CN111186862A - Preparation method of battery-grade high-purity trimanganese tetroxide - Google Patents
Preparation method of battery-grade high-purity trimanganese tetroxide Download PDFInfo
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- CN111186862A CN111186862A CN202010124782.5A CN202010124782A CN111186862A CN 111186862 A CN111186862 A CN 111186862A CN 202010124782 A CN202010124782 A CN 202010124782A CN 111186862 A CN111186862 A CN 111186862A
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Abstract
The invention discloses a preparation method of battery-grade high-purity trimanganese tetroxide, which comprises the steps of preparing manganous oxide into slurry, and adding sulfuric acid solution for leaching; adding an impurity removing agent into the manganese sulfate solution to react and remove impurities to obtain high-purity manganese sulfate liquid; adjusting the temperature in the reaction kettle, adding manganese sulfate liquid with certain concentration, ammonia water and oxygen at different speeds respectively, and stirring for reaction; after the reaction is finished, filtering the reaction system, rinsing and drying to obtain manganese tetroxide particles; and separating out spherical particles with uniform size and proper specific gravity and particle size by using a jet mill classifier to obtain the high-purity trimanganese tetroxide. The manganous-manganic oxide prepared by the preparation method has uniform particles, the particle size of the manganous-manganic oxide meets the international standard, the purity of the manganous-manganic oxide is high, and the preparation method is simple and easy to operate.
Description
Technical Field
The invention relates to the technical field of battery material preparation, in particular to a preparation method of battery-grade high-purity trimanganese tetroxide.
Background
The battery-grade high-purity manganous-manganic oxide is a high-quality battery raw material for preparing lithium manganate. Because trimanganese tetroxide and lithium manganate have the same spinel structure in structure. The shape, particle size distribution and specific gravity of the manganous-manganic oxide all influence the stability, safety and cycle performance of the lithium manganate. Therefore, it is necessary to find a preparation method of battery grade high-purity trimanganese tetroxide with high purity, spherical particles, proper particle size distribution and large specific gravity.
At present, domestic manufacturers mainly use electrolytic manganese metal suspension oxidation to prepare trimanganese tetroxide, the method mainly uses electrolytic manganese metal as raw material, grinds the electrolytic manganese metal into suspension, and introduces air to oxidize the suspension to produce trimanganese tetroxide products. The electrolytic manganese metal raw material used by the method is high in price, and the obtained product manganous-manganic oxide has high impurity content, irregular particle appearance and poor performance, and cannot meet the requirements of high-end lithium manganate cathode materials; the other common method for producing mangano-manganic oxide is a manganese salt wet oxidation method, which mainly comprises the steps of firstly adding alkali into manganese salt to convert the manganese salt into manganese hydroxide precipitate, and oxidizing the manganese hydroxide precipitate into mangano-manganic oxide by utilizing air. Therefore, the demand of battery grade high-purity trimanganese tetroxide on the market is difficult to meet.
Disclosure of Invention
The invention aims to: aiming at the problems, the preparation method of the battery-grade high-purity trimanganese tetroxide is provided, and the problems of irregular particle appearance, unqualified particle size, higher impurity content, overlong air oxidation time, lower manganese content of the product and the like in the traditional trimanganese tetroxide preparation process are solved.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of battery-grade high-purity trimanganese tetroxide comprises the following steps:
(1) leaching: adding water into certain mass of manganese monoxide to prepare slurry, and adding a sulfuric acid solution to react to obtain manganese sulfate leachate;
(2) removing impurities: adding an impurity removing agent into the manganese sulfate solution obtained in the step (1), fully mixing uniformly, reacting to remove impurities, and filtering to obtain a high-purity manganese sulfate liquid;
(3) reaction: adjusting the temperature in the reaction kettle, adding manganese sulfate liquid with certain concentration, ammonia water and oxygen at different speeds, and simultaneously keeping a certain stirring speed for stirring reaction;
(4) drying: after the reaction is finished, filtering the reaction system, rinsing and drying to obtain manganese tetroxide particles;
(5) grading: and (4) separating the manganese tetroxide particles in the step (4) by using a jet milling classifier to obtain spherical particles with uniform size and proper specific gravity particle size, returning the rest particles to the step (3) again for reaction, drying and classification, and obtaining the spherical particles meeting the requirements, namely the high-purity trimanganese tetroxide.
