CN102040248A - Preparation method of active manganese dioxide - Google Patents
Preparation method of active manganese dioxide Download PDFInfo
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- CN102040248A CN102040248A CN 201010567325 CN201010567325A CN102040248A CN 102040248 A CN102040248 A CN 102040248A CN 201010567325 CN201010567325 CN 201010567325 CN 201010567325 A CN201010567325 A CN 201010567325A CN 102040248 A CN102040248 A CN 102040248A
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- manganese dioxide
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- roasting
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000011572 manganese Substances 0.000 claims abstract description 35
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 28
- 230000001590 oxidative effect Effects 0.000 claims abstract description 23
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000002699 waste material Substances 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000000428 dust Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000007323 disproportionation reaction Methods 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 8
- 239000002184 metal Substances 0.000 claims abstract description 8
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007800 oxidant agent Substances 0.000 claims description 15
- GOPYZMJAIPBUGX-UHFFFAOYSA-N [O-2].[O-2].[Mn+4] Chemical class [O-2].[O-2].[Mn+4] GOPYZMJAIPBUGX-UHFFFAOYSA-N 0.000 claims description 8
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000012295 chemical reaction liquid Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- 229940099596 manganese sulfate Drugs 0.000 description 4
- 239000011702 manganese sulphate Substances 0.000 description 4
- 235000007079 manganese sulphate Nutrition 0.000 description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 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
- 230000003213 activating effect Effects 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a preparation process of manganese oxide, and particularly discloses a preparation method of active manganese dioxide, which comprises the following steps: the method comprises the steps of taking waste manganese mud recovered by wet dust removal in the production of metal manganese powder as a raw material, and sequentially carrying out the steps of raw material drying, oxidizing roasting, sulfuric acid disproportionation, heavy oxidation, solid-liquid separation, washing, neutralization and product drying to obtain the high-discharge active manganese dioxide. The preparation process has the advantages of high resource utilization rate, low cost, excellent product performance and the like.
Description
Technical Field
The invention relates to a preparation method of a manganese compound, in particular to a preparation process of a manganese oxide.
Background
Manganese dioxide is the main positive electrode material of dry batteries, and the quality of the manganese dioxide plays a decisive role in the performance of zinc-manganese batteries. In the past, natural manganese dioxide has been used in large quantities as a depolarizer. Since natural manganese dioxide resources have been exhausted due to many years of exploitation, the search for high-quality manganese dioxide raw materials suitable for discharge has been an important issue in the field of dry batteries. Although electrolytic manganese dioxide is excellent in performance for dry batteries, it is expensive, consumes much power, has a long production cycle and requires a large investment, and therefore chemical manganese dioxide and active manganese dioxide are being actively developed in various countries around the world in addition to the expansion of the production scale of electrolytic manganese dioxide. Active manganese dioxide is increasingly favored by various battery factories due to its low price, low investment, short production cycle and excellent discharge performance.
The active manganese dioxide is prepared by crushing, reducing and roasting natural manganese ore, activating acid and then oxidizing heavy manganese ore. In recent years, active manganese dioxide has been widely used as a substitute for electrolytic manganese dioxide, and the reason for rapid popularization is that, in addition to its low price, it has excellent liquid absorption performance and good discharge performance, especially heavy-load continuous discharge performance. Therefore, it is crucial to those skilled in the art how to improve and optimize the preparation process of activated manganese dioxide.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the preparation method of the active manganese dioxide with high resource utilization rate, low cost and excellent product performance.
In order to solve the technical problems, the technical scheme provided by the invention is a preparation method of active manganese dioxide, which comprises the following steps: the method takes waste manganese mud recovered by wet dedusting in the production of manganese metal powder as a raw material, and sequentially comprises the steps of raw material drying, oxidizing roasting, sulfuric acid disproportionation, heavy oxidation, solid-liquid separation, washing, neutralization and product drying to prepare the high-discharge active manganese dioxide.
In the preparation method of the active manganese dioxide, in the step of drying the raw materials, the drying temperature is preferably controlled to be 100-300 ℃, and the drying time is preferably controlled to be 1-4 h.
In the above preparation method of active manganese dioxide, the oxidizing roasting is performed in hot air, the roasting temperature is preferably controlled to 300-600 ℃, and the roasting time is preferably controlled to 1-4 h.
