CN112551589A - Energy-saving reduction method of manganese dioxide, manganese dioxide and application - Google Patents
Energy-saving reduction method of manganese dioxide, manganese dioxide and application Download PDFInfo
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- CN112551589A CN112551589A CN202011327983.1A CN202011327983A CN112551589A CN 112551589 A CN112551589 A CN 112551589A CN 202011327983 A CN202011327983 A CN 202011327983A CN 112551589 A CN112551589 A CN 112551589A
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- C01G45/10—Sulfates
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25B1/00—Electrolytic production of inorganic compounds or non-metals
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- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention belongs to the technical field of electrolytic manganese, and discloses an energy-saving reduction method of manganese dioxide, manganese dioxide and application, wherein the energy-saving reduction method comprises the following steps: grinding electrolytic manganese anode slag or low-iron manganese dioxide ore until 98% of electrolytic manganese anode slag passes through 100 meshes, and simultaneously grinding sulfur powder until 100% of electrolytic manganese anode slag passes through 100 meshes; uniformly mixing the ground sulfur powder and the ground manganese dioxide ore powder or electrolytic manganese anode slag according to a proportion to obtain mixed ore powder; placing the mixed mineral powder in a closed reaction kettle, and heating the mineral powder to more than 60 ℃ or heating the reaction kettle to more than 60 ℃ by using a combustible organic solvent as a fuel for an initial reaction; after the reaction is completed, manganese sulfate and manganese monoxide can be obtained; cooling manganese sulfate and manganese monoxide, and packaging in a sealed packaging can. The invention provides a method for preparing bivalent manganese ores such as manganese monoxide and manganese sulfate from manganese dioxide ore with high efficiency and low energy consumption.
Description
Technical Field
The invention belongs to the technical field of electrolytic manganese, and particularly relates to an energy-saving reduction method of manganese dioxide, manganese dioxide and application.
Background
At present: manganese ore resources in China only account for 5% of the world, electrolytic manganese production capacity accounts for 98.6% of the world, electrolytic manganese production capacity accounts for 97.4% of the world, and the first world of the electrolytic industry exists. The raw material of the electrolytic manganese mainly comprises manganese carbonate, however, because the distribution of manganese ore resources in China is unbalanced, ore deposits are mostly small and medium, the ore quality is poor and lean ores are mainly used, and the raw material of electrolytic manganese production enterprises is in a situation of extreme tension.
In recent years, in order to relieve the situation of the shortage of manganese carbonate supply, a new process flow of electrolytic manganese dioxide is developed in China to utilize manganese dioxide ores with huge reserves, however, manganese grades of manganese dioxide ores provided by most mines are low, and most of manganese grades are below 18%, so that the process cost of electrolytic manganese dioxide is high, and many manufacturers have to give up the process.
In order to solve the problem, manufacturers in China prepare manganese monoxide by a method of reducing manganese dioxide in a rotary kiln by using carbon, and then prepare manganese sulfate by using the manganese monoxide to obtain a better manganese sulfate raw material.
However, the carbon reduction method needs to be heated to over 700 ℃, the external heating mode causes low heat utilization rate and high energy consumption, and 7000 kilocalories of standard coal can be consumed to prepare over 0.3 ton of manganese sulfate. The high energy consumption and high cost of the carbon-reduced manganese dioxide production process makes it difficult for many manufacturers to bear the process. How to prepare high-grade divalent manganese ore powder by utilizing manganese dioxide with high efficiency and low energy consumption, which provides high-quality raw materials for a plurality of domestic electrolytic manganese production enterprises and reduces the production cost of electrolytic manganese, has become a big subject of the current electrolysis industry.
Through the above analysis, the problems and defects of the prior art are as follows: the existing manganese dioxide garden method has low heat utilization rate, high energy consumption and high cost.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an energy-saving reduction method of manganese dioxide, manganese dioxide and application.
The invention is realized in such a way that the energy-saving reduction method of manganese dioxide comprises the following steps:
grinding electrolytic manganese anode slag or low-iron manganese dioxide ore until 98% of electrolytic manganese anode slag or low-iron manganese dioxide ore passes through 100 meshes, and grinding sulfur powder until 100% of sulfur powder passes through 100 meshes;
step two, uniformly mixing the ground sulfur powder and the ground manganese dioxide ore powder or electrolytic manganese anode slag according to a proportion to obtain mixed ore powder;
putting the mixed mineral powder into a closed reaction kettle, and heating the mineral powder to be more than 60 ℃ or heating the reaction kettle to be more than 60 ℃ by using a combustible organic solvent as a fuel for an initial reaction;
step four, after the reaction is completed, manganese sulfate and manganese monoxide can be obtained; cooling manganese sulfate and manganese monoxide, and packaging in a sealed packaging can.