Further, in the step (1), the preparation is carried out in such a manner that the solid-to-liquid ratio of the slurry is 1: (2-4), the concentration of the added sulfuric acid solution is 85-98%, and the temperature is 50-80 ℃ when the sulfuric acid solution is added.
Further, in the step (2), the impurity removing agent comprises manganese dioxide, hydrogen peroxide, manganese hydroxide, sodium hydroxide, ammonia water, ammonium sulfide and barium sulfide, the amount of the added impurity removing agent is 1-2% of the mass of manganese monoxide, and the impurities are iron, lead, zinc, copper, nickel, cobalt, cadmium, chromium and other trace heavy metal elements.
Further, in the step (3), the temperature of the reaction kettle is 40-80 ℃, the stirring speed is 500r/min, the manganese concentration of the manganese sulfate is 40-120g/L, the feeding speed of the manganese sulfate is 300-600mL/h, the concentration of the ammonia water is 3-15%, the feeding speed of the ammonia water is 400-700mL/h, the pH value is kept at 7-9, the oxygen flow is 10-30L/h, and the stirring reaction time is 3-6 h.
Further, in the step (4), the rinsing is continuously performed by flowing pure water, and the drying temperature is 60-90 ℃.
Further, in the step (5), the frequency of a pole separating wheel of the jet mill classifier is 60-70HZ, the air pressure is 0.8-1MPa, and the feeding frequency is 2-4 Hz.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
the method uses manganese monoxide as a raw material, ammonia water as a neutralizer to control the pH value in the reaction process, liquid oxygen as an oxidant to carry out oxidation reaction, controls the reaction temperature, reacts for several hours at a certain stirring speed, and after washing, filtering and drying the slurry, battery-grade high-purity trimanganese tetroxide with uniform particle size, qualified particle size and proper specific gravity is sorted out by a jet mill classifier. The method solves the problems of irregular particle appearance, unqualified particle size, high impurity content, overlong air oxidation time, low manganese content of the product and the like of the traditional preparation process of the trimanganese tetroxide, and has the advantages of simple preparation method, easy operation and low energy consumption, and the purity of the prepared trimanganese tetroxide is as high as 99.99 percent.
Drawings
FIG. 1 is a flow chart of the operation of the present invention;
FIG. 2 is an electron microscope image of trimanganese tetroxide prepared in example 3 of the present invention;
FIG. 3 is an electron microscope image of trimanganese tetroxide prepared in example 4 of the present invention;
FIG. 4 is an electron micrograph of trimanganese tetroxide prepared in example 5 of the present invention;
FIG. 5 is an electron micrograph of trimanganese tetroxide prepared in example 6 of the present invention;
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to preferred embodiments. It should be noted, however, that the numerous details set forth in the description are merely for the purpose of providing the reader with a thorough understanding of one or more aspects of the present invention, which may be practiced without these specific details.
Example 1
(1) Leaching: taking 500g of manganese oxide powder of a certain chemical plant of Qinzhou, Guangxi, with the manganese content of 30%, adding water according to the solid-to-liquid ratio of 1: 2, preparing the mixture into slurry, adding 85% sulfuric acid solution, and reacting at 50 ℃ to obtain manganese sulfate leaching solution;
(2) removing impurities: adding impurity-removing agents such as manganese dioxide, hydrogen peroxide, manganese hydroxide, sodium hydroxide, ammonia water, ammonium sulfide, barium sulfide and the like into the manganese sulfate solution obtained in the step (1), wherein the addition amount of the impurity-removing agents is 1% of the mass of manganese monoxide, fully and uniformly mixing, reacting, removing impurities such as lead, zinc, copper, nickel, cobalt, cadmium, chromium and other trace heavy metal elements, and filtering to obtain high-purity manganese sulfate liquid;
(3) reaction: adjusting the temperature in the reaction kettle to 40 ℃, respectively adding manganese sulfate liquid with certain concentration, ammonia water and oxygen at different speeds, wherein the manganese concentration of the manganese sulfate is 40g/L, the feeding speed of the manganese sulfate is 300mL/h, the ammonia water concentration is 3%, the feeding speed of the ammonia water is 400mL/h, the pH is kept at 7, the oxygen flow is 10L/h, and meanwhile, the stirring speed of 200 plus materials is kept at 500r/min for stirring reaction, and the stirring reaction time is 3 h;
(4) drying: after the reaction is finished, filtering the reaction system, continuously washing the reaction system by flowing purified water, and drying the reaction system at the temperature of 60 ℃ to obtain manganese tetroxide particles;
(5) grading: and (3) sorting the manganese tetroxide particles in the step (4) by using a jet milling classifier to obtain spherical particles with uniform size and proper specific gravity particle size, returning the rest particles to the step (3) again for reaction, drying and classification, and obtaining the spherical particles meeting the requirements, namely the high-purity trimanganese tetroxide, wherein the frequency of a pole separating wheel of the jet milling classifier is 60HZ, the air pressure is 0.8MPa, and the feeding frequency is 2 Hz.
