CN110759384A - Method for preparing spheroidal manganous manganic oxide by manganese sulfate solution - Google Patents
Method for preparing spheroidal manganous manganic oxide by manganese sulfate solution Download PDFInfo
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- CN110759384A CN110759384A CN201911087945.0A CN201911087945A CN110759384A CN 110759384 A CN110759384 A CN 110759384A CN 201911087945 A CN201911087945 A CN 201911087945A CN 110759384 A CN110759384 A CN 110759384A
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- sulfate solution
- manganese sulfate
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- 229940099596 manganese sulfate Drugs 0.000 title claims abstract description 44
- 235000007079 manganese sulphate Nutrition 0.000 title claims abstract description 44
- 239000011702 manganese sulphate Substances 0.000 title claims abstract description 44
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 42
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 28
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 26
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 26
- 239000011572 manganese Substances 0.000 claims abstract description 20
- 239000012535 impurity Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 6
- 239000007800 oxidant agent Substances 0.000 claims abstract description 6
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- -1 iron ions Chemical class 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000003570 air Substances 0.000 claims description 5
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 4
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 2
- 239000001433 sodium tartrate Substances 0.000 claims description 2
- 229960002167 sodium tartrate Drugs 0.000 claims description 2
- 235000011004 sodium tartrates Nutrition 0.000 claims description 2
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 56
- 239000002245 particle Substances 0.000 description 27
- 229910052748 manganese Inorganic materials 0.000 description 14
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000004626 scanning electron microscopy Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000003921 particle size analysis Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- 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
- C01P2006/11—Powder tap density
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- 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
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- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention discloses a method for preparing spheroidal manganous manganic oxide by a manganese sulfate solution, which comprises the following steps: dissolving electrolytic manganese metal sheets, and removing impurities and purifying to obtain a manganese sulfate solution with low impurity content; adding a manganese sulfate solution, ammonia water and an additive into a reaction kettle in parallel, adding sufficient oxidant under the stirring condition, and carrying out one-step oxidation at the reaction temperature of 50-90 ℃; and after the manganese sulfate solution is added, continuously adding ammonia water for 6-10 hours, controlling the pH value of the reaction system to be 4.5-9.5, stopping adding ammonia water, continuously stirring, preserving heat and aging for 4-20 hours, filtering and washing the product, and drying at 120 ℃ to obtain the spheroidal manganous manganic oxide. The sphere-like manganous-manganic oxide D50 prepared by the invention is 4-20 mu m, and the tap density is more than or equal to 2.0g/cm3And the Mn content is more than or equal to 70.5 percent. The method has simple process flow and low production cost, and is easy to realize industrial production.
Description
Technical Field
The invention relates to a method for preparing spheroidal manganous manganic oxide by using manganese oxide and a manganese sulfate solution thereof, in particular to a method for preparing spheroidal manganous manganic oxide by using a manganese sulfate solution.
Background
The lithium ion battery has the characteristics of high output voltage, high energy density, long cycle life, no memory effect and the like, and is widely applied to the fields of electronic equipment, electric automobiles, energy storage batteries and the like. In recent years, with the development of green industries such as new energy automobiles, the market demand of positive electrode materials of power lithium ion batteries is gradually increasing.
