CN1127726A - Method for producing manganese sulfate using waste residue from production of potassium permanganate - Google Patents
Method for producing manganese sulfate using waste residue from production of potassium permanganate Download PDFInfo
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Abstract
The process for producing manganese sulfate with waste dregs from production of potassium permanganate includes treating said waste dregs with sulfuric acid, addition of powdered troilite ore and sulfuric acid for reaction and leaching, evaporation concentration and standing. Obtained manganese sulfate may be used in industry or as feed.
Description
The invention relates to a method for preparing a manganese compound in the field of inorganic chemistry, in particular to a method for preparing manganese sulfate.
Currently, there are four main methods for producing manganese sulfate: the first method is a sulfuric acid leaching method of manganese carbonate ore; the second method is a high-temperature roasting reduction method of pyrolusite; the third is leaching pyrolusite with pyrite and sulfuric acid, namely wet leaching; the fourth is a byproduct recovery process for the production of hydroquinone. The raw materials of the first three methods are mineral resources of manganese carbonate ore or pyrolusite, and the production cost of manganese sulfate produced by the method is high. As for the fourth process, it is only applicable to the specific case of hydroquinone production, and the quality of manganese sulfate obtained is also poor.
The potassium permanganate can be produced to finally obtain the potassium permanganate with a large amount of dioxideThe manganese is obtained into waste slag, and the content of manganese dioxide in wet slag accounts for about 10 percent. The waste residue also contains KOH and K2CO3、KMnO4、Ca(OH)2、CaCO3、Al2O3、SiO2、MgO、Fe2O3Etc. of KOH and K2CO3、KMnO4、Ca(OH)2The components have serious environmental pollution and are not allowed to be poured everywhere, so that the potassium permanganate storage tank only occupies a large amount of land and is specially piled up to store, and waste residues which are the same as those in hills are piled up in each potassium permanganate production plant. Although environmental protection departments mandate treatment of waste residues for many years, and a great deal of research and tests are carried out on the treatment and utilization of the waste residues by many colleges, research institutions and manufacturers, the treatment and utilization of the waste residues are not successful all the time because the waste residues contain low manganese content, contain many impurities and are difficult to develop and utilize.
The invention aims to provide a method for producing manganese sulfate by using waste residues generated in potassium permanganate production.
The process flow for preparing the sulfur and the manganese by using the manganese ore through a wet leaching process comprises the following steps:
(pyrolusite + sulfuric acid + pyrite) combined leaching → oxidation to remove Fe2+→ neutralization and pH adjustment for Fe removal3+、Al3+→ removal of heavy metal ion → filter pressing → preparation of finished product liquid → standing → filter pressing → evaporative crystallization → centrifugal separation → drying → crushing → manganese sulfate finished product
The invention also adopts a wet leaching process, which comprises the following process flows:
treating waste slag with sulfuric acid → adding pyrite and sulfuric acid for combination leaching → oxidizing to remove Fe2+→ neutralization and pH adjustment for Fe removal3+、Al3+→ removal of heavy metal ion → filter pressing → preparation of dilute product liquid → evaporative concentration → standing → filter pressing → preparation of concentrated product liquid → evaporative crystallization → centrifugal separation → drying → crushing → manganese sulfate finished product
It is characterized in that:
a. the raw material used by the method is waste residue for producing potassium permanganate;
b. first with sulfuric acidTreating waste residues: adding water into the waste residue, adding sulfuric acid, heating to react, press-filtering the treated waste residue, washing with water until the washing water is neutral, and taking Mg and K in the original waste residue as soluble Mg2+、K+Entering the solution, separating out from reactants after filter pressing and water washing, wherein the reaction is as follows:
c. adding pyrite and sulfuric acid for combination leaching: adding water and pyrite powder into the waste residue after washing, adding sulfuric acid, and heating for reaction, wherein the reaction comprises the following steps:
FeSO in three products after reaction4All, H2SO3Part of (1), H2Can react with oxidation and reduction:
MnO in waste residue after reaction2Conversion to MnSO4Into solution.
d. After the dilute product liquid is prepared, evaporation concentration is firstly carried out, then standing is carried out, and then pressure filtration is carried out to prepare concentrated product liquid. Since the dilute product liquid is evaporatedand concentrated and then is stood, the CaSO in the concentrated product liquid is generated due to the same ion effect4Will be greatly reduced in solubility, and thus most of the CaSO4Precipitating while the settling velocity is lower2SO3Colloid, Al (OH)3Most of the precipitate is also precipitated and can be removed in the next filter pressing procedure.