Further, in the second step, the step of uniformly mixing the ground sulfur powder and the ground manganese dioxide ore powder or the electrolytic manganese anode slag according to the proportion comprises the following steps:
mixing manganese ions with positive valence 4 and sulfur according to the mass ratio of 3:1, or mixing manganese dioxide content and sulfur content in the ore powder according to the weight ratio of 8.15625: 1, and mixing.
Further, uniformly mixing the ground sulfur powder and the ground manganese dioxide ore powder or electrolytic manganese anode slag according to a proportion further comprises:
when the content of manganese dioxide is lower than 40%, determining the actual addition amount of sulfur according to the content of positive 4-valent manganese in the manganese dioxide ore; the actual addition amount of the sulfur can exceed 1-3% of the theoretical addition amount.
Further, in the third step, the flammable organic solvent may be one of ethanol, methanol, or diesel oil.
Further, the energy-saving reduction chemical equation of the manganese dioxide is as follows:
S+3MnO2＝2MnO+MnSO4。
another object of the present invention is to provide a method for electrolyzing manganese dioxide, which uses the energy-saving method for reducing manganese dioxide.
Another object of the present invention is to provide a manganese dioxide obtained by the energy-saving reduction method of manganese dioxide.
Another object of the present invention is to provide a dry battery using the manganese dioxide as a polarizing agent
By combining all the technical schemes, the invention has the advantages and positive effects that: the invention provides a method for preparing bivalent manganese ores such as manganese monoxide and manganese sulfate from manganese dioxide ore with high efficiency and low energy consumption. The invention is based on that manganese dioxide and elemental sulfur can generate oxidation-reduction reaction at lower temperature to generate two divalent manganese compounds of manganese monoxide and manganese sulfate, and simultaneously, a great deal of reaction heat released in the reaction process can effectively promote the reaction speed to be improved by ten thousand times, so that the reaction can be completed in a very short time. The manganese dioxide is reduced into bivalent manganese by using sulfur as a reducing agent, the products are manganese monoxide and manganese sulfate which are very easily dissolved in a dilute sulfuric acid solution, and the reaction process is an exothermic reaction, so that the production process does not need to be heated, and the required energy consumption can be completely met only by reaction heat.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments of the present application will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present application, and it is obvious for those skilled in the art that other drawings can be obtained from the drawings without creative efforts.
FIG. 1 is a flow chart of a method for energy-saving reduction of manganese dioxide according to an embodiment 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 is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problems in the prior art, the invention provides an energy-saving reduction method of manganese dioxide, manganese dioxide and application thereof, and the invention is described in detail with reference to the accompanying drawings.
As shown in fig. 1, the energy-saving reduction method of manganese dioxide provided by the embodiment of the present invention includes:
s101, grinding the electrolytic manganese anode slag or the low-iron manganese dioxide ore until 98% of the electrolytic manganese anode slag or the low-iron manganese dioxide ore passes through 100 meshes, and simultaneously grinding sulfur powder until 100% of the sulfur powder passes through 100 meshes;
s102, uniformly mixing the ground sulfur powder with the ground manganese dioxide ore powder or electrolytic manganese anode slag according to a proportion to obtain mixed ore powder;
s103, placing the mixed mineral powder in a closed reaction kettle, and heating the mineral powder to more than 60 ℃ or heating the reaction kettle to more than 60 ℃ by using a combustible organic solvent as a fuel for an initial reaction;
s104, obtaining manganese sulfate and manganese monoxide after complete reaction; cooling manganese sulfate and manganese monoxide, and packaging in a sealed packaging can.
In step S102, the step of uniformly mixing the ground sulfur powder and the ground manganese dioxide ore powder or the electrolytic manganese anode slag according to the proportion provided by the embodiment of the present invention includes:
mixing manganese ions with positive valence 4 and sulfur according to the mass ratio of 3:1, or mixing manganese dioxide content and sulfur content in the ore powder according to the weight ratio of 8.15625: 1, and mixing.
The embodiment of the invention provides a method for uniformly mixing ground sulfur powder and ground manganese dioxide ore powder or electrolytic manganese anode slag according to a proportion, which further comprises the following steps:
when the content of manganese dioxide is lower than 40%, determining the actual addition amount of sulfur according to the content of positive 4-valent manganese in the manganese dioxide ore; the actual addition amount of the sulfur can exceed 1-3% of the theoretical addition amount.