Example 2
(1) Leaching: taking 500g of manganese oxide powder from a certain chemical plant of Qinzhou, Guangxi, adding water with the manganese content of 35% according to the solid-liquid ratio of 1:4, preparing the mixture into slurry, adding 98% sulfuric acid solution, and reacting at 80 ℃ to obtain manganese sulfate leaching solution;
(2) removing impurities: adding impurity-removing agents such as manganese dioxide, hydrogen peroxide, manganese hydroxide, sodium hydroxide, ammonia water, ammonium sulfide, barium sulfide and the like into the manganese sulfate solution obtained in the step (1), wherein the addition amount of the impurity-removing agents is 2% of the mass of manganese monoxide, fully and uniformly mixing, reacting to remove impurities such as lead, zinc, copper, nickel, cobalt, cadmium, chromium and other trace heavy metal elements, and filtering to obtain high-purity manganese sulfate liquid;
(3) reaction: adjusting the temperature in a reaction kettle to 80 ℃, respectively adding manganese sulfate liquid with certain concentration, ammonia water and oxygen at different speeds, wherein the manganese concentration of manganese sulfate is 120g/L, the feeding speed of manganese sulfate is 600mL/h, the ammonia water concentration is 3-15%, the feeding speed of ammonia water is 700mL/h, the pH is kept to 9, the oxygen flow is 30L/h, and meanwhile, the stirring speed of 500r/min is kept for stirring reaction, and the stirring reaction time is 6 h;
(4) drying: after the reaction is finished, filtering the reaction system, continuously washing by flowing purified water, and drying at 90 ℃ to obtain manganese tetraoxide particles;
(5) grading: and (3) sorting the manganese tetroxide particles in the step (4) by using a jet milling classifier to obtain spherical particles with uniform size and proper specific gravity particle size, returning the rest particles to the step (3) again for reaction, drying and classification, and obtaining the spherical particles meeting the requirements, namely the high-purity trimanganese tetroxide, wherein the frequency of a pole separating wheel of the jet milling classifier is 70HZ, the air pressure is 1MPa, and the feeding frequency is 4 Hz.
Example 3
(1) Taking 500g of manganese oxide powder of a certain chemical plant in Qinzhou, Guangxi, and adding 155ml of concentrated sulfuric acid of the theoretical amount for leaching after the manganese content is 32 percent and the slurry is mixed according to the solid-to-liquid ratio of 1: 4;
(2) after manganese sulfate leachate is obtained, 8g of manganese dioxide is added, the mixture is stirred for 0.5h at 70 ℃, ammonia water is used for adjusting the pH of the solution to 5.8, 9g of barium sulfide is added, the mixture is stirred for 1h at 70 ℃, and a manganese sulfate solution is obtained after filtration;
(3) setting the temperature at 60 ℃, stirring at 300r/min, simultaneously adding manganese sulfate and ammonia water, keeping the pH at 8, introducing oxygen, controlling the oxygen flow at 15L/h and the reaction time at 5h, and drying to obtain the high-purity trimanganese tetroxide, wherein the manganese concentration of the manganese sulfate is 80g/L, the feeding speed is 500mL/h, the ammonia water concentration is 6% and the feeding speed is 700 mL/h.
