CN113088997A - Preparation method of low-impurity electrolytic manganese dioxide - Google Patents
Preparation method of low-impurity electrolytic manganese dioxide Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
- C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C25B1/21—Manganese oxides
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Abstract
The invention discloses a preparation method of low-impurity electrolytic manganese dioxide, which comprises the steps of reacting manganese oxide mineral powder, pyrite mineral powder, industrial sulfuric acid and electrolytic waste liquid, then adding calcium carbonate or superfine manganese oxide mineral powder for deironing and filter-pressing, adding manganese sulfide into filtrate for impurity removal and filter-pressing, then adding manganous fluoride for impurity removal and filtering to obtain electrolyte, then electrolyzing to obtain electrolytic manganese dioxide semi-finished products, and carrying out the working procedures of crushing, rinsing, filter-pressing, drying and the like to obtain the products. The method refines the electrolytic manganese dioxide semi-finished product, effectively removes impurities in the product, and obtains the electrolytic manganese dioxide with low impurities.
Description
Technical Field
The invention belongs to the technical field of electrolytic manganese dioxide production, and particularly relates to a preparation method of low-impurity electrolytic manganese dioxide.
Background
At present, a manganese sulfate solution is usually produced by a two-ore method and then Electrolytic Manganese Dioxide (EMD) is prepared by electrolysis, but a large amount of impurities are easily brought in the leaching process of manganese ore and the purification process of leachate, and how to effectively remove the impurities, so that the preparation of the EMD with low impurities is the key point of the research of the production process.
Disclosure of Invention
Aiming at the defects, the invention discloses a preparation method of low-impurity electrolytic manganese dioxide, which can effectively remove impurities and refine an EMD semi-finished product to obtain low-impurity EMD.
The invention is realized by adopting the following technical scheme:
a preparation method of low-impurity electrolytic manganese dioxide comprises the following steps:
(1) adding manganese oxide ore powder, pyrite powder, industrial sulfuric acid and electrolytic waste liquid into a leaching reaction tank, and reacting for 3-4 hours at 90-95 ℃ under the stirring of 200-300 r/min to obtain mixed slurry; the weight ratio of the manganese oxide mineral powder to the pyrite powder is 1 (0.16-0.30), the ratio of the sum of the weights of the manganese oxide mineral powder and the pyrite powder to the sum of the weights of the industrial sulfuric acid and the sulfuric acid in the electrolytic waste liquid is 1 (0.25-0.35), and the ratio of the sum of the weights of the manganese oxide mineral powder and the pyrite powder to the weight of the electrolytic waste liquid is 1 (5-7);
(2) adding calcium carbonate into the mixed slurry at 90-95 ℃ to adjust the pH value to 4.0-4.5, detecting the content of ferrous ions in the mixed slurry, and if the content of ferrous ions is more than or equal to 10-5When mol/L, adding the superfine manganese oxide ore powder until the content of ferrous ions is less than 10-5And (3) continuing adding calcium carbonate into the mixed slurry to adjust the pH to 6.0-6.5, detecting the content of ferric ions in the mixed slurry, and if the content of the ferric ions is more than or equal to 10-5When the mol/L is higher, the calcium carbonate is continuously added until the content of ferric ions is less than 10-5Performing pressure filtration on the mixed slurry to obtain a filtrate A;
(3) heating the filtrate A to 80-90 ℃, adding the electrolytic waste liquid to adjust the pH value to 3.5-4.0, then slowly adding manganese sulfide and an auxiliary agent B, stirring and reacting for 1-2 hours, and performing filter pressing to obtain a filtrate C; the volume ratio of the weight of the manganese sulfide to the volume of the filtrate A is (50-60) g:1L, the auxiliary agent B is any one or combination of ethanol, propanol and isopropanol, and the volume ratio of the auxiliary agent B to the volume of the filtrate A is (1-3) to 100;