In step S103, the flammable organic solvent provided by the embodiment of the present invention may be one of ethanol, methanol, and diesel oil.
The energy-saving reduction chemical equation of manganese dioxide provided by the embodiment of the invention is as follows:
S+3MnO2＝2MnO+MnSO4。
the technical solution of the present invention is further illustrated by the following specific examples.
Example 1:
in the electrolytic manganese production process, an anode in an electrolytic cell is subjected to oxidation reaction, the produced anode slag mainly contains manganese dioxide, and the rest is a small amount of undissolved electrolytic manganese metal sheets, precipitated ammonium sulfate crystals and a small amount of impurities. The manganese dioxide content can reach more than 70 percent, the manganese element grade is more than or equal to 50 percent, the content of heavy metal elements such as iron, cobalt, nickel and the like influencing electrolysis is extremely low, the manganese dioxide is reduced into bivalent manganese, and the high-quality mineral powder raw material can be provided for electrolytic manganese production.
The invention grinds electrolytic manganese anode slag or low-iron manganese dioxide ore to 98 percent of manganese dioxide ore which passes 100 meshes, and simultaneously, 100 percent of sulfur powder which passes 100 meshes is uniformly mixed with the ground manganese dioxide ore powder or the electrolytic manganese anode slag according to a proper proportion, specifically, the mixture is mixed according to the proportion of manganese ions with positive valence 4 and sulfur substances of 3:1, or according to the proportion of manganese dioxide content and sulfur content in the ore powder of 8.15625: 1, placing the mixed mineral powder into a closed reaction kettle after uniform mixing, taking an inflammable organic solvent such as ethanol, methanol or diesel oil as fuel for initial reaction, igniting the mixed mineral powder, starting redox reaction when the temperature of the mixed mineral at an ignition position in the reaction kettle reaches 60 ℃, discharging a large amount of heat in the reaction process, raising the temperature in the reaction kettle, promoting the rapid reaction of the rest mixed mineral powder, completing the reaction process in a very short time, generating manganese monoxide which is easy to dissolve in dilute sulfuric acid and manganese sulfate which is easy to dissolve in water, generating no other new compounds, generating no gas in reactants, and enabling the reaction kettle to be free of pressure. The ignition temperature is determined according to the content of manganese dioxide in the used manganese dioxide ore powder, the initial temperature of reduction is low when the content of manganese dioxide is high, and the required initial temperature is high when the content of manganese dioxide is low, specifically determined according to the content of manganese dioxide.
Example 2:
grinding manganese dioxide raw ore or electrolytic manganese anode slag until 98% of manganese dioxide raw ore or electrolytic manganese anode slag passes through 100 meshes, grinding ore grains to be 0.074-0.149mm, grinding sulfur ore until 98% of manganese dioxide raw ore or electrolytic manganese anode slag passes through 100 meshes, and then mixing the manganese dioxide ore and sulfur powder according to the mass ratio of manganese to sulfur of 3:1, or mixing manganese dioxide and sulfur in the mineral powder according to a weight ratio of 8.15625: 1, and mixing. When the content of manganese dioxide is less than 40%, the amount of sulfur used may exceed 1% to 3% of the theoretical amount of usage in order to prevent incomplete reduction due to non-uniform mixing, and the amount of sulfur used exceeding the theoretical amount of usage is determined according to the content of positive 4-valent manganese in the manganese dioxide ore. Putting the mixed mineral powder of sulfur dioxide and sulfur mixed according to the proportion into a sealed reaction furnace, igniting the mixed mineral powder in a reaction kettle by alcohol or fuel oil and other combustible substances, raising the temperature of the mineral powder at the ignition position to be more than 60 ℃, releasing a large amount of heat by redox reaction between manganese dioxide and sulfur at the ignition position, promoting the temperature in the reaction kettle to be rapidly raised, automatically carrying out reduction reaction on the rest mixed mineral powder, obtaining manganese sulfate and manganese monoxide after the reaction is completed, cooling, and filling into a sealed packaging tank. The compositional analysis is shown in tables 1 and 2.
TABLE 1 electrolytic manganese Anode slags Main chemical composition
TABLE 2 main chemical composition of ore powder after reduction of electrolytic manganese anode slag
The applicable manganese oxide ore raw materials are as follows:
1. when the manganese content of the manganese dioxide ore is more than 13%, the reaction heat energy promotes the reaction to be spontaneously carried out, and when the manganese content is less than 13%, the reaction heat is not enough to spontaneously carry out the reaction and can be carried out only by external heating, so that the energy consumption is high, and compared with the traditional reduction method, the reduction method has the advantage of high energy consumption.