Example 4
(1) 500g of manganese oxide powder of a certain chemical plant in Qinzhou, Guangxi, with the manganese content of 34 percent, is taken, and after the manganese oxide powder is mixed according to the solid-to-liquid ratio of 1:3, 165ml of concentrated sulfuric acid with the theoretical amount is added for leaching.
(2) After manganese sulfate leachate is obtained, 10g of manganese dioxide is added, the mixture is stirred for 0.5h at 80 ℃, then ammonia is used for adjusting the pH of the solution to 5.8, 10g of barium sulfide is added, the mixture is stirred for 0.5h at 70 ℃, and the manganese sulfate solution is obtained by filtration.
(3) Setting the temperature at 70 ℃, stirring at 350r/min, simultaneously adding manganese sulfate and ammonia water, keeping the manganese concentration of the manganese sulfate at 100g/L and the feeding speed at 550mL/h, keeping the ammonia water concentration at 8% and the feeding speed at 750mL/h, keeping the pH at 8.5, introducing oxygen, keeping the oxygen flow at 15L/h and the reaction time at 4h, and drying to obtain the high-purity trimanganese tetroxide.
Example 5
The high-purity trimanganese tetroxide obtained in the example 3 is sorted by a jet mill classifier under the conditions of a pole-separating wheel frequency of 60Hz, an air pressure of 0.85MPa and a feeding frequency of 3.0Hz to obtain the battery grade high-purity trimanganese tetroxide with uniform spherical particles, qualified particle size and proper specific gravity.
Example 6
The manganous-manganic oxide obtained in the example 4 is sorted by an airflow crushing and grading machine under the conditions of a pole-separating wheel frequency of 65Hz, an air pressure of 0.90MPa and a feeding frequency of 3.5Hz to obtain the battery-grade high-purity manganous-manganic oxide with uniform spherical particles, qualified particle size and proper specific gravity.
The manganous-manganic oxide prepared in the embodiment 3 and the embodiment 4, the embodiment 5 and the embodiment 6 is tested according to the industrial standard, the indexes of the manganous-manganic oxide prepared in the four embodiments all meet the requirements of the industrial standard, but the manganous-manganic oxide classified by the jet mill classifier has larger tap density, smaller specific surface area and better quality. Specific test data are shown in table 1.
TABLE 1 trimanganese tetroxide quality of examples 3-6
The trimanganese tetroxide prepared in example 3, example 4, example 5 and example 6 is analyzed by a scanning electron microscope, and the surface topography under the scanning electron microscope is respectively shown in fig. 2, fig. 3, fig. 4 and fig. 5, wherein the trimanganese tetroxide prepared in example 3 and example 4 is not classified, the particle size is not uniform, the particle diameter difference is large, the degree of compaction is slightly worse than that in fig. 4 and fig. 5, and the trimanganese tetroxide in fig. 4 and fig. 5 has uniform particle size, tight distribution and better quality. Therefore, the manganous-manganic oxide prepared by the method has regular shape, the grain diameter meets the requirement and the specific gravity is suitable.
The preparation method is integrated with the above embodiments, and is implemented only completely according to the operation steps in the application, manganese monoxide is used as a raw material, ammonia water is used as a neutralizer to control the pH value in the reaction process, liquid oxygen is used as an oxidant to perform oxidation reaction, the reaction temperature is controlled, the reaction is carried out for several hours at a certain stirring speed, slurry is washed, filtered and dried, and then is separated by a jet milling classifier to prepare the mangano-manganic oxide with the purity of 99.99%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (6)
1. A preparation method of battery-grade high-purity trimanganese tetroxide is characterized by comprising the following steps: the method comprises the following steps:
(1) leaching: adding water into certain mass of manganese monoxide to prepare slurry, and adding a sulfuric acid solution to react to obtain manganese sulfate leachate;
(2) removing impurities: adding an impurity removing agent into the manganese sulfate solution obtained in the step (1), fully mixing uniformly, reacting to remove impurities, and filtering to obtain a high-purity manganese sulfate liquid;
(3) reaction: adjusting the temperature in the reaction kettle, adding manganese sulfate liquid with certain concentration, ammonia water and oxygen at different speeds, and simultaneously keeping a certain stirring speed for stirring reaction;
(4) drying: after the reaction is finished, filtering the reaction system, rinsing and drying to obtain manganese tetroxide particles;
(5) grading: and (4) separating the manganese tetroxide particles in the step (4) by using a jet milling classifier to obtain spherical particles with uniform size and proper specific gravity particle size, returning the rest particles to the step (3) again for reaction, drying and classification, and obtaining the spherical particles meeting the requirements, namely the high-purity trimanganese tetroxide.