In order to fully react impurities in the waste residue, when the waste residue is treated by sulfuric acid, the amount of the added sulfuric acid can be converted according to the following proportion: the weight ratio of the dry-based waste residue to the 100% sulfuric acid is as follows: 1: 0.35-1: 0.5, the PH value is 2-6, the reaction temperature is not lower than 70 ℃, the reaction time is more than 0.5 hour, and the stirring is carried out during the reaction.
In the process of adding pyrite and sulfuric acid for combined leaching, MnO in waste slag is used2Fully reacting, and converting the weight ratio of each reactant according to the following ratio: manganese dioxide, 100% concentration sulfuric acid and ferrous disulfide (1: 0.98-1.5: 1.1-0.18), reaction temperature not lower than 70 deg.C, reaction time more than 2 hr, stirring during reaction.
When the waste slag is treated with sulfuric acid and the pyrite and sulfuric acid are added for chemical leaching, the water is added in such an amount that the solid-to-liquid ratio of reactants is 1: 3-1: 6 and 1: 2-1: 5, respectively.
In addition, Fe is removed by oxidation2+The oxidant used in the traditional wet leaching process in the working procedure is pyrolusite or hydrogen peroxide or air, and in the method, the oxidant can be waste residue treated by sulfuric acid, and the dosage of the oxidant is 2-3% of the total combined residue (the dosage of thewaste residue is Fe2+Except for the reaction), the reaction temperature is not lower than 70 ℃, and the reaction time is more than 0.5 hour.
The reaction is as follows:
removing Fe by neutralizing and adjusting pH value3+、Al3+In the working procedure, the neutralizer in the traditional wet leaching process is lime or manganese carbonate ore or limestone powder, and the neutralizer in the method can be lime or manganese carbonate ore or limestone powderThe light calcium carbonate is used, so that impurity ions are not introduced and local overbasing is not caused, the dosage of the light calcium carbonate is such that the pH value is 5-6.5 at the end of the reaction, the reaction temperature is not lower than 70 ℃, and the reaction time is more than 0.5 hour. The reaction is as follows:
the raw material of manganese sulfate produced by the method is waste residue from potassium permanganate production, so the production cost is greatly lower than that of manganese sulfate produced by pyrolusite or manganese carbonate ore, and mineral resources are saved. More importantly, the method solves the problems of land occupation and environmental pollution caused by the waste residue in the production of potassium permanganate. The final waste residue of manganese sulfate produced by said method contains no acid, alkali and oxidant, and its main component is CaSO4、Fe(OH)SO4And a small amount of SiO2、AlO3、FeO3They are environmentally friendly. Therefore, the method changes waste into valuable, not only has considerable economic benefit, but also has great social benefit, and solves the problem that people want to solve but do not solve for a long time. In addition, the method adopts the processes of firstly treating the waste manganese slag by using sulfuric acid to prepare a dilute product liquid, then carrying out evaporation concentration, then standing, using light calcium carbonate as a neutralizer and the like, so that the prepared manganese sulfate product has good quality and meets the standards of GB 1622-86 industrial manganese sulfate and GB 8213-87 feed-grade manganese sulfate.
Example one
1. Treating waste residues with sulfuric acid: putting 1 ton wet waste residue with water content of 34.3% into a reaction tank, adding 2.5 ton water, stirring, slowly adding 93% H after stirring uniformly2SO4247Kg, in this case converted into dry residue: 100% sulfuric acid 1: 0.35. The reaction was heated to 70 ℃ and allowed to react at this temperature for 2 hours, at which time the pH of the solution was determined to be 3. And (3) conveying the slag to a filter press for filter pressing, pumping water into the filter press after filter pressing to wash the slag until the pH value of washing water is 6, and unloading the filter slag.