The main reaction principle of the oxidizing roasting step is as follows: 4Mn 3 O 4 + O 2 =6Mn 2 O 3 。
In the above preparation method of active manganese dioxide, in the step of disproportionation of sulfuric acid, the mass concentration of the sulfuric acid is preferably 10% to 60%, and the disproportionation temperature is preferably controlled at 70 ℃ to 98 ℃.
The main reaction principle of the sulfuric acid disproportionation step is as follows: mn 2 O 3 +H 2 SO 4 = MnO 2 +MnSO 4 +H 2 O；
Mn 3 O 4 +2H 2 SO 4 = MnO 2 +2MnSO 4 + 2H 2 O 。
In the above method for producing active manganese dioxide, the oxidizing agent used in the heavy oxidation step may be potassium chlorate, sodium chlorate, potassium permanganate, or the like, but an aqueous solution of sodium chlorate having a mass concentration of 30% to 50% is preferable in terms of cost, safety, and ease of use. The amount of oxidizing agent used can be determined at the discretion of the person skilled in the art according to the actual needs of the heavy oxidation reaction. When the intermediate product (mainly, manganese mud powder obtained after roasting) and the oxidizing agent are added, the intermediate product and the oxidizing agent can be added at one time, but the operation is preferably carried out in three times: firstly, adding 1/2 of the total amount of the intermediate product and the oxidant, secondly adding 1/4 of the total amount, and thirdly adding the balance. The temperature is kept at 90-95 ℃ after each addition of the oxidant or the intermediate product, and the temperature keeping time is preferably 1-2 h.
The main reaction principle of the heavy oxidation step is as follows:
5MnSO 4 +2NaClO 3 +4H 2 O=5MnO 2 +2NaHSO 4 +Cl 2 +3H 2 SO 4 。
in the above method for preparing active manganese dioxide, the neutralizing agent used in the neutralization step may be ammonium bicarbonate, sodium hydroxide, etc., and it is preferably a sodium hydroxide aqueous solution having a mass concentration of 3% to 20%.
The main reaction principle of the neutralization step is as follows: h 2 SO 4 +2NaOH=Na 2 SO 4 +2H 2 O。
In the preparation method of the active manganese dioxide, in the product drying step, the drying temperature is preferably controlled to be 70-120 ℃, and the drying time is preferably controlled to be 4-24 hours.
In the technical scheme of the invention, one very important characteristic is that the process takes the waste manganese mud recovered by wet dedusting in the production of the manganese metal powder as a raw material. In the existing process of electrolyzing the metal manganese powder, an electrolytic manganese sheet with the manganese content of more than 99.7 percent is used as a raw material, and the metal manganese powder is easy to oxidize in production, so that the metal manganese powder is very easy to catch fire or even explode as long as the dust in a production place is large, and therefore, a closed place is generally utilized and the dust is forcibly sucked by a high-pressure fan so as to reduce the dust concentration. However, when dust is collected by a dry method or a cloth bag, a dry dust collector or a cloth bag is easily caused to fire and explode, so that dust is generally collected by a wet dust collector, and after the dust is collected by the wet dust collector, metal manganese in the dust is oxidized into manganese hydroxide after being circulated with water and air for a long time, and further oxidized into waste manganese mud which takes manganic oxide or manganic oxide and the like as main substances; the manganese-containing waste mud is generally sold to a manganese ore factory at low price and is matched with ores for sale, but by the technical scheme of the invention, the waste manganese mud recovered in the production of the manganese metal powder can be used for producing high-purity active manganese dioxide, so that the added value of industrial waste is greatly improved, the production cost is reduced, and the recycling of resources and environmental protection are facilitated.
Compared with the prior art, the invention has the advantages that: mnO in active manganese dioxide prepared by adopting the process of the invention 2 The content is more than 85 percent, the content of Fe is less than 0.5 percent, and the content of Co, cu, pb and Ni impurities is below 100 ppm. The heavy-load continuous discharge performance of the active manganese dioxide product reaches or even exceeds the standard of an electrolytic manganese dioxide first-grade product, the intermittent discharge performance can be comparable with the electrolytic manganese dioxide second-grade product, and the use of a battery manufacturer shows that the high-purity active manganese dioxide prepared by the invention completely or partially replaces electrolytic manganese dioxide, the performance of the battery product is basically not reduced, and even the liquid absorption performance and the high-power continuous discharge performance are obviously improved compared with the situation of singly using electrolytic manganese dioxide. Therefore, the method of the invention not only can change waste into valuable and protect the environment, but also can relieve the current crisis that high-grade ore is gradually exhausted, thereby relieving the high-purity activity IIThe current situation that manganese oxide is in short supply brings great economic benefit to enterprises.