The lithium manganate is one of the most potential power lithium ion battery positive electrode materials at present, and has the remarkable advantages of rich storage, low price, high safety performance, no environmental pollution and the like. At present, the lithium manganate is mainly produced by taking electrolytic manganese dioxide as a manganese source and sintering the manganese source, lithium carbonate and corresponding additives in a solid phase manner, and the problems of low gram specific capacity, poor cycle performance, poor high-temperature performance and the like exist, mainly because electrolytic manganese dioxide particles are poor in appearance, generally are amorphous particles, are uneven in particle size distribution and high in impurity content, and various indexes such as the particle size, appearance, impurity content and the like of the manganese source directly influence the electrical performance of the lithium manganate material. The manganous-manganic oxide and the lithium manganate have the same spinel structure, spherical manganous-manganic oxide and lithium carbonate with low impurity content are used as raw materials, violent structural change does not exist in the process of synthesizing the lithium manganate through solid-phase reaction, the caused internal stress is smaller, the crystal structure of the material is more stable, and the prepared lithium manganate has more excellent electrical property. Compared with the lithium manganate synthesized by taking electrolytic manganese dioxide as a manganese source, the lithium manganate synthesized by taking manganous-manganic oxide as the manganese source has the advantages that the battery capacity, the cycle performance and the like are obviously improved. Therefore, the production of lithium manganate by using trimanganese tetroxide instead of electrolytic manganese dioxide is a current development trend.
The manganous manganic oxide is used as a main raw material for preparing the lithium manganate serving as the cathode material of the lithium ion battery, and various indexes such as tap density, granularity, micro morphology, impurity content and the like can influence the performance of the lithium manganate. At present, the method for preparing spheroidal manganous manganic oxide by using a main manganese sulfate solution of manganous manganic oxide mainly comprises a metal manganese suspension oxidation method, a high-valence manganese oxidation method, a manganese carbonate salt method and a manganese salt hydrothermal oxidation method. At present, the domestic preparation of mangano-manganic oxide mostly adopts a metal manganese powder suspension oxidation method, and the process flow is as follows: adding metal manganese powder with a certain particle size range into deionized water to prepare suspension with a certain solid-to-liquid ratio, adding ammonium salt as a catalyst, and introducing air for oxidation under a heating condition to prepare the trimanganese tetroxide. The process is mature and simple, but is greatly influenced by raw materials, the production cost is high, and the impurity content is high. In recent years, a method for preparing trimanganese tetroxide by hydrolysis, precipitation and oxidation of a manganese sulfate solution in an alkaline medium is studied successively, and the technical process comprises the following steps: hydrolyzing manganese ions in the manganese salt solution by using alkali to precipitate manganese hydroxide, and adding an oxidant to oxidize to prepare the trimanganese tetroxide. The process has low cost and easy operation, but the prepared manganous-manganic oxide has large specific surface area, irregular shape, low tap density, easy generation of basic manganese sulfate, difficult control of reaction and long reaction time.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process for preparing spheroidal trimanganese tetroxide by using a manganese sulfate solution, which is simple to operate and low in production cost, and the produced spheroidal trimanganese tetroxide has uniform particle size distribution, high tap density and low impurity content.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for preparing spheroidal manganous manganic oxide by a manganese sulfate solution comprises the following steps:
(1) dissolving: adding an electrolytic manganese metal sheet and deionized water into a dissolving tank according to the weight ratio of 1: 5-20, adding 98% industrial concentrated sulfuric acid into the dissolving tank for reaction, wherein the weight ratio of the electrolytic manganese metal sheet to the industrial concentrated sulfuric acid is 1: 1.8-2.0;
(2) primary impurity removal: adjusting the pH value of the solution obtained in the step (1) to 3.0-5.5 by using manganese powder, adding hydrogen peroxide to remove iron ions, and uniformly stirring, wherein the using amount of the hydrogen peroxide is 100-120 wt% of the theoretical using amount;
(3) secondary impurity removal: adding a vulcanizing agent into the solution obtained in the step (2) to remove heavy metal ions, and uniformly stirring, wherein the consumption of the vulcanizing agent is 100-120 wt% of the theoretical consumption;
(4) and (3) filtering: filtering the solution obtained in the step (3) to obtain a manganese sulfate solution;
(5) and (3) oxidation: adding deionized water into a reaction kettle to serve as a base solution, and heating to 50-90 ℃ in a water bath; under the stirring condition, the stirring speed is 150-500 r/min, the manganese sulfate solution, the ammonia water and the additive solution obtained in the step (4) are added into a reaction kettle in a parallel flow mode, and meanwhile, an oxidant is added for oxidation; in the reaction process, controlling the pH value of a reaction system to be 4.5-9.5 by adjusting the adding amount of ammonia water, reacting for 4-10 h, stopping adding ammonia water after the reaction is finished, continuing stirring, and preserving heat and aging for 4-20 h;
(6) washing and drying: and (5) filtering the solution obtained in the step (5), taking filter residues, washing, and drying for 6-15 hours at the temperature of 120 ℃ to obtain the spheroidal manganous manganic oxide.