(4) slowly adding manganous fluoride and an auxiliary agent D into the filtrate C under the conditions of 80-90 ℃ and pH 6.0-6.5, stirring for reaction for 2-3 h, and filtering to obtain a purified manganese sulfate solution; the volume ratio of the weight of the manganous fluoride to the volume of the filtrate C is (80-100) g:1L, the auxiliary agent D is obtained by mixing and reacting chitosan and citric acid in equal volumes, and the volume ratio of the weight of the auxiliary agent D to the volume of the filtrate C is (10-20) g: 1000L;
(5) feeding the manganese sulfate solution into an electrolytic bath for electrolysis, wherein the temperature of the electrolyte is 98-100 ℃, and the current density of an anode is 55-80A/m2The concentration of sulfuric acid in the electrolyte is 0.35-0.70 mol/L, the concentration of manganese sulfate is 0.30-0.50 mol/L, the cell voltage is 2.0-4.0V, the electrolysis period is 10-12 days, and electrolytic manganese dioxide semi-finished products and electrolytic waste liquid are obtained after electrolysis;
(6) crushing the electrolytic manganese dioxide semi-finished product into particles with the particle size of 10-30 mm, then adding hot water for rinsing at the rinsing temperature of 90-95 ℃ until the content of sulfuric acid in rinsing liquid is lower than 1g/L, then rinsing with a lithium hydroxide solution at the temperature of 60-70 ℃, adjusting the pH value to 6.5-7.0, then rinsing with hot water at the temperature of 90-95 ℃ for 8-10 hours, and then grinding the particles to obtain electrolytic manganese dioxide powder with the particle size of less than 325 meshes;
(7) adding a potassium permanganate solution into electrolytic manganese dioxide powder to react for 1 hour, wherein the reaction temperature is 90-95 ℃, then adding a lithium hydroxide solution, continuing to react for 0.5 hour, the reaction temperature is 90-95 ℃, when the pH value reaches 6.5-7.0, the reaction is qualified, then performing filter pressing, performing flash evaporation cyclone drying at 100-105 ℃ to obtain electrolytic manganese dioxide powder, and then conveying the electrolytic manganese dioxide powder to a gravity mixing bin by adopting a dense-phase pneumatic conveying mode to mix for 16-24 hours to obtain a low-impurity electrolytic manganese dioxide product.
Further, in the step (1), the manganese oxide ore powder with the granularity smaller than 200 meshes accounts for 90-95% and the mass content of manganese metal is 16-18%; the pyrite powder with the granularity smaller than 120 meshes accounts for 90-95%, the mass content of effective sulfur participating in the reaction is 30-40%, and the industrial sulfuric acid is 98% in mass fraction.
Further, in the step (2), the superfine manganese oxide ore powder with the granularity smaller than 325 meshes accounts for 90-95%, and the calcium carbonate is nano calcium carbonate.
Further, the stirring speed in the step (3) is 200-300 r/min.
Further, the stirring speed in the step (4) is 50-100 r/min.
Further, the mass fraction of the lithium hydroxide solution is 20-25%, and the mass fraction of the potassium permanganate solution is 30-40%.
Further, the weight ratio of the potassium permanganate solution added in the step (7) to the electrolytic manganese dioxide powder is 25: 1000.
Further, the weight ratio of the lithium hydroxide solution added in the step (7) to the electrolytic manganese dioxide powder is 30: 1000.
According to the invention, the manganese sulfide is quantitatively added to remove heavy metal ions, so that a large amount of manganese sulfide is required to be added for effectively removing the heavy metal ions (particularly metal ions such as lead, antimony and the like), but the viscosity of the solution is increased along with the increase of the concentration of the manganese sulfide, so that the manganese sulfide is adhered together in a block shape and is difficult to diffuse in the solution, and the impurity removal effect of the manganese sulfide is greatly reduced.
According to the method, calcium and magnesium ions are removed by quantitatively adding manganous fluoride, and meanwhile, an auxiliary agent B prepared by mixing chitosan and citric acid is added to have a synergistic effect with the manganous fluoride, so that the dispersity of the manganous fluoride in a solution is improved, the combination of the manganous fluoride with the calcium and magnesium ions is promoted, and the impurity removal effect of the manganous fluoride is improved.