2. Adding pyrite and sulfuric acid for combination leaching: the weight of the filter residue is 987Kg and contains MnO after measurement and test210.1 percent. In MnO form2100% of H2SO4∶FeS2Feeding materials according to the proportion of 1: 0.98: 1.1. Adding 950Kg of filter residue into a reaction tank, adding 1 ton of water into 200-mesh pyrite powder containing 35% of sulfur, stirring uniformly, and then adding 101Kg of 93% of H2SO4The reaction mixture was heated to 70 ℃ and reacted at this temperature for 6 hours, whereupon the combined slurry was white gray.
3. Removal of Fe by oxidation2+: after the chemical leaching, 20Kg of waste residue treated with sulfuric acid, which is about 2.1% of the total chemical residue amount, was added and reacted at 70 ℃ for 2 hours. Through inspection, Fe2+Is removed.
4. Neutralizing and adjusting pH value to remove Fe3+、Al3+: then, precipitated calcium carbonate was added to the reaction solution to give a solution having a pH of 6, and the reaction was carried out at 70 ℃ for 2 hours.
5. Removing heavy metal ions: and adding a BaS saturated solution into the solution, wherein the reaction temperature is 70 ℃, and the reaction time is 2 hours, so as to remove heavy metal ions.
6. And (3) filter pressing: the slurry is sent to a filter press for filter pressing, and water is pumped into the filter pressing after the filter pressingThe filter residue is washed by water, and the washing water is used as the next combination water. At this time, a diluted product solution of manganese sulfate of 1m is obtained3The baume degree is 14.5 DEG Be, and the washing water is 0.95m3The baume degree is 3 ° baume.
7. And (3) evaporation and concentration: the diluted product liquid is sent to an evaporator for evaporation and concentration to 37 DEG Be, and the volume is 0.37m3。
8. Standing: and putting the product after evaporation concentration into a settling pond and standing for 12 hours.
9. And (3) filter pressing: and (4) conveying the product liquid obtained after standing to a filter press for filter pressing, and preparing concentrated product liquid at the moment.
10. Evaporating, crystallizing, centrifugally separating, drying, crushing, conveying the concentrated product liquid into an evaporator to evaporate to 50 degrees Be, and conveying the concentrated product liquid into a centrifugal machine for separation while the concentrated product liquid is hot to obtain wet crystals and mother liquid with the Baume degree of 38 degrees Be. And (4) using the mother liquor for next evaporation crystallization, drying the wet crystals for 4 hours in a dryer, taking out and crushing to obtain the finished product. The assay results were as follows: index name national Standard measurement result appearanceWhite or pinkish crystal MnSO4H2O% is not less than 98.098.3, Fe% is not less than 0.0040.002, Cl% is not less than 0.0040.003, water-insoluble substance is not less than 0.050.02, and pH value is 5-76
Meets the GB 1622-86 industrial manganese sulfate standard.