In the above technical solution, as a preferable mode, the content of both calcium and magnesium in the electrolytic manganese metal sheet in the step (1) is not more than 0.02 wt%.
In the above technical solution, as a preferable mode, the vulcanizing agent in the step (3) is one or two of sodium dimethyl dithiocarbamate, ammonium sulfide and manganese sulfide.
In the above technical solution, preferably, the concentration of the additive in the step (5) is 1 to 50 g/L.
In the above technical solution, as a preferable mode, the additive in the step (5) is one or two of sodium tartrate, ammonium lauryl sulfate, cetyl trimethyl ammonium bromide, cyclopentadimethyl siloxane, TX-10, ethyl acetate, citric acid monohydrate, and polyvinylpyrrolidone.
In the above technical solution, preferably, the concentration of the ammonia water in the step (5) is 1 to 10 mol/L.
In the technical scheme, as a preferable mode, the feeding speed of the manganese sulfate solution in the step (5) is 1-20 mL/min.
In the above technical solution, preferably, the oxidizing agent in the step (5) is any one of air, oxygen and hydrogen peroxide.
In the technical scheme, the granularity index D50 of the prepared spheroidal manganous-manganic oxide is 4-20 mu m, and the tap density is more than or equal to 2.0g/cm3And the Mn content is more than or equal to 70.5 percent.
In the technical scheme, the additive is added to better control the spheroidal manganomanganic oxide particles, the growth of crystal faces can be promoted or inhibited through the selective adsorption of the additive on the crystal surface, and the surface state of crystal nuclei in the oxidation process is changed, so that the size and the microstructure of the manganomanganic oxide particles are regulated and controlled, and the manganomanganic oxide particles can be favorably formed into the spheroidal manganomanganic oxide particles with uniform particle size distribution.
Has the advantages that: the invention relates to a method for preparing spheroidal manganous manganic oxide by manganese sulfate solution, which is characterized in that electrolytic metal manganese sheets are dissolved, impurity removal and purification are carried out to prepare the manganese sulfate solution with low impurity content, the manganese sulfate solution is used for preparing the manganous manganic oxide with controllable granularity by a one-step oxidation method, the impurity content of a product is obviously reduced by controlling the impurity content of raw materials and carrying out impurity removal and purification treatment, and the prepared spheroidal manganous manganic oxide particles have uniform and controllable granularity distribution, high tap density and low specific surface area. The process is simple to operate, low in production cost and easy to realize industrial production.
Drawings
FIG. 1 is an XRD pattern of spheroidal trimanganese tetroxide prepared in example 1 of the present invention.
FIG. 2 is an SEM photograph of spheroidal mangano-manganic oxide prepared in example 1 of the invention.
FIG. 3 is a graph showing the particle size distribution of spheroidal manganomanganic oxide prepared in example 1 of the present invention.
FIG. 4 is an XRD pattern of spheroidal trimanganese tetroxide prepared in example 2 of the present invention.
FIG. 5 is an SEM photograph of spheroidal mangano-manganic oxide prepared in example 2 of the invention.
FIG. 6 is a graph showing the particle size distribution of spheroidal manganomanganic oxide prepared in example 2 of the present invention.
FIG. 7 is an XRD pattern of spheroidal trimanganese tetroxide prepared in example 3 of the present invention.