In the rinsing process, a lithium hydroxide solution and a potassium permanganate solution are used, so that impurity sodium can be prevented from being brought into an EMD product; a small amount of potassium permanganate is added to play an oxidizing role, and low-valence manganese remained in the EMD is removed.
Compared with the prior art, the technical scheme has the following beneficial effects:
1. the method can effectively remove impurities in the manganese sulfate solution, avoid the impurities from being brought into the EMD product, reduce the difficulty of refining the subsequent product, and improve the production efficiency, thereby obtaining the low-impurity EMD product.
2. The method has the advantages of simple process, simplified production flow, high controllability and suitability for large-scale and automatic production of low-impurity EMD products.
Drawings
FIG. 1 is a table showing the results of EMD detection in Experimental example 1.
FIG. 2 is a table showing the results of EMD detection in Experimental example 2.
FIG. 3 is a table showing the results of EMD detection in Experimental example 3.
Detailed Description
The invention is further illustrated by the following examples, which are not to be construed as limiting the invention thereto.
Example 1:
a preparation method of low-impurity electrolytic manganese dioxide comprises the following steps:
(1) adding manganese oxide ore powder, pyrite powder, industrial sulfuric acid and electrolytic waste liquid into a leaching reaction tank, and reacting for 3-4 hours at 90-95 ℃ under the stirring of 200-300 r/min to obtain mixed slurry; the weight ratio of the manganese oxide ore powder to the pyrite powder is 1:0.22, the weight ratio of the sum of the manganese oxide ore powder and the pyrite powder to the sum of the industrial sulfuric acid and the sulfuric acid in the electrolytic waste liquid is 1:0.28, and the weight ratio of the sum of the manganese oxide ore powder and the pyrite powder to the electrolytic waste liquid is 1: 6.5; the manganese oxide ore powder accounts for 90-95% of the manganese oxide ore powder with the granularity smaller than 200 meshes, and the mass content of the manganese metal is 16-18%; 90-95% of the pyrite powder with the granularity smaller than 120 meshes and 30-40% of the mass content of effective sulfur participating in the reaction, wherein the industrial sulfuric acid is 98% of industrial sulfuric acid in mass fraction;
(2) adding nano calcium carbonate into the mixed slurry at 90-95 ℃ to adjust the pH value to 4.0-4.5, and detecting the mixtureThe ferrous ion content in the slurry is 10 or more-5When mol/L, adding the superfine manganese oxide ore powder until the content of ferrous ions is less than 10-5And (3) continuing adding nano calcium carbonate into the mixed slurry to adjust the pH to 6.0-6.5, detecting the content of ferric ions in the mixed slurry, and if the content of the ferric ions is more than or equal to 10-5When mol/L, continuing to add the nano calcium carbonate until the content of ferric ions is less than 10-5Performing pressure filtration on the mixed slurry to obtain a filtrate A; the superfine manganese oxide ore powder accounts for 95% of the superfine manganese oxide ore powder with the granularity smaller than 325 meshes;
(3) heating the filtrate A to 86 ℃, adding the electrolytic waste liquid to adjust the pH value to 3.8, then slowly adding manganese sulfide and an auxiliary agent B, reacting for 1h under the stirring of 200r/min, and carrying out filter pressing to obtain a filtrate C; the volume ratio of the weight of the manganese sulfide to the volume of the filtrate A is 50g:1L, the assistant B is the combination of propanol and isopropanol, and the volume ratio of the assistant B to the volume of the filtrate A is 1: 100;
(4) slowly adding manganous fluoride and the aid D into the filtrate C under the conditions of 85 ℃ and pH of 6.0, reacting for 2 hours under the stirring of 50r/min, and filtering to obtain a purified manganese sulfate solution; the volume ratio of the weight of the manganous fluoride to the volume of the filtrate C is 100g:1L, the auxiliary agent D is obtained by mixing and reacting chitosan and citric acid in equal volumes, and the volume ratio of the weight of the auxiliary agent D to the volume of the filtrate C is 15g: 1000L;
(5) feeding the manganese sulfate solution into an electrolytic bath for electrolysis, wherein the temperature of the electrolyte is 98-100 ℃, and the current density of an anode is 55-80A/m2The concentration of sulfuric acid in the electrolyte is 0.35-0.70 mol/L, the concentration of manganese sulfate is 0.30-0.50 mol/L, the cell voltage is 2.0-4.0V, the electrolysis period is 10-12 days, and electrolytic manganese dioxide semi-finished products and electrolytic waste liquid are obtained after electrolysis;
(6) crushing the electrolytic manganese dioxide semi-finished product into particles with the particle size of 10-30 mm, then adding hot water for rinsing at the rinsing temperature of 90-95 ℃ until the content of sulfuric acid in rinsing liquid is lower than 1g/L, then rinsing with a lithium hydroxide solution at the temperature of 60-70 ℃, adjusting the pH value to 6.5-7.0, then rinsing with hot water at the temperature of 90-95 ℃ for 8-10 hours, and then grinding the particles to obtain electrolytic manganese dioxide powder with the particle size of less than 325 meshes;
(7) adding a potassium permanganate solution into electrolytic manganese dioxide powder to react for 1 hour, wherein the reaction temperature is 90-95 ℃, then adding a lithium hydroxide solution, continuing to react for 0.5 hour, the reaction temperature is 90-95 ℃, when the pH value reaches 6.5-7.0, the reaction is qualified, then performing filter pressing, performing flash evaporation cyclone drying at 100-105 ℃ to obtain electrolytic manganese dioxide powder, and then conveying the electrolytic manganese dioxide powder to a gravity mixing bin by adopting a dense-phase pneumatic conveying mode to mix for 16-24 hours to obtain a low-impurity electrolytic manganese dioxide product; the mass fraction of the lithium hydroxide solution is 20-25%, and the mass fraction of the potassium permanganate solution is 30-40%; the weight ratio of the added potassium permanganate solution to the electrolytic manganese dioxide powder is 25: 1000; the weight ratio of the added lithium hydroxide solution to the electrolytic manganese dioxide powder was 30: 1000.
Example 2:
it differs from the process described in example 1 only in that: the weight ratio of the manganese oxide mineral powder to the pyrite powder is 1:0.16, the weight ratio of the sum of the manganese oxide mineral powder and the pyrite powder to the sum of the industrial sulfuric acid and the sulfuric acid in the electrolytic waste liquid is 1:0.25, and the weight ratio of the sum of the manganese oxide mineral powder and the pyrite powder to the electrolytic waste liquid is 1: 5; heating the filtrate A to 80 ℃, adjusting the pH value to 3.5, then slowly adding manganese sulfide and an auxiliary agent B, and reacting for 2 hours under the stirring of 250 r/min; the volume ratio of the weight of the manganese sulfide to the volume of the filtrate A is 55g to 1L, the auxiliary agent B is ethanol, and the volume ratio of the auxiliary agent B to the volume of the filtrate A is 2 to 100; slowly adding manganous fluoride and the auxiliary agent D into the filtrate C under the conditions of 80 ℃ and pH 6.2, and reacting for 2.5 hours under the stirring of 80 r/min; the volume ratio of the weight of the manganous fluoride to the volume of the filtrate C is 80g:1L, and the volume ratio of the weight of the auxiliary agent D to the volume of the filtrate C is 10g: 1000L.
Example 3:
it differs from the process described in example 1 only in that: the weight ratio of the manganese oxide mineral powder to the pyrite powder is 1:0.30, the weight ratio of the sum of the manganese oxide mineral powder and the pyrite powder to the sum of the industrial sulfuric acid and the sulfuric acid in the electrolytic waste liquid is 1:0.35, and the weight ratio of the sum of the manganese oxide mineral powder and the pyrite powder to the electrolytic waste liquid is 1: 7; heating the filtrate A to 90 ℃, adjusting the pH value to 4.0, then slowly adding manganese sulfide and an auxiliary agent B, and reacting for 1.5h under the stirring of 300 r/min; the volume ratio of the weight of the manganese sulfide to the volume of the filtrate A is 60g:1L, the assistant B is propanol, and the volume ratio of the assistant B to the volume of the filtrate A is 3: 100; slowly adding manganous fluoride and the auxiliary agent D into the filtrate C under the conditions of 90 ℃ and pH 6.5, and reacting for 3 hours under the stirring of 100 r/min; the volume ratio of the weight of the manganous fluoride to the volume of the filtrate C is 90g:1L, and the volume ratio of the weight of the auxiliary agent D to the volume of the filtrate C is 20g: 1000L.
Comparative example 1:
it differs from the process described in example 1 only in that, in step (3), only barium sulphide is added.
Comparative example 2:
it differs from the process described in example 1 only in that, in step (3), only manganese sulphide is added.
Comparative example 3:
it differs from the process described in example 1 only in that, in step (4), only a polyacrylamide solution having a concentration of 100ppm is added; the volume ratio of the weight of the polyacrylamide solution to the filtrate B is 10g:80m3。
Comparative example 4:
this differs from the process described in example 1 only in that, in step (4), only manganous fluoride is added.
Experimental example 1:
EMD samples 1-3 are correspondingly obtained by the production according to the methods in the embodiments 1-3, EMD samples 4-7 are correspondingly obtained by the production according to the methods in the comparative examples 1-4, and the purity and impurity content of the samples are detected, wherein the specific result is shown in the attached figure 1.
Experimental example 2:
according to the method of the embodiment 1, in the step (3), the volume ratios of the assistant B and the filtrate A are respectively 0.5:100, 0.8:100, 1:100, 2:100, 3:100, 4:100 and 5:100, the purity and the impurity content of the obtained product are detected, the specific result is shown in the attached figure 2, and the data show that the impurity removal effect of manganese sulfide can be promoted only when the usage ratios of the assistant B and the filtrate A and the manganese sulfide are controlled within a certain range, the assistant B excessively disperses the manganese sulfide, the generated heavy metal sulfide is not easy to aggregate, precipitate and remove, and the impurity removal effect is reduced; and the auxiliary agent B is too little, the manganese sulfide is bonded along with the increase of the concentration, the manganese sulfide cannot be effectively diffused, the bonding efficiency with heavy metal ions is reduced, and the impurity removal effect cannot be achieved.
Experimental example 3:
according to the method described in example 1, in the step (4), the weight ratio of the assistant D to the volume ratio of the filtrate C are 1g:1000L, 5g:1000L, 10g:1000L, 15g:1000L, 20g:1000L, 25g:1000L, 30g:1000L, 35g:1000L, and 40g:1000L, respectively, and the purity and the impurity content of the obtained product are detected, and the specific result is shown in fig. 3, and it can be seen from the data that the dosage ratio between the assistant D and the filtrate C and between the filtrate C and manganous fluoride need to be controlled within a certain range to promote the dispersion of manganous fluoride, so that the impurity removal effect of calcium and magnesium ions is achieved.
Claims (2)
1. A preparation method of low-impurity electrolytic manganese dioxide is characterized by comprising the following steps: the method comprises the following steps:
(1) adding manganese oxide ore powder, pyrite powder, industrial sulfuric acid and electrolytic waste liquid into a leaching reaction tank, and reacting for 3-4 hours at the temperature of 90-95 ℃ and the stirring speed of 200-300 r/min to obtain mixed slurry; the weight ratio of the manganese oxide mineral powder to the pyrite powder is 1 (0.16-0.30), the ratio of the sum of the weights of the manganese oxide mineral powder and the pyrite powder to the sum of the weights of the industrial sulfuric acid and the sulfuric acid in the electrolytic waste liquid is 1 (0.25-0.35), and the ratio of the sum of the weights of the manganese oxide mineral powder and the pyrite powder to the weight of the electrolytic waste liquid is 1 (5-7);
(2) under the condition that the temperature is 90-95 ℃, adding calcium carbonate into the mixed slurry, adjusting the pH value of the mixed slurry to 4.0-4.5, and detecting the content of ferrous ions in the mixed slurry, wherein if the content of the ferrous ions is more than or equal to 10-5When the concentration is mol/L, adding the superfine manganese oxide ore powder into the mixed slurry until the content of ferrous ions is less than 10-5Adding calcium carbonate into the mixed slurry continuously and adjusting the mixed slurryThe pH value of the solution is 6.0-6.5, and then the content of ferric ions in the mixed slurry is detected, if the content of the ferric ions is more than or equal to 10-5When the mol/L is higher than the preset value, calcium carbonate is continuously added into the mixed slurry until the content of ferric ions is less than 10-5Performing pressure filtration on the mixed slurry to obtain a filtrate A;
(3) heating the filtrate A to 80-90 ℃, adjusting the pH of the filtrate A to 3.5-4.0 by using the electrolytic waste liquid, then slowly adding manganese sulfide and an auxiliary agent B, stirring and reacting for 1-2 hours, and performing filter pressing to obtain a filtrate C; the volume ratio of the weight of the manganese sulfide to the volume of the filtrate A is (50-60) g:1L, the auxiliary agent B is any one or combination of ethanol, propanol and isopropanol, and the volume ratio of the auxiliary agent B to the volume of the filtrate A is (1-3) to 100;
(4) slowly adding manganous fluoride and the aid D into the filtrate C under the conditions that the temperature is 80-90 ℃ and the pH value is 6.0-6.5, stirring for reacting for 2-3 hours, and filtering to obtain a purified manganese sulfate solution; the volume ratio of the weight of the manganous fluoride to the volume of the filtrate C is (80-100) g:1L, the auxiliary agent D is obtained by mixing and reacting chitosan and citric acid in equal volumes, and the volume ratio of the weight of the auxiliary agent D to the volume of the filtrate C is (10-20) g: 1000L;
(5) feeding the manganese sulfate solution into an electrolytic bath for electrolysis, wherein the temperature of the electrolyte is 98-100 ℃, and the current density of an anode is 55-80A/m2The concentration of sulfuric acid in the electrolyte is 0.35-0.70 mol/L, the concentration of manganese sulfate is 0.30-0.50 mol/L, the cell voltage is 2.0-4.0V, the electrolysis period is 10-12 days, and electrolytic manganese dioxide semi-finished products and electrolytic waste liquid are obtained after electrolysis;
(6) crushing the electrolytic manganese dioxide semi-finished product into particles with the particle size of 10-30 mm, then adding hot water for rinsing at the rinsing temperature of 90-95 ℃ until the content of sulfuric acid in rinsing liquid is lower than 1g/L, then rinsing with a lithium hydroxide solution at the temperature of 60-70 ℃, adjusting the pH value to 6.5-7.0, then rinsing with hot water at the temperature of 90-95 ℃ for 8-10 hours, and then grinding the particles into powder to obtain electrolytic manganese dioxide powder with the particle size of less than 325 meshes;
(7) adding a potassium permanganate solution into electrolytic manganese dioxide powder to react for 1 hour, wherein the reaction temperature is 90-95 ℃, then adding a lithium hydroxide solution, continuing to react for 0.5 hour, the reaction temperature is 90-95 ℃, when the pH value reaches 6.5-7.0, the reaction is qualified, then performing filter pressing, performing flash evaporation and rotational flow drying at the temperature of 100-105 ℃ to obtain electrolytic manganese dioxide powder, and then conveying the electrolytic manganese dioxide powder to a gravity mixing bin in a dense phase pneumatic conveying mode for mixing for 16-24 hours to obtain a low-impurity electrolytic manganese dioxide product.
2. The method of claim 1, wherein the method comprises: in the step (2), the superfine manganese oxide ore powder with the granularity smaller than 325 meshes accounts for 90-95%, and the calcium carbonate is nano calcium carbonate.
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