2. The moisture content of the manganese oxide ore is lower than 10%, otherwise, the evaporation of moisture needs to absorb a large amount of reaction heat, so that the reaction temperature is difficult to reach, and the reaction cannot be carried out spontaneously.
The above description is only for the purpose of illustrating the present invention and the appended claims are not to be construed as limiting the scope of the invention, which is intended to cover all modifications, equivalents and improvements that are within the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The energy-saving reduction method of manganese dioxide is characterized by comprising the following steps:
grinding electrolytic manganese anode slag or low-iron manganese dioxide ore, and grinding sulfur powder;
uniformly mixing the ground sulfur powder and the ground manganese dioxide ore powder or electrolytic manganese anode slag according to a proportion to obtain mixed ore powder;
placing the mixed mineral powder in a closed reaction kettle, and heating the mineral powder or heating the reaction kettle by using a combustible organic solvent as a fuel for an initial reaction;
after the reaction is completed, manganese sulfate and manganese monoxide are obtained; cooling manganese sulfate and manganese monoxide, and packaging in a sealed packaging can.
2. The energy saving reduction method of manganese dioxide according to claim 1, wherein the electrolytic manganese anode slag or low iron manganese dioxide ore is ground to 98% passing 100 mesh while the sulfur powder is ground to 100% passing 100 mesh.
3. The energy-saving reduction method of manganese dioxide according to claim 1, wherein the mixing of the ground sulfur powder and the ground manganese dioxide ore powder or the electrolytic manganese anode slag uniformly in proportion comprises:
mixing manganese ions with positive valence 4 and sulfur according to the mass ratio of 3:1, or mixing manganese dioxide content and sulfur content in the ore powder according to the weight ratio of 8.15625: 1, and mixing.
4. The energy-saving manganese dioxide reduction method according to claim 1, wherein the step of uniformly mixing the ground sulfur powder with the ground manganese dioxide ore powder or the electrolytic manganese anode slag in proportion further comprises:
when the content of manganese dioxide is lower than 40%, determining the actual addition amount of sulfur according to the content of positive 4-valent manganese in the manganese dioxide ore; the actual addition amount of the sulfur can exceed 1-3% of the theoretical addition amount.
5. The energy saving reduction method of manganese dioxide according to claim 1, wherein said flammable organic solvent is one of ethanol, methanol or diesel.
6. The energy-saving reduction method of manganese dioxide according to claim 1, wherein the mixed ore powder is placed in a closed reaction vessel, and the ore powder is heated to 60 ℃ or more or the reaction vessel is heated to 60 ℃ or more using a flammable organic solvent as a fuel for an initial reaction.
7. The energy efficient reduction method of manganese dioxide according to claim 1, wherein said energy efficient reduction chemical equation of manganese dioxide is as follows:
S+3MnO2＝2MnO+MnSO4。
8. a method for electrolyzing manganese dioxide, characterized in that the energy-saving method for reducing manganese dioxide according to any one of claims 1 to 7 is used.
9. Manganese dioxide obtainable by an energy-efficient reduction process of manganese dioxide according to any one of claims 1 to 7.
10. Use of the manganese dioxide of claim 9 as a polarizer in a dry battery.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157481A (en) * | 2007-07-24 | 2008-04-09 | 汪云华 | Method for preparing manganese sulfate by manganese oxide ore |
| CN101837959A (en) * | 2010-05-14 | 2010-09-22 | 湖南省泸溪县金旭冶化有限责任公司 | Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace |
| CN101914676A (en) * | 2010-09-08 | 2010-12-15 | 中南大学 | Manganese oxide mineral sulfur-based fire reduction method |
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- 2020-11-24 CN CN202011327983.1A patent/CN112551589A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157481A (en) * | 2007-07-24 | 2008-04-09 | 汪云华 | Method for preparing manganese sulfate by manganese oxide ore |
| CN101837959A (en) * | 2010-05-14 | 2010-09-22 | 湖南省泸溪县金旭冶化有限责任公司 | Method for reducing pyrolusite and co-producing sulfuric acid by utilizing sulfur in fluidized bed furnace |
| CN101914676A (en) * | 2010-09-08 | 2010-12-15 | 中南大学 | Manganese oxide mineral sulfur-based fire reduction method |
Non-Patent Citations (1)
| Title |
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| 张元波等: "低品位氧化锰矿硫磺还原焙烧技术条件研究", 《矿冶工程》 * |
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