Detailed Description
The invention is further described below with reference to specific examples, without thereby limiting the scope of protection of the invention.
Example 1:
the preparation method of the active manganese dioxide comprises the following steps:
(1) Drying raw materials: taking about 2kg of waste manganese mud recovered by wet dust removal in the production of metal manganese powder as a raw material, placing the raw material in a constant-temperature oven, drying at 200 ℃ for 4h, and sieving with a 80-mesh sieve for later use;
(2) Oxidizing roasting: taking 1kg of dried raw material waste manganese mud, putting the raw material waste manganese mud into a stainless steel vessel, placing the stainless steel vessel in a muffle furnace heated to about 300 ℃ for roasting for 4 hours, wherein the muffle furnace does not need to be closed during roasting, a certain number of air inlets are reserved so that the roasting is carried out in hot air, and manganese mud powder is obtained after the roasting is finished;
3) Sulfuric acid disproportionation: adding 3L of water and 500mL of 98% concentrated sulfuric acid (the mass concentration is about 14%) into a 5L beaker, heating while stirring, adding 500g of the manganese mud powder obtained after roasting when the temperature is raised to over 70 ℃ (no more than 98 ℃), performing disproportionation reaction, and then continuing heating;
(4) Heavy oxidation: after the temperature is raised to 90 ℃, the temperature is kept for 1h, and then 500mL of oxidant solution is added for oxidation reaction; keeping the temperature at 90 ℃ for 1h, adding 250g of manganese mud powder obtained after oxidizing roasting, keeping the temperature for 1h, and continuously adding 250mL of oxidant solution; keeping the temperature for 1h, adding 250g of manganese mud powder obtained after oxidizing roasting, keeping the temperature for 1h, adding 250ml of oxidant solution, supplementing a little evaporated water in the process, keeping the temperature for 4h, filtering the reaction liquid, detecting the content of manganese sulfate in the reaction liquid, and taking the reaction end point when the content of manganese sulfate is lower than 10 g/L; the oxidant solution used in the step is a sodium chlorate solution prepared by adding 500g of sodium chlorate into 1000mL of water;
(5) Solid-liquid separation, washing, neutralization and drying: and after the reaction liquid is naturally cooled, carrying out solid-liquid separation on the reaction liquid by using filter cloth through a Brinell filter, taking filter residues, putting the filter residues into a 5L beaker, washing the beaker by using hot water at 80 ℃ until the pH value is more than 2.5, neutralizing the washed product by using a sodium hydroxide solution with the mass concentration of 5% until the pH value is 5.5, washing the beaker twice by using the hot water, carrying out solid-liquid separation again, drying the filtrate by using hot air at 110 ℃, crushing the filtrate when the moisture content is less than 3% after drying for 6 hours, and sieving the filtrate by using a 120-mesh sieve to obtain the finished product of the active manganese dioxide.
As a result of analysis, the contents of heavy metal impurities Fe, cu, pb, co, ni and Cd in the activated manganese dioxide prepared in this example were 1643.8ppm, 60.5pm, 58ppm, 27.9ppm, 10.4ppm and 1.3ppm, respectively. Through detection, the total manganese content in the finished product reaches 55.8 percent, and the manganese dioxide content is 86.2 percent; the discharge result of the RS20 battery is as follows: open circuit voltage 1.73V, 1.8 omega 0.9V continuous discharge 202min, 3.9 omega 0.9V continuous discharge 468min, have reached first grade electrolytic manganese standard.
Example 2:
the preparation method of the active manganese dioxide comprises the following steps:
(1) Drying raw materials: taking about 200kg of waste manganese mud recovered by wet dust removal in the production of metal manganese powder as a raw material, carrying out solid-liquid separation on the raw material by using a plate-and-frame filter press, then placing a recovered waste manganese mud filter cake into a constant-temperature oven, drying at the temperature of 200 ℃ for 4 hours, and sieving the dried waste manganese mud with a 80-mesh sieve for later use;
(2) Oxidizing roasting: taking 100kg of dried raw material waste manganese mud, putting the raw material waste manganese mud into a stainless steel vessel, placing the vessel in a reverberatory furnace with the temperature rising to about 500 ℃ for roasting for 4h, wherein the reverberatory furnace does not need to be closed during roasting, a certain number of air inlets are reserved so that the roasting is carried out in hot air, and manganese mud powder is obtained after the roasting is finished;
(3) Sulfuric acid disproportionation: adding 300L of water and 50L of concentrated sulfuric acid with the concentration of 98% into a reaction kettle lined with the acid-resistant ceramic tile, heating while stirring, adding 50kg of manganese mud powder obtained after roasting when the temperature is raised to be more than 70 ℃ (not more than 98 ℃), carrying out disproportionation reaction, and then continuously heating;
(4) Heavy oxidation: after the temperature is raised to 90 ℃, preserving the heat for 1h, and then adding 50L of oxidant solution to carry out oxidation reaction; keeping the temperature at 90 ℃ for 1h, adding 25kg of manganese mud powder obtained after oxidizing roasting, keeping the temperature for 1h, and continuously adding 25L of oxidant solution; keeping the temperature for 1h, adding 25kg of manganese mud powder obtained after oxidizing roasting, keeping the temperature for 1h, adding 25L of oxidant solution, supplementing a little evaporated water in the midway, keeping the temperature for 4h, filtering the reaction liquid, detecting the content of manganese sulfate in the reaction liquid, and taking the reaction end point when the content of manganese sulfate is lower than 10 g/L; the oxidant solution used in the step is a sodium chlorate solution prepared by adding 50kg of sodium chlorate into 100L of water;
(5) Solid-liquid separation, washing, neutralization and drying: and after the reaction liquid is naturally cooled, performing solid-liquid separation on the reaction liquid through a plate-and-frame filter press, wherein the filtrate is mainly waste acid and can be recycled, filter residue is washed with hot water at 80 ℃ until the pH value is more than 2.5, the washed product is neutralized by a sodium hydroxide solution with the mass concentration of 5% until the pH value is 6.8, then the product is washed twice with hot water, the solid-liquid separation is performed again, the drying is performed through hot air at 120 ℃, the crushing can be performed when the moisture content is lower than 3% after the drying is performed for 4 hours, and the active manganese dioxide finished product is obtained after the sieving through a 120-mesh sieve.
As a result of analysis, the contents of heavy metal impurities Fe, cu, pb, co, ni and Cd in the activated manganese dioxide prepared in this example were 1731.2ppm, 55.3pm, 66ppm, 19.6ppm, 11.2ppm and 1.0ppm, respectively. Through detection, the total manganese content in the finished product reaches 55.31%, and the manganese dioxide content is 85.76%; the discharge result of the RS20 battery is as follows: open circuit voltage is 1.72V, 1.8 omega 0.9V continuous discharge is 207min, 3.9 omega 0.9V continuous discharge is 456min, and the standard of first-level electrolytic manganese is achieved.
Claims (7)
1. A preparation method of active manganese dioxide comprises the following steps: the method comprises the steps of taking waste manganese mud recovered by wet dust removal in the production of metal manganese powder as a raw material, and sequentially carrying out the steps of raw material drying, oxidizing roasting, sulfuric acid disproportionation, heavy oxidation, solid-liquid separation, washing, neutralization and product drying to obtain the high-discharge active manganese dioxide.
2. The method for preparing activated manganese dioxide according to claim 1, wherein in the raw material drying step, the drying temperature is controlled to 100-300 ℃ and the drying time is controlled to 1-4 h.
3. The method of claim 1, wherein the oxidizing roasting is performed in hot air, the roasting temperature is controlled to 300-600 ℃, and the roasting time is controlled to 1-4 h.
4. The method for preparing activated manganese dioxide according to claim 1, wherein in said step of disproportionation of sulfuric acid, the mass concentration of sulfuric acid used is 10-60%, and the disproportionation temperature is controlled at 70-98 ℃.
5. The method for producing activated manganese dioxide according to claim 1, wherein an aqueous solution of sodium chlorate having a mass concentration of 30 to 50% is used as the oxidizing agent in the heavy oxidation step.
6. The method for producing activated manganese dioxide according to claim 1, wherein the neutralizing agent used in the neutralizing step is an aqueous solution of sodium hydroxide having a mass concentration of 3% to 20%.
7. The method for preparing activated manganese dioxide according to claim 1, wherein in the step of drying the product, the drying temperature is controlled to 70 ℃ to 120 ℃ and the drying time is controlled to 4h to 24h.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275994A (en) * | 2011-05-24 | 2011-12-14 | 南昌航空大学 | Oxidation-activation method for regeneration and reuse of manganese oxide waste residue in organic synthesis |
| CN102876897A (en) * | 2012-09-26 | 2013-01-16 | 中信锦州金属股份有限公司 | Recovery and purification method of manganese dioxide in electrolytic manganese anode mud |
| CN102963937A (en) * | 2012-10-31 | 2013-03-13 | 铜陵市祥英锌业有限公司 | Novel refining method with by-product manganese dioxide |
| CN106315683A (en) * | 2016-08-22 | 2017-01-11 | 武汉科技大学 | Method for preparing manganese ferrite by using waste zinc manganese dry cell as manganese source |
| CN109205678A (en) * | 2018-10-10 | 2019-01-15 | 北京科技大学 | A method of preparing high-visual density chemical manganese bioxide |
| CN109682799A (en) * | 2018-12-18 | 2019-04-26 | 四川华景国贸实业有限责任公司 | Method for quickly judging availability of natural discharge manganese powder for zinc-manganese battery and method for quickly detecting availability of natural discharge manganese powder for zinc-manganese battery |
| CN114105206A (en) * | 2021-11-25 | 2022-03-01 | 贵州大龙汇成新材料有限公司 | Preparation method of zinc-manganese dry battery active material |
| CN114275819A (en) * | 2021-12-16 | 2022-04-05 | 湖南化工研究院有限公司 | Efficient recovery method of active manganese dioxide |
| CN114956186A (en) * | 2022-04-19 | 2022-08-30 | 广西汇元锰业有限责任公司 | Porous manganese dioxide and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102275994A (en) * | 2011-05-24 | 2011-12-14 | 南昌航空大学 | Oxidation-activation method for regeneration and reuse of manganese oxide waste residue in organic synthesis |
| CN102275994B (en) * | 2011-05-24 | 2013-04-10 | 南昌航空大学 | Oxidation-activation method for regeneration and reuse of manganese oxide waste residue in organic synthesis |
| CN102876897A (en) * | 2012-09-26 | 2013-01-16 | 中信锦州金属股份有限公司 | Recovery and purification method of manganese dioxide in electrolytic manganese anode mud |
| CN102963937A (en) * | 2012-10-31 | 2013-03-13 | 铜陵市祥英锌业有限公司 | Novel refining method with by-product manganese dioxide |
| CN102963937B (en) * | 2012-10-31 | 2015-12-09 | 铜陵市祥英锌业有限公司 | A kind of refining method of by-product Manganse Dioxide |
| CN106315683A (en) * | 2016-08-22 | 2017-01-11 | 武汉科技大学 | Method for preparing manganese ferrite by using waste zinc manganese dry cell as manganese source |
| CN109205678A (en) * | 2018-10-10 | 2019-01-15 | 北京科技大学 | A method of preparing high-visual density chemical manganese bioxide |
| CN109205678B (en) * | 2018-10-10 | 2020-04-10 | 北京科技大学 | Method for preparing high apparent density chemical manganese dioxide |
| CN109682799A (en) * | 2018-12-18 | 2019-04-26 | 四川华景国贸实业有限责任公司 | Method for quickly judging availability of natural discharge manganese powder for zinc-manganese battery and method for quickly detecting availability of natural discharge manganese powder for zinc-manganese battery |
| CN109682799B (en) * | 2018-12-18 | 2021-09-03 | 四川华景国贸实业有限责任公司 | Method for quickly judging availability of natural discharge manganese powder for zinc-manganese battery and method for quickly detecting availability of natural discharge manganese powder for zinc-manganese battery |
| CN114105206A (en) * | 2021-11-25 | 2022-03-01 | 贵州大龙汇成新材料有限公司 | Preparation method of zinc-manganese dry battery active material |
| CN114275819A (en) * | 2021-12-16 | 2022-04-05 | 湖南化工研究院有限公司 | Efficient recovery method of active manganese dioxide |
| CN114275819B (en) * | 2021-12-16 | 2024-03-01 | 湖南化工研究院有限公司 | Efficient recovery method of active manganese dioxide |
| CN114956186A (en) * | 2022-04-19 | 2022-08-30 | 广西汇元锰业有限责任公司 | Porous manganese dioxide and preparation method thereof |
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