FIG. 8 is an SEM photograph of spheroidal mangano-manganic oxide prepared in example 3 of the invention.
FIG. 9 is a graph showing the particle size distribution of spheroidal manganomanganic oxide prepared in example 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
(1) adding 110g of electrolytic metal manganese pieces and 2000mL of pure water into a dissolving tank, adding 110mL of industrial concentrated sulfuric acid with the mass percent of 98% into the dissolving tank for reaction, adjusting the pH value of the solution to 3.0-4.0 by using manganese powder after the manganese pieces are dissolved, adding 5mL of hydrogen peroxide, stirring for 30min, adding 0.5g of ammonium sulfide, continuing stirring for 30min, and finally filtering to obtain a manganese sulfate solution;
(2) preparing 2000mL of 2.5mol/L ammonia water and 200mL of 15g/L cyclopentasiloxane solution by using deionized water;
(3) adding deionized water into a reaction kettle to serve as a base solution, wherein the volume of the deionized water just submerges a stirring paddle, and heating in a water bath to 70 ℃; under the condition of stirring, the stirring speed is 300r/min, the manganese sulfate solution, the ammonia water and the cyclopenta dimethyl siloxane solution obtained in the step are added into a reaction kettle in a parallel flow mode, the feeding speed of the manganese sulfate solution is 15mL/min, and the feeding speed of the cyclopenta dimethyl siloxane solution is 1.5mL/min, and the same is true for the manganese sulfate solution, the ammonia water and the cyclopenta dimethyl siloxane solutionAdding oxygen for oxidation at an oxygen flow rate of 0.1m3H; in the reaction process, the pH value of the reaction system is controlled to be 6.5-7.5 by adjusting the adding amount of ammonia water; after the manganese sulfate solution and the cyclopentadienyldimethylsiloxane solution are added, continuously adding ammonia water for 6 hours to maintain the pH value unchanged, then stopping adding the ammonia water, continuously stirring, and preserving heat and aging for 4 hours;
(4) and (4) filtering the product obtained in the step (3), washing the product with deionized water for a plurality of times, putting the product into an oven, and drying the product at 120 ℃ for 10 hours to obtain the spheroidal manganous manganic oxide.
The spheroidal mangano-manganic oxide prepared in the embodiment has the particle diameter D50 of 11.71 mu m and the tap density of 2.35g/cm3And the Mn content was 70.8%. An XRD diffractometer is adopted to determine the crystal structure of the product, and the result is shown in figure 1, the product is pure mangano-manganic oxide, and no impurity phase exists; the microscopic morphology of the particles was analyzed by Scanning Electron Microscopy (SEM), and the particles were spheroidal, with the results shown in FIG. 2; the product was subjected to particle size analysis using a laser particle sizer, and the particle size results are shown in fig. 3.
Example 2:
(1) adding 220g of electrolytic metal manganese sheet and 2000mL of deionized water into a dissolving tank, adding 220mL of industrial concentrated sulfuric acid with the mass percent of 98% into the dissolving tank for reaction, adjusting the pH value of the solution to 3.5-4.5 by adopting manganese powder after the manganese sheet is dissolved, adding 10mL of hydrogen peroxide, stirring for 30min, adding 1.0g of ammonium sulfide, continuing stirring for 30min, and finally filtering to obtain a manganese sulfate solution;
(2) preparing 2000mL of 5.0mol/L ammonia water and 200mL of 20g/L hexadecyl trimethyl ammonium bromide solution by using deionized water;
(3) adding deionized water into a reaction kettle to serve as a base solution, wherein the volume of the deionized water just submerges a stirring paddle, and heating in a water bath to 70 ℃; under the condition of stirring, the stirring speed is 250r/min, the manganese sulfate solution, the ammonia water and the cetyl trimethyl ammonium bromide solution obtained in the step are added into a reaction kettle in a parallel flow mode, the feeding speed of the manganese sulfate solution is 10mL/min, the feeding speed of the cetyl trimethyl ammonium bromide solution is 1.0mL/min, oxygen is added for oxidation, and the oxygen flow is 0.12m3H; in the reaction processIn the process, the pH value of the reaction system is controlled to be 7.5-8.5 by adjusting the adding amount of ammonia water; after the manganese sulfate solution and the hexadecyl trimethyl ammonium bromide solution are added, continuously adding ammonia water for 8 hours to maintain the pH value unchanged, then stopping adding the ammonia water, continuously stirring, and preserving heat and aging for 4 hours;
(4) and (4) filtering the product obtained in the step (3), washing the product with deionized water for a plurality of times, putting the product into an oven, and drying the product at 120 ℃ for 10 hours to obtain the spheroidal manganous manganic oxide.
