CN112553468A - Method for producing high-purity manganese sulfate by adopting metal manganese anode mud - Google Patents
Method for producing high-purity manganese sulfate by adopting metal manganese anode mud 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
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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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/008—Wet processes by an alkaline or ammoniacal leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for producing high-purity manganese sulfate by adopting metal manganese anode slime, which comprises the following steps: and adding water, carbonate solution, acid solution and water into the electrolytic manganese metal anode mud in sequence for cleaning to obtain anode mud with low calcium and magnesium and low acid content, adding water, sulfuric acid and iron powder into the anode mud with low calcium and magnesium and low acid content, adding a reducing agent, neutralizing after the reaction is finished, removing heavy metals, filtering out precipitates, crystallizing, and obtaining a crystallized product, namely the high-purity manganese sulfate. The method can remove the metal impurities such as ammonium sulfate, calcium, magnesium, potassium and the like in the anode slime, and then reduce and leach Mn from the anode slime product2+To obtain high-purity manganese sulfate.
Description
Technical Field
The invention relates to the technical field of electrolytic manganese metal anode mud treatment, in particular to a method for producing high-purity manganese sulfate by adopting manganese metal anode mud.
Background
The electrolytic manganese metal anode mud is a small amount of Mn in the electrolyte during the production of electrolytic manganese metal2+Discharge of MnO on anode plate2The by-product formed on the anode plate is generally black brown and has complex components and mainly contains MnO2MnO, etc., and impurities such as Fe, Pb, Se, Co, Ca, Mg, etc. Because the anode slime contains impurities such as Pb, Se, Co, Ca, Mg and the like, the mineral composition and the structure of the electrolytic manganese anode slime are complex, the symbiotic relationship of lead and hydrated oxides of manganese is very close, most of crystal forms are not developed completely, and therefore, manganese cannot be purified and lead cannot be recovered by adopting a mechanical separation method, most of domestic manufacturers do not have a proper method for recycling at present, and the anode slime is stockpiled as industrial solid waste or sold at low cost, so that resource waste and environmental pollution are caused.
At present, the state clearly lists the electrolytic manganese anode slag in dangerous waste management, the method of directly selling the anode slag is not feasible in future, and if the anode slag is stacked conventionally, the anode slag occupies land and reduces the economic benefit of enterprises, so that the problem of treating the anode slag of companies is urgent.
According to analysis and test, the content of Mn in anode slime is about 42-55%, which is a good manganese resource, in recent years, people have developed a series of researches on utilization of electrolytic manganese anode slime, but the problems of low conversion rate and recovery rate, high energy consumption, long process route, high cost, difficulty in forming scale benefit and the like still exist, so that how to efficiently and quickly treat the anode slime becomes a problem to be solved urgently.
Disclosure of Invention
The invention discloses a method for producing high-purity manganese sulfate by adopting metal manganese anode slime, which can quickly and efficiently remove metal impurities such as ammonium sulfate, calcium, magnesium, potassium and the like in the anode slime, and then reduce and leach Mn from an anode slime product2+And crystallizing to obtain the high-purity manganese sulfate.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for producing high-purity manganese sulfate by adopting metal manganese anode slime comprises the following steps:
s1, adding water into the electrolytic manganese metal anode slime for cleaning and filtering, wherein the cleaning and filtering operations are not repeated or are repeated for 1-3 times to obtain anode slime washing slag and anode slime washing liquid;
s2, adding carbonate solution into the anode mud first washing slag for cleaning, and filtering to obtain anode mud second washing slag and anode mud second washing liquid;
s3, adding an acid solution into the second washing residue of the anode mud for cleaning, and filtering to obtain third washing residue of the anode mud and third washing liquid of the anode mud, wherein the third washing residue of the anode mud contains low calcium and magnesium impurities;
s4, washing the three anode mud washing residues with water for 1-3 times, and filtering to obtain anode mud with low calcium and magnesium and low acid content;
and S5, adding water, sulfuric acid and iron powder into the anode mud with low calcium, magnesium and acid content, adding a reducing agent, controlling the pH value of the solution to be 1.2-2.5 when the reaction is close to the end point, neutralizing after the precipitation is complete, removing heavy metals, filtering the precipitation, and crystallizing to obtain the high-purity manganese sulfate.
Further, in step S5, the reducing agent is one of hydrogen peroxide, hydrogen peroxide and glucose, hydrogen peroxide and molasses. Furthermore, when the reducing agent is hydrogen peroxide, the dosage of the hydrogen peroxide is 0.