of simple operation, short reaction time, high yield and good product quality.
Description
Technical Field
The invention relates to the technical field of inorganic material preparation, in particular to a method for preparing flaky manganese dioxide by a continuous flow microwave method and the prepared flaky manganese dioxide.
Background
Manganese dioxide is black, black brown, brown amorphous powder or crystal, and is insoluble in water, weak acid and weak base; it is insoluble in water, nitric acid and cold sulfuric acid, and is dissolved in hot concentrated hydrochloric acid to produce chlorine gas. Manganese dioxide has a wide variety of applications and has important applications in the chemical industry, such as a negative electrode in dry cells; as an oxidant in organic synthesis reactions; used as oxidant and glaze color in the production of ceramics and enamel; the glass is used for eliminating impurities and manufacturing decorative glass in glass production; can be used as a catalyst in polymer reaction. The crystal structure of manganese dioxide is roughly divided into 3 major categories, namely a one-dimensional tunnel structure, a two-dimensional sheet structure and a three-dimensional net structure, and 5 kinds of crystals (the one-dimensional tunnel structure has three crystal forms of 3 kinds, namely alpha, beta and gamma, the two-dimensional tunnel structure has three crystal forms of 1 kind, namely delta crystal form, and the three-dimensional tunnel structure has 1 kind, namely lambda crystal form) and more than 30 kinds of paracrystals [ Xixi, crystal structure, preparation and discharge performance (1) of manganese dioxide and related manganese oxides [ J xi, J]Battery 2004,6 (34): 411-414]. MnO of different crystal forms 2 Are substantially identical, but differ greatly in their properties due to differences in lattice structure and unit cell parameters, i.e., geometry and size.
According to the preparation method, manganese dioxide can be classified into Natural Manganese Dioxide (NMD) and synthetic manganese dioxide, and the synthetic manganese dioxide can be classified into Electrolytic Manganese Dioxide (EMD) and chemically synthetic manganese dioxide (CMD). The preparation methods of manganese dioxide are various, mainly including sol-gel method, electrochemical deposition method, rheological phase reaction method, micro-emulsion method, hydrothermal synthesis method, coprecipitation method, liquid phase method, template method, solid phase synthesis method and the like, and the method adopted by each type of manganese dioxide is different, and manganese dioxide with different crystal forms can be prepared by the same preparation method.
Chinese patent application publication No. CN111268735A discloses a method for preparing flaky manganese dioxide, which comprises dissolving ammonium persulfate in sodium hydroxide solution and/or potassium hydroxide solution, adding manganese salt under stirring, and reacting to obtain a precursor; calcining the precursor to obtain sheet manganese dioxide with a crystal structure of beta phase, wherein the sheet manganese dioxide needs to be calcined and has the defect of long reaction time; chinese patent application publication No. CN114835166A discloses a method for preparing layered chemical manganese dioxide, comprising: purifying, crystallizing and pretreating a manganese sulfate solution to obtain a pretreated manganese sulfate crystal; dissolving the pretreated manganese sulfate crystals in deionized water, and magnetically stirring for a period of time under the ice bath condition to obtain a mixed solution A; adding an ammonium bicarbonate solution into the obtained mixed solution A, continuing to magnetically stir for a period of time under the ice bath condition, and carrying out solid-liquid separation to obtain a mixed solution B; and (2) carrying out microwave heating on the mixed solution B, carrying out suction filtration, washing the precipitate by using distilled water, and drying the washed precipitate to obtain the layered chemical manganese dioxide.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a novel method for preparing flaky manganese dioxide, which has the characteristics of simple operation, short reaction time and high yield.
The invention solves the technical problems through the following technical means:
a method for preparing flaky manganese dioxide by a continuous flow microwave method comprises the following steps:
s1, mixing a divalent manganese salt, a heptavalent manganese salt, alkali and water to obtain a mixed solution; wherein the molar ratio of the base to the heptavalent manganese salt is > 1:2;
s2, injecting the mixed solution into a microwave chemical reactor to perform continuous flow microwave reaction, flowing out of the microwave chemical reactor, filtering and drying to obtain the flaky manganese dioxide; wherein the power of the microwave chemical reactor is more than or equal to 300W, and the injection speed of the mixed liquid is less than or equal to 10mL/min.