The trimanganese tetroxide prepared in the example has a particle size D50 of 7.32 μm and a tap density of 2.39g/cm3And the Mn content was 70.6%. An XRD diffractometer is adopted to determine the crystal structure of the product, and the result is shown in figure 4, the product is pure mangano-manganic oxide, and no impurity phase exists; the microscopic morphology of the particles was analyzed by Scanning Electron Microscopy (SEM), and the particles were spheroidal, with the results shown in FIG. 5; the product was subjected to particle size analysis using a laser particle sizer, and the results are shown in FIG. 6.
Example 3:
(1) adding 275g of electrolytic metal manganese pieces and 2000mL of deionized water into a dissolving tank, adding 272mL of industrial concentrated sulfuric acid with the mass percent of 98% into the dissolving tank for reaction, adjusting the pH value of the solution to 4.0-5.0 by adopting manganese powder after the manganese pieces are dissolved, adding 15mL of hydrogen peroxide, stirring for 30min, adding 1.5g of sodium ferbamate, continuously stirring for 30min, and finally filtering to obtain a manganese sulfate solution;
(2) preparing 2000mL of 6mol/L ammonia water and 200mL of 5g/L ethyl acetate solution by using deionized water;
(3) adding deionized water into a reaction kettle to serve as a base solution, wherein the volume of the deionized water just submerges a stirring paddle, and heating in a water bath to 80 ℃; under the condition of stirring, the stirring speed is 300r/min, the manganese sulfate solution, ammonia water and ethyl acetate solution obtained in the above steps are added into a reaction kettle in a cocurrent mode, the feeding speed of the manganese sulfate solution is 18mL/min, the feeding speed of the ethyl acetate solution is 0.8mL/min, air is added for oxidation, and the air flow is 3.5m3H; in the reaction process, the pH value of the reaction system is controlled to be 5.5-6.5 by adjusting the adding amount of ammonia water; after the manganese sulfate solution and the ethyl acetate solution are added, ammonia is continuously addedKeeping the pH value of the water unchanged for 8 hours, then stopping adding ammonia water, continuing stirring, and preserving heat and aging for 4 hours.
(4) And (4) filtering the product obtained in the step (3), washing the product with deionized water for a plurality of times, putting the product into an oven, and drying the product at 120 ℃ for 10 hours to obtain the spheroidal manganous manganic oxide.