Example two
Putting 1 ton wet waste residue with water content of 31.7% into a reaction tank, adding 3 tons of water, stirring, slowly adding 70% H2SO4In this case, the ratio of the dry residue to 100% sulfuric acid is 1: 0.45. The reaction was heated to 100 ℃ and allowed to react at this temperature for 0.5 h, at which time the solution PH was determined to be 4.7. And (3) conveying the residue to a filter press for filter pressing, pumping water into the filter press after filter pressing to wash the filter residue until the pH value of the washing water is 7, and unloading the filter residue. After measurement and test, the filter residue weighs 1006Kg and contains MnO211.2 percent. In MnO form2100% of H2SO4∶FeS2Feeding the materials according to the proportion of 1: 1.5: 0.18. Putting 980Kg of filter residueinto a reaction tank, adding 30Kg of 180 mesh pyrite powder containing 35% of sulfur, and adding 0.95m of water3Stirring, adding 93% H2SO4177Kg, heated to 100 ℃ and reacted at this temperature for 2.5 hours, at which time the combined slurry was off-white. 20Kg of waste slag treated with sulfuric acid, which accounts for about 2% of the total amount of the combined slag, was added to the slurry and reacted at 100 ℃ for 0.5 hour, which was completely removed by assay. Then, precipitated calcium carbonate was added to the reaction solution to give a solution having a pH of 6, and the reaction was carried out at 100 ℃ for 0.5 hour. Then adding saturated BaS solution, reacting at 100 deg.C for 1 hr to remove heavy metal ions. And then the slurry is sent to a filter press for filter pressing, water is pumped into the filter press after filter pressing, filter residues are washed by water, and washing water is used as combination water for the next time. At this time, the dilute manganese sulfate is obtainedProduct liquid 1.3m3The baume degree is 14 Be, and the washing water is 1.1m3Its baume degree is 3.5 ° baume. The dilute product liquor is sent to an evaporator for evaporation and concentration to 33 DEG Be, and the volume of the dilute product liquor is 0.61m3. And then the product liquid after evaporation concentration is sent into a settling pond to be stood for 24 hours. Will stand stillAnd (5) sending the product liquid to a filter press for filter pressing to obtain concentrated product liquid. The concentrated product liquid is sent to an evaporator for evaporation and concentration to 55 DEG Be, and is sent to a centrifuge for separation while the concentrated product liquid is hot, so that wet crystals and 0.12m of which the Baume degree is 38 DEG Be are obtained3Mother liquor is used for next evaporation crystallization, wet crystals are sent to a dryer to be dried for 4 hours, and the wet crystals are taken out and crushed to obtain 95Kg of finished product. The assay criteria are as follows: index name national standard determination result MnSO with white or pinkish crystal4H2O％≥ 98.0 98.3 Mn ％ ≤ 31.8 31.9
The fineness (through a w-2.50 mu m sieve) of more than or equal to 9597 is that the percentage of heavy metal (counted by P6) is more than or equal to 0.0005 and less than or equal to 0.050.03
Meets the GB 8213-87 feed-grade manganese sulfate standard.
EXAMPLE III
1 ton of wet waste residue with water content of 30.5% is put into a reaction tank, 3.5 tons of water are added, stirring is started, after the mixture is uniform, 66.4% of sulfuric acid which is 1: 0.49 relative to dry waste residue and 100% of sulfuric acid is slowly added, the mixture is heated to 90 ℃, the reaction is carried out for 1 hour at the temperature, and the PH value is measured to be 2.3. And (3) conveying the residue to a filter press for filter pressing, pumping water into the filter press after filter pressing, washing the filter residue with water until the pH value is 6, and discharging the filter residue. The weight of the filter residue is 991Kg and contains MnO after measurement and test212.1 percent. In MnO form2100% of H2SO4∶FeS2＝1∶1.21∶0.72 feed. 960Kg of waste residue is put into a reaction tank, 127.5Kg of pyrite powder with the sulfur content of 35 percent and 100 meshes is added, and 1.1m of water is added3Stirring, adding 93% H2SO4151Kg, heated to 90 ℃ and reacted at this temperature for 4 hours, at which time the combined slurry was white gray. 25Kg of waste slag treated with sulfuric acid, which accounts for about 2.6% of the total amount of the combined slag, was added to the slurryand reacted at 90 ℃ for 1 hour, which was completely removed by assay. Then, precipitated calcium carbonate was added to the reaction solution to give a solution having a pH of 5.5, and the reaction was carried out at 90 ℃ for 1 hour. Then adding BaS saturated solution to react for 1 hour at 90 ℃ to remove heavy metal ions. And then the slurry is sent to a filter press for filter pressing, water is pumped into the filter press after filter pressing, filter residues are washed by water, and the washing water is used as combination water for the next time. At this time, a dilute product solution of manganese sulfate of 1.3m is obtained3The baume degree of which is 14 ° Be, 1m of washing water3The baume degree is 3 ° baume. The dilute product liquor is sent to an evaporator for evaporation and concentration to 35 DEG Be, and the volume of the dilute product liquor is 0.6m3. And then the product liquid after evaporation concentration is sent into a settling pond to be stood for 24 hours. And (4) conveying the product liquid after standing to a filter press for filter pressing to obtain concentrated product liquid. The concentrated product liquid is sent to an evaporator for evaporation and concentration to 45 DEG Be, and is sent to a centrifuge for separation while the concentrated product liquid is hot, so that wet crystals and 0.17m of which the Baume degree is 38 DEG Be are obtained3And (3) mother liquor, wherein the mother liquor is used for next evaporation crystallization, the wet crystals are sent to a far infrared oven for quick drying for 50 minutes, and the wet crystals are taken out and crushed to obtain the finished product of 99 Kg. The test indexes of the finished product are as follows:index name national standard determination result MnSO with white or pinkish crystal4H2O% is more than or equal to 98.098.1, Fe% is more than or equal to 0.0040.004 Cl% and more than or equal to 0.0040.003, water insoluble is more than or equal to 0.050.03, and the pH value is 5-76.0
Meets the GB 1622-86 industrial manganese sulfate standard.