2. The method for preparing battery grade high purity trimanganese tetroxide as claimed in claim 1, wherein: in the step (1), the solid-liquid ratio of the prepared slurry is 1: (2-4), the concentration of the added sulfuric acid solution is 85-98%, and the temperature is 50-80 ℃ when the sulfuric acid solution is added.
3. The method for preparing battery grade high purity trimanganese tetroxide as claimed in claim 1, wherein: in the step (2), the impurity removing agent comprises manganese dioxide, hydrogen peroxide, manganese hydroxide, sodium hydroxide, ammonia water, ammonium sulfide and barium sulfide, the amount of the added impurity removing agent is 1-2% of the mass of manganese monoxide, and the impurities are iron, lead, zinc, copper, nickel, cobalt, cadmium, chromium and other trace heavy metal elements.
4. The method for preparing battery grade high purity trimanganese tetroxide as claimed in claim 1, wherein: in the step (3), the temperature of the reaction kettle is 40-80 ℃, the stirring speed is 500r/min, the manganese concentration of the manganese sulfate is 40-120g/L, the feeding speed of the manganese sulfate is 600mL/h, the ammonia water concentration is 3-15%, the feeding speed of the ammonia water is 700mL/h, the pH value is 7-9, the oxygen flow is 10-30L/h, and the stirring reaction time is 3-6 h.
5. The method for preparing battery grade high purity trimanganese tetroxide as claimed in claim 1, wherein: in the step (4), the rinsing is continuously carried out by flowing pure water, and the drying temperature is 60-90 ℃.
6. The method for preparing battery grade high purity trimanganese tetroxide as claimed in claim 5, wherein: in the step (5), the frequency of a pole separating wheel of the jet milling classifier is 60-70HZ, the air pressure is 0.8-1MPa, and the feeding frequency is 2-4 Hz.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113479935A (en) * | 2021-07-13 | 2021-10-08 | 贵州金瑞新材料有限责任公司 | Low-cost preparation method of battery-grade trimanganese tetroxide |
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| CN1644513A (en) * | 2004-12-28 | 2005-07-27 | 北京科技大学 | Direct production of electron grade high purity trimangnese tetraoxide from ores |
| CN101704554A (en) * | 2009-07-16 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for preparing manganese sulfate |
| CN101898797A (en) * | 2010-08-04 | 2010-12-01 | 湖南汇通科技有限责任公司 | High-purity trimanganese tetroxide and preparation method thereof |
| US20150125366A1 (en) * | 2012-04-30 | 2015-05-07 | Industry Foundation Of Chonnam National University | Method for producing high-purity trimanganese tetraoxide and high-purity trimanganese tetraoxide produced by the method |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1644513A (en) * | 2004-12-28 | 2005-07-27 | 北京科技大学 | Direct production of electron grade high purity trimangnese tetraoxide from ores |
| CN101704554A (en) * | 2009-07-16 | 2010-05-12 | 贵州红星发展股份有限公司 | Method for preparing manganese sulfate |
| CN101898797A (en) * | 2010-08-04 | 2010-12-01 | 湖南汇通科技有限责任公司 | High-purity trimanganese tetroxide and preparation method thereof |
| US20150125366A1 (en) * | 2012-04-30 | 2015-05-07 | Industry Foundation Of Chonnam National University | Method for producing high-purity trimanganese tetraoxide and high-purity trimanganese tetraoxide produced by the method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113479935A (en) * | 2021-07-13 | 2021-10-08 | 贵州金瑞新材料有限责任公司 | Low-cost preparation method of battery-grade trimanganese tetroxide |
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