The trimanganese tetroxide prepared in the example has a particle size D50 of 4.74 μm and a tap density of 2.05g/cm3And the Mn content was 70.9%. The crystal structure of the product is determined by an XRD diffractometer, and the result is shown in figure 7, and the product is pure mangano-manganic oxide; the microscopic morphology of the particles can be seen to be spheroidal by observation with a Scanning Electron Microscope (SEM), and the result is shown in FIG. 8; the product was subjected to particle size analysis using a laser particle sizer, and the results are shown in FIG. 9.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
1. A method for preparing spheroidal manganous manganic oxide by a manganese sulfate solution comprises the following steps:
(1) dissolving: adding an electrolytic manganese metal sheet and deionized water into a dissolving tank according to the weight ratio of 1: 5-20, adding 98% industrial concentrated sulfuric acid into the dissolving tank for reaction, wherein the weight ratio of the electrolytic manganese metal sheet to the industrial concentrated sulfuric acid is 1: 1.8-2.0;
(2) primary impurity removal: adjusting the pH value of the solution obtained in the step (1) to 3.0-5.5 by using manganese powder, adding hydrogen peroxide to remove iron ions, and uniformly stirring, wherein the using amount of the hydrogen peroxide is 100-120 wt% of the theoretical using amount;
(3) secondary impurity removal: adding a vulcanizing agent into the solution obtained in the step (2) to remove heavy metal ions, and uniformly stirring, wherein the consumption of the vulcanizing agent is 100-120 wt% of the theoretical consumption;
(4) and (3) filtering: filtering the solution obtained in the step (3) to obtain a manganese sulfate solution;
(5) and (3) oxidation: adding deionized water into a reaction kettle to serve as a base solution, and heating to 50-90 ℃ in a water bath; under the stirring condition, the stirring speed is 150-500 r/min, the manganese sulfate solution, the ammonia water and the additive solution obtained in the step (4) are added into a reaction kettle in a parallel flow mode, and meanwhile, an oxidant is added for oxidation; in the reaction process, controlling the pH value of a reaction system to be 4.5-9.5 by adjusting the adding amount of ammonia water, reacting for 4-10 h, stopping adding ammonia water after the reaction is finished, continuing stirring, and preserving heat and aging for 4-20 h;
(6) washing and drying: and (5) filtering the solution obtained in the step (5), taking filter residues, washing, and drying for 6-15 hours at the temperature of 120 ℃ to obtain the spheroidal manganous manganic oxide.
2. The method for preparing spheroidal manganous manganic oxide by using the manganese sulfate solution as claimed in claim 1, wherein the method comprises the following steps: the content of calcium and magnesium in the electrolytic manganese metal sheet in the step (1) is not more than 0.02 wt%.
3. The method for preparing spheroidal manganous manganic oxide by using the manganese sulfate solution as claimed in claim 1, wherein the method comprises the following steps: and (3) the vulcanizing agent in the step (3) is one or two of sodium dimethyl dithiocarbamate, ammonium sulfide and manganese sulfide.
4. The method for preparing spheroidal manganous manganic oxide by using the manganese sulfate solution as claimed in claim 1, wherein the method comprises the following steps: the concentration of the additive in the step (5) is 1-50 g/L.
5. The method for preparing spheroidal manganous manganic oxide by using the manganese sulfate solution as claimed in claim 1, wherein the method comprises the following steps: the additive in the step (5) is one or two of sodium tartrate, ammonium dodecyl sulfate, hexadecyl trimethyl ammonium bromide, cyclopentadimethyl siloxane, TX-10, ethyl acetate, citric acid monohydrate and polyvinylpyrrolidone.
6. The method for preparing spheroidal manganous manganic oxide by using the manganese sulfate solution as claimed in claim 1, wherein the method comprises the following steps: the concentration of the ammonia water in the step (5) is 1-10 mol/L.
7. The method for preparing spheroidal manganous manganic oxide by using the manganese sulfate solution as claimed in claim 1, wherein the method comprises the following steps: and (3) feeding the manganese sulfate solution in the step (5) at a speed of 1-20 mL/min.
8. The method for preparing spheroidal manganous manganic oxide by using the manganese sulfate solution as claimed in claim 1, wherein the method comprises the following steps: the oxidant in the step (5) is any one of air, oxygen and hydrogen peroxide.
9. The method for preparing spheroidal trimanganese tetroxide from a manganese sulfate solution according to any one of claims 1 to 8, wherein the method comprises the following steps: the granularity index D50 of the prepared quasi-spherical manganous-manganic oxide is 4-20 mu m, and the tap density is more than or equal to 2.0g/cm3And the Mn content is more than or equal to 70.5 percent.
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