Claims (6)
1. A process for preparing manganese sulfate from the waste dregs generated in preparing potassium permanganate includes oxidizing to remove Fe2+Neutralizing and adjusting pH value to remove Fe3+、Al3+Removing heavy metal ions, and performing filter pressing to obtain a dilute product liquid, wherein the concentrated product liquid is subjected to evaporative concentration, centrifugal separation, drying and crushing, and the method is characterized in that:
a. the raw material used by the method is waste residue for producing potassium permanganate;
b. firstly, treating waste residues by using sulfuric acid: adding water into the waste residues, adding sulfuric acid, heating to react, then carrying out filter pressing on the treated waste residues, washing with water after filter pressing, and washing until the washing water is neutral;
c. adding pyrite and sulfuric acid for combination leaching: adding water and pyrite powder into the waste residue after water washing, adding sulfuric acid, and heating for reaction;
d. after the dilute product liquid is prepared, evaporation concentration is firstly carried out, then standing is carried out, and then the concentrated product liquid is prepared by filter pressing.
2. The method for producing manganese sulfate from waste residue generated in potassium permanganate production according to claim 1, which comprises the following steps: when the waste residue is treated by sulfuric acid, the amount of sulfuric acid is added soas to control the reaction liquid to be acidic at the end of the reaction.
3. The method for producing manganese sulfate from waste residue generated in potassium permanganate production according to claim 1, which comprises the following steps: when the pyrite and the sulfuric acid are added for combination leaching, the weight of each reactant is converted according to the following proportion: manganese dioxide, 100% concentration sulfuric acid and ferrous disulfide (1: 0.98-1.5: 1.1-0.18), reaction temperature not lower than 70 deg.C, reaction time more than 2 hr, stirring during reaction.
4. The method for producing manganese sulfate from waste residue from potassium permanganate production as claimed in claim 1, 2 or 3, wherein: when the waste slag is treated by sulfuric acid and the pyrite and sulfuric acid are added for chemical combination leaching, the addition of water is made so that the solid-liquid ratio of reactant is 1: 3-1: 6 and 1: 2-1: 5 respectively.
5. The method for producing manganese sulfate from waste residue generated in potassium permanganate production according to claim 4, which comprises the following steps: the oxidant used in the oxidation removal procedure is waste residue treated by sulfuric acid, the consumption of the oxidant is 2-3% of the total combined residue, the reaction temperature is not lower than 70 ℃, and the reaction time is more than 0.5 hour.
6. The method for producing manganese sulfate from waste residue generated in potassium permanganate production according to claim 4, which comprises the following steps: removing Fe by neutralizing and adjusting pH value3+、Al3+The neutralizing agent used in the working procedure is light calcium carbonate, the dosage of the neutralizing agent is such that the pH value is 5-6.5 when the reaction is finished, the reaction temperature is not lower than 70 ℃, and the reaction time is more than 0.5 hour.
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2554519A4 (en) * | 2010-03-29 | 2013-09-04 | Guizhou Redstar Developing Co | Method for preparing manganese sulfate monohydrate |
| CN103594697A (en) * | 2013-11-11 | 2014-02-19 | 甘肃大象能源科技有限公司 | Method of using potassium permanganate waste residue to prepare lithium manganate cathode material |
| CN103757228A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching pyrolusite |
| CN103757433A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757271A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757430A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757267A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757234A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching pyrolusite |
| CN104004919A (en) * | 2014-06-11 | 2014-08-27 | 张安良 | Environment-friendly recycling process of waste residues in electrolytic manganese production |
| CN105967240A (en) * | 2016-04-19 | 2016-09-28 | 东北大学 | Method for preparing ammonium jarosite and trimanganese tetroxide by using potassium permanganate waste residues |
| CN109319844A (en) * | 2018-12-07 | 2019-02-12 | 贵州大龙汇成新材料有限公司 | A kind of Impure Manganese-Sulfate method of purification |
| CN112246848A (en) * | 2020-10-23 | 2021-01-22 | 麻崇明 | Application of clover to treatment of residual compound solution after potassium permanganate preparation of oxygen |
| CN113909260A (en) * | 2021-11-11 | 2022-01-11 | 湖南广义节能装备有限公司 | Manganese product clean production and resource recycling treatment process |
-
1995
- 1995-05-19 CN CN 95110459 patent/CN1127726A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2554519A4 (en) * | 2010-03-29 | 2013-09-04 | Guizhou Redstar Developing Co | Method for preparing manganese sulfate monohydrate |
| CN103594697B (en) * | 2013-11-11 | 2015-12-30 | 甘肃大象能源科技有限公司 | A kind of method being prepared manganate cathode material for lithium by potassium permanganate manganese waste slag |
| CN103594697A (en) * | 2013-11-11 | 2014-02-19 | 甘肃大象能源科技有限公司 | Method of using potassium permanganate waste residue to prepare lithium manganate cathode material |
| CN103757271B (en) * | 2013-12-29 | 2016-01-20 | 四川师范大学 | The leaching method again of the waste residue that sulfuric acid leaching manganese carbonate ore produces |
| CN103757267B (en) * | 2013-12-29 | 2016-01-20 | 四川师范大学 | The leaching method again of the waste residue that sulfuric acid leaching manganese carbonate ore produces |
| CN103757430A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757267A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757234A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching pyrolusite |
| CN103757271A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757433A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for re-leaching waste residue generated through leaching manganese carbonate ore with sulfuric acid |
| CN103757228A (en) * | 2013-12-29 | 2014-04-30 | 四川师范大学 | Method for leaching pyrolusite |
| CN103757234B (en) * | 2013-12-29 | 2016-01-20 | 四川师范大学 | The leaching method of pyrolusite |
| CN103757228B (en) * | 2013-12-29 | 2016-01-20 | 四川师范大学 | The leaching method of pyrolusite |
| CN104004919A (en) * | 2014-06-11 | 2014-08-27 | 张安良 | Environment-friendly recycling process of waste residues in electrolytic manganese production |
| CN104004919B (en) * | 2014-06-11 | 2016-03-23 | 张安良 | The environment-protective circulating recycling technique of waste residue in a kind of electrolytic manganese production |
| CN105967240A (en) * | 2016-04-19 | 2016-09-28 | 东北大学 | Method for preparing ammonium jarosite and trimanganese tetroxide by using potassium permanganate waste residues |
| CN105967240B (en) * | 2016-04-19 | 2018-04-13 | 东北大学 | A kind of method that ammonium jarosite and mangano-manganic oxide are prepared using potassium permanganate waste residue |
| CN109319844A (en) * | 2018-12-07 | 2019-02-12 | 贵州大龙汇成新材料有限公司 | A kind of Impure Manganese-Sulfate method of purification |
| CN112246848A (en) * | 2020-10-23 | 2021-01-22 | 麻崇明 | Application of clover to treatment of residual compound solution after potassium permanganate preparation of oxygen |
| CN113909260A (en) * | 2021-11-11 | 2022-01-11 | 湖南广义节能装备有限公司 | Manganese product clean production and resource recycling treatment process |
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