Has the beneficial effects that: the method is a novel method for preparing the flaky manganese dioxide, and has the characteristics of simple operation, short reaction time, high yield and good product quality.
Preferably, in S1, the mass ratio of the divalent manganese salt to the heptavalent manganese salt is 1.5.
Preferably, in S1, the divalent manganese salt is one or more of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
Preferably, in S1, the heptavalent manganese salt is one or a mixture of potassium permanganate and sodium permanganate.
Preferably, the heptavalent manganese salt is potassium permanganate.
Preferably, in S1, the base is one or a mixture of more of sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, ammonia water, and lithium hydroxide.
Preferably, in S1, a manganous salt is dissolved in water to obtain a manganous salt solution; dissolving a heptavalent manganese salt in an aqueous solution of alkali to obtain a heptavalent manganese salt solution; and mixing the divalent manganese salt solution and the heptavalent manganese salt solution to obtain a mixed solution.
Preferably, the alkali aqueous solution is one of a sodium hydroxide aqueous solution with the mass fraction of 2.0%, a potassium hydroxide aqueous solution with the mass fraction of 2.0% and an ammonia aqueous solution with the mass fraction of 28%.
Preferably, in S2, the power of the microwave chemical reactor is 300-600W.
Preferably, in S2, the microwave chemical reactor is flowed out after being left for 1min or more in the microwave chemical reactor.
The invention also provides flaky manganese dioxide prepared by the method for preparing flaky manganese dioxide by the continuous flow microwave method.
The invention has the advantages that:
the method is a novel method for preparing the flaky manganese dioxide, reactants can continuously react through a microwave cavity, the reaction is not limited by a reactor, and the method has the characteristics of simple operation, short reaction time, high yield and good product quality.
Drawings
FIG. 1 is an internal view of a microwave chemical reactor apparatus used in an embodiment of the present invention;
FIG. 2 is a diagram of a donut-shaped glass tube inside a microwave chemical reactor used in an embodiment of the present invention;
FIG. 3 is a TEM spectrum of manganese dioxide flakes prepared in example 4 of the present invention;
FIG. 4 is a TEM spectrum of manganese dioxide prepared in comparative example 4 of the present invention;
fig. 5 is a TEM spectrum of manganese dioxide prepared in comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
The microwave chemical reactor adopted in the embodiment of the invention is a WBFY-205 microwave chemical reactor, which is produced by Zyguy instruments of China, and the internal diagram of the microwave chemical reactor is shown in figure 1, and the internal annular glass tube is shown in figure 2.
Example 1
A method for preparing flaky manganese dioxide by a continuous flow microwave method comprises the following steps:
weighing 25.4g (0.15 mol) of manganese sulfate monohydrate, and dissolving the manganese sulfate monohydrate in 150mL of water to obtain a manganese sulfate solution; weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 150g of sodium hydroxide aqueous solution with the mass fraction of 2.0 percent to obtain a potassium permanganate solution; mixing a manganese sulfate solution and a potassium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 300W, enabling the mixed solution to flow into an annular glass tube in the microwave chemical reactor by adopting the peristaltic pump, enabling the solid manganese dioxide and the reaction solution to flow out of the microwave chemical reactor together after flowing for 1 minute, filtering and drying to obtain 16.1g of flaky manganese dioxide, wherein the yield is 74.2%.
Example 2
A method for preparing flaky manganese dioxide by a continuous flow microwave method comprises the following steps:
weighing 25.4g (0.15 mol) of manganese sulfate monohydrate, and dissolving the manganese sulfate monohydrate in 150mL of water to obtain a manganese sulfate solution; weighing 15.8g (0.1 mol) of potassium permanganate, and dissolving the potassium permanganate in 150g of sodium hydroxide aqueous solution with the mass fraction of 2.0% to obtain a potassium permanganate solution; mixing a manganese sulfate solution and a potassium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 400W, enabling the mixed solution to flow into an annular glass tube in the microwave chemical reactor by adopting the peristaltic pump, flowing the solid manganese dioxide and the reaction liquid out of the microwave chemical reactor together for 1 minute, filtering and drying to obtain 18.6g of flaky manganese dioxide, wherein the yield is 85.7%.
Example 3
A method for preparing flaky manganese dioxide by a continuous flow microwave method comprises the following steps:
weighing 25.4g (0.15 mol) of manganese sulfate monohydrate, and dissolving the manganese sulfate monohydrate in 150mL of water to obtain a manganese sulfate solution; weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 150g of sodium hydroxide aqueous solution with the mass fraction of 2.0 percent to obtain a potassium permanganate solution; mixing a manganese sulfate solution and a potassium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 500W, enabling the mixed solution to flow into an annular glass tube in the microwave chemical reactor by adopting the peristaltic pump, enabling the solid manganese dioxide and the reaction solution to flow out of the microwave chemical reactor together after flowing for 1 minute, filtering and drying to obtain 20.9g of flaky manganese dioxide, wherein the yield is 96.3%.
Example 4
A method for preparing flaky manganese dioxide by a continuous flow microwave method comprises the following steps:
weighing 25.4g (0.15 mol) of manganese sulfate monohydrate, and dissolving the manganese sulfate monohydrate in 150mL of water to obtain a manganese sulfate solution; weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 150g of sodium hydroxide aqueous solution with the mass fraction of 2.0 percent to obtain a potassium permanganate solution; mixing a manganese sulfate solution and a potassium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 600W, enabling the mixed solution to flow into an annular glass tube in the microwave chemical reactor by adopting the peristaltic pump, enabling the solid manganese dioxide and the reaction liquid to flow out of the microwave chemical reactor together after flowing for 1 minute, filtering and drying to obtain 21.0g of flaky manganese dioxide, wherein the yield is 96.8%; the TEM spectrum of the prepared manganese dioxide flakes is shown in fig. 3, and it can be seen from fig. 3 that the prepared manganese dioxide flakes have a thin and thin structure.
Example 5
A method for preparing flaky manganese dioxide by a continuous flow microwave method comprises the following steps:
weighing 18.9g (0.15 mol) of manganese chloride and dissolving in 150mL of water to obtain a manganese chloride solution; weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 150g of sodium hydroxide aqueous solution with the mass fraction of 2.0 percent to obtain a potassium permanganate solution; mixing a manganese chloride solution and a potassium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 500W, enabling the mixed solution to flow into an annular glass tube in the microwave chemical reactor by adopting the peristaltic pump, flowing the solid manganese dioxide and the reaction liquid out of the microwave chemical reactor together for 1 minute, filtering and drying to obtain 20.5g of flaky manganese dioxide, wherein the yield is 94.5%.
Example 6
A method for preparing flaky manganese dioxide by a continuous flow microwave method comprises the following steps:
weighing 26.8g (0.15 mol) of manganese nitrate, and dissolving the manganese nitrate in 150mL of water to obtain a manganese nitrate solution; weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 150g of sodium hydroxide aqueous solution with the mass fraction of 2.0 percent to obtain a potassium permanganate solution; mixing a manganese nitrate solution and a potassium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 500W, enabling the mixed solution to flow into an annular glass tube in the microwave chemical reactor by adopting the peristaltic pump, enabling the solid manganese dioxide and the reaction solution to flow out of the microwave chemical reactor together after flowing for 1 minute, filtering and drying to obtain 20.8g of flaky manganese dioxide, wherein the yield is 95.9%.
Example 7
A method for preparing flaky manganese dioxide by a continuous flow microwave method comprises the following steps:
weighing 38.1g (0.15 mol) of manganese acetate tetrahydrate, and dissolving the manganese acetate tetrahydrate in 150mL of water to obtain a manganese acetate solution; weighing 15.8g (0.1 mol) of potassium permanganate, and dissolving the potassium permanganate in 150g of sodium hydroxide aqueous solution with the mass fraction of 2.0% to obtain a potassium permanganate solution; mixing a manganese acetate solution and a potassium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 500W, enabling the mixed solution to flow into an annular glass tube in the microwave chemical reactor by adopting the peristaltic pump, flowing the solid manganese dioxide and the reaction liquid out of the microwave chemical reactor together for 1 minute, filtering and drying to obtain 20.2g of flaky manganese dioxide, wherein the yield is 93.1%.
Example 8
A method for preparing flaky manganese dioxide by a continuous flow microwave method comprises the following steps:
weighing 25.4g (0.15 mol) of manganese sulfate monohydrate, and dissolving the manganese sulfate monohydrate in 150mL of water to obtain a manganese sulfate solution; weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 150g of potassium hydroxide aqueous solution with the mass fraction of 2.0% to obtain a potassium permanganate solution; mixing a manganese sulfate solution and a potassium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 700W, enabling the mixed solution to flow into an annular glass tube in the microwave chemical reactor by adopting the peristaltic pump, flowing the solid manganese dioxide and the reaction liquid out of the microwave chemical reactor together for 1 minute, filtering and drying to obtain 21.0g of flaky manganese dioxide, wherein the yield is 96.7%.
Example 9
A method for preparing flaky manganese dioxide by a continuous flow microwave method comprises the following steps:
weighing 25.4g (0.15 mol) of manganese sulfate monohydrate, and dissolving the manganese sulfate monohydrate in 150mL of water to obtain a manganese sulfate solution; weighing 14.2g (0.1 mol) of sodium permanganate and dissolving the sodium permanganate in 200g of sodium hydroxide aqueous solution with the mass fraction of 2.0% to obtain sodium permanganate solution; mixing a manganese sulfate solution and a sodium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 500W, enabling the mixed solution to flow into an annular glass tube in the microwave chemical reactor by adopting the peristaltic pump, enabling the solid manganese dioxide and the reaction solution to flow out of the microwave chemical reactor together after flowing for 1 minute, filtering and drying to obtain 20.7g of flaky manganese dioxide, wherein the yield is 95.3%.
Example 10
A method for preparing flaky manganese dioxide by a continuous flow microwave method comprises the following steps:
weighing 25.4g (0.15 mol) of manganese sulfate monohydrate, and dissolving the manganese sulfate monohydrate in 150mL of water to obtain a manganese sulfate solution; weighing 15.8g (0.1 mol) of potassium permanganate, and dissolving the potassium permanganate in 150g of 28 mass percent ammonia water solution to obtain a potassium permanganate solution; mixing a manganese sulfate solution and a potassium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 500W, enabling the mixed solution to flow into an annular glass tube in the microwave chemical reactor by adopting the peristaltic pump, flowing the solid manganese dioxide and the reaction liquid out of the microwave chemical reactor together for 1 minute, filtering and drying to obtain 20.1g of flaky manganese dioxide, wherein the yield is 92.8%.
Example 11
The only difference from example 10 is that: the flow rate is set to be 5mL/min; to obtain 20.5g of flaky manganese dioxide, the yield was 94.5%.
Example 12
The only difference from example 10 is that: the flow rate is set to be 3mL/min; 21.1g of flaky manganese dioxide was obtained in a yield of 97.2%.
Example 13
The only difference from example 4 is that: weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 200g of sodium hydroxide aqueous solution with the mass fraction of 2.0% to obtain a potassium permanganate solution; manganese dioxide of a lamellar structure was obtained in a yield of 96.5%.
Example 14
The only difference from example 4 is that: weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 250g of sodium hydroxide aqueous solution with the mass fraction of 2.0 percent to obtain a potassium permanganate solution; manganese dioxide of a lamellar structure was obtained with a yield of 95.6%.
Example 15
The only difference from example 4 is that: weighing 15.8g (0.1 mol) of potassium permanganate, and dissolving the potassium permanganate in 300g of sodium hydroxide aqueous solution with the mass fraction of 2.0% to obtain a potassium permanganate solution; manganese dioxide with a plate-like structure was obtained in a yield of 96.2%.
Example 16
The difference from example 4 is that: the power was set at 800W to obtain 21.0g of flake manganese dioxide with a yield of 96.8%.
Comparative example 1
Weighing 25.4g (0.15 mol) of manganese sulfate monohydrate, and dissolving the manganese sulfate monohydrate in 150mL of water to obtain a manganese sulfate solution; weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 100g of sodium hydroxide aqueous solution with the mass fraction of 2.0 percent to obtain a potassium permanganate solution; mixing a manganese sulfate solution and a potassium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 500W, enabling the mixed solution to flow into a ring-shaped glass tube in the microwave chemical reactor by using the peristaltic pump, flowing the solid manganese dioxide out of the microwave chemical reactor together with the reaction liquid for 1 minute, filtering and drying to obtain 20.5g of manganese dioxide mixed in a sheet shape and a column shape, wherein the yield is 94.5%, and a TEM image of the manganese dioxide is shown in a figure 5, and the manganese dioxide prepared is mixed in the sheet shape and the column shape according to the knowledge of the figure 5.
Comparative example 2
Weighing 25.4g (0.15 mol) of manganese sulfate monohydrate, and dissolving the manganese sulfate monohydrate in 200mL of water to obtain a manganese sulfate solution; weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 150g of sodium hydroxide aqueous solution with the mass fraction of 1.0% to obtain a potassium permanganate solution; mixing a manganese sulfate solution and a potassium permanganate solution to obtain a mixed solution; starting a peristaltic pump, setting the flow rate to be 10mL/min, starting the microwave chemical reactor, setting the power to be 500W, enabling the mixed solution to flow into an annular glass tube in the microwave chemical reactor by adopting the peristaltic pump, flowing the solid manganese dioxide and the reaction liquid out of the microwave chemical reactor together for 1 minute, filtering and drying to obtain 20.3g of non-flaky manganese dioxide, wherein the yield is 93.5%.
Comparative example 3
The difference from example 4 is that: the power was set at 200W to obtain 13.6g of manganese dioxide in a non-plate structure at a yield of 62.7%.
Comparative example 4
The difference from example 4 is that: weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 50g of sodium hydroxide aqueous solution with the mass fraction of 2.0 percent to obtain a potassium permanganate solution; manganese dioxide with a non-flaky structure is obtained, and the yield is 91.5%; the TEM spectrum of the prepared non-flaky manganese dioxide is shown in FIG. 4, and it can be seen from FIG. 4 that it is columnar.
Comparative example 5
The difference from example 4 is that: weighing 15.8g (0.1 mol) of potassium permanganate and dissolving the potassium permanganate in 100g of sodium hydroxide aqueous solution with the mass fraction of 2.0 percent to obtain a potassium permanganate solution; manganese dioxide of a non-lamellar structure was obtained with a yield of 93.8%.
From the above examples and comparative examples it can be seen that: when the amount of sodium hydroxide (2.0%) is less than 150g, the product obtained is non-manganese dioxide, 150g of sodium hydroxide with a content of 2.0% being suitable for this experiment.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing flaky manganese dioxide by a continuous flow microwave method is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing a divalent manganese salt, a heptavalent manganese salt, alkali and water to obtain a mixed solution; wherein the molar ratio of the base to the heptavalent manganese salt is > 1;
s2, injecting the mixed solution into a microwave chemical reactor to perform continuous flow microwave reaction, flowing out of the microwave chemical reactor, filtering and drying to obtain the flaky manganese dioxide; wherein the power of the microwave chemical reactor is more than or equal to 300W, and the injection speed of the mixed liquid is less than or equal to 10mL/min.
2. The continuous-flow microwave process for preparing manganese dioxide flakes according to claim 1, wherein: in S1, the mass ratio of the divalent manganese salt to the heptavalent manganese salt is 1.5.
3. The continuous-flow microwave process for preparing manganese dioxide flakes according to claim 1, wherein: in S1, the divalent manganese salt is one or a mixture of manganese sulfate, manganese chloride, manganese nitrate and manganese acetate.
4. The continuous-flow microwave process for preparing manganese dioxide flakes according to claim 1, wherein: in S1, the heptavalent manganese salt is one or a mixture of potassium permanganate and sodium permanganate.
5. The method of claim 1, wherein the step of preparing manganese dioxide flakes comprises: in S1, the alkali is one or a mixture of more of sodium hydroxide, calcium hydroxide, potassium hydroxide, barium hydroxide, ammonia water and lithium hydroxide.
6. The method of claim 1, wherein the step of preparing manganese dioxide flakes comprises: in S1, dissolving a divalent manganese salt in water to obtain a divalent manganese salt solution; dissolving a heptavalent manganese salt in an aqueous solution of alkali to obtain a heptavalent manganese salt solution; and mixing the divalent manganese salt solution and the heptavalent manganese salt solution to obtain a mixed solution.
7. The continuous-flow microwave process of claim 6, wherein the manganese dioxide flake is prepared by: the alkali aqueous solution is one of a sodium hydroxide aqueous solution with the mass fraction of 2.0%, a potassium hydroxide aqueous solution with the mass fraction of 2.0% and an ammonia aqueous solution with the mass fraction of 28%.
8. The continuous-flow microwave process for preparing manganese dioxide flakes according to claim 1, wherein: in S2, the power of the microwave chemical reactor is 300-600W.
9. The continuous-flow microwave process for preparing manganese dioxide flakes according to any one of claims 1 to 8, wherein: in S2, the mixture flows out of the microwave chemical reactor after being left in the microwave chemical reactor for more than or equal to 1 min.
10. A flaky manganese dioxide characterized by: prepared by a method for preparing manganese dioxide flakes according to the continuous-flow microwave method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211443253.7A CN115744995A (en) | 2022-11-17 | 2022-11-17 | Method for preparing flaky manganese dioxide by continuous flow microwave method and prepared flaky manganese dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211443253.7A CN115744995A (en) | 2022-11-17 | 2022-11-17 | Method for preparing flaky manganese dioxide by continuous flow microwave method and prepared flaky manganese dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115744995A true CN115744995A (en) | 2023-03-07 |
Family
ID=85373013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211443253.7A Pending CN115744995A (en) | 2022-11-17 | 2022-11-17 | Method for preparing flaky manganese dioxide by continuous flow microwave method and prepared flaky manganese dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115744995A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502853A (en) * | 2011-12-18 | 2012-06-20 | 中国科学院电工研究所 | Method for preparing nanometer manganese dioxide by microwave reflux method |
| CN111268735A (en) * | 2020-02-12 | 2020-06-12 | 广东工业大学 | Flaky manganese dioxide and preparation method and application thereof |
| CN113964300A (en) * | 2021-09-15 | 2022-01-21 | 广东邦普循环科技有限公司 | Layered sodium-ion battery positive electrode material and preparation method thereof |
| JP7038455B1 (en) * | 2021-11-04 | 2022-03-18 | 日本重化学工業株式会社 | Manganese dioxide and its manufacturing method |
-
2022
- 2022-11-17 CN CN202211443253.7A patent/CN115744995A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102502853A (en) * | 2011-12-18 | 2012-06-20 | 中国科学院电工研究所 | Method for preparing nanometer manganese dioxide by microwave reflux method |
| CN111268735A (en) * | 2020-02-12 | 2020-06-12 | 广东工业大学 | Flaky manganese dioxide and preparation method and application thereof |
| CN113964300A (en) * | 2021-09-15 | 2022-01-21 | 广东邦普循环科技有限公司 | Layered sodium-ion battery positive electrode material and preparation method thereof |
| JP7038455B1 (en) * | 2021-11-04 | 2022-03-18 | 日本重化学工業株式会社 | Manganese dioxide and its manufacturing method |
Non-Patent Citations (3)
| Title |
|---|
| MARTIN ECKERT等: "Fast Microwave-Assisted Hydrothermal Synthesis of Pure Layered δ-MnO2 for Multivalent Ion Intercalation", 《MATERIALS》, vol. 11, no. 2399, 28 November 2018 (2018-11-28), pages 2 - 18 * |
| MARTIN ECKERT等: "Fast Microwave-Assisted Hydrothermal Synthesis of Pure Layered δ-MnO2 for Multivalent Ion Intercalation", 《MATERIALS》, vol. 11, no. 2399, pages 1 - 18 * |
| NAFTALI N.OPEMBE等: "Microwave-assisted synthesis of manganese oxide octahedral molecular sieve(OMS-2) Nanomaterials under continuous flow conditions", 《J.PHYS.CHEM.C》, vol. 114, 8 June 2010 (2010-06-08), pages 14417 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110451525B (en) | Method for rapidly preparing Prussian blue analogue with monoclinic crystal structure | |
| CN112209409B (en) | Method for rapidly preparing Prussian white serving as positive electrode material of sodium-ion battery | |
| CN109422297B (en) | Method for regulating and controlling nucleation in crystallization process of nickel-cobalt-manganese precursor | |
| CN108011101A (en) | A kind of big uniform particle sizes mix the preparation method of aluminium cobaltosic oxide | |
| CN110217832A (en) | A kind of bulky grain narrow ditribution mixes the preparation method of aluminium cobaltosic oxide | |
| CN108455686B (en) | Preparation method of niobium-doped tungsten tantalum cobaltosic oxide | |
| CN112939095B (en) | Spherical high-nickel cobalt-free single crystal precursor and preparation method thereof | |
| CN102299299A (en) | Preparation method for aluminum-cladded lithium ion battery anode material | |
| CN102306751B (en) | The preparation method of wet-processed aluminium-coated lithium ion battery cathode material | |
| CN105810925A (en) | Small-particle-size nickel-cobalt-aluminum oxide and preparation method thereof | |
| CN101293677A (en) | Method for preparing cobaltic-cobaltous oxide powder with octahedron shape | |
| CN110112386B (en) | Preparation method of high-nickel ternary positive electrode precursor | |
| CN104649336B (en) | A kind of preparation method of spherical nickel-cobalt aluminium hydroxide presoma | |
| CN105742568B (en) | A kind of nickel cobalt aluminum oxide and preparation method thereof | |
| NO319152B1 (en) | Spheroidally agglomerated basic cobalt (II) carbonates, spheroidally agglomerated cobalt (II) hydroxides, and processes for the preparation and use thereof | |
| KR20130055692A (en) | Manganese oxide and method for producing same, and method for producing lithium manganese composite oxide using same | |
| CN111732131B (en) | Preparation method of core-shell structure ternary cathode material | |
| CN108439489A (en) | A kind of preparation method of high jolt ramming battery-grade cobaltosic oxide | |
| CN107732232A (en) | A kind of preparation method of Hydrothermal Synthesiss nickel-cobalt lithium manganate cathode material | |
| CN104108749A (en) | Preparing method of doped strontium titanate | |
| CN113571694B (en) | Multi-ion modified ternary material precursor and preparation method of anode material | |
| CN108264096A (en) | A kind of preparation method of high density little particle nickel cobalt manganese hydroxide | |
| CN113772748A (en) | Preparation method of lithium ion battery anode material | |
| CN116239161A (en) | Nickel-iron-manganese ternary precursor, preparation method and sodium ion battery anode material | |
| CN111697235A (en) | NCMA quaternary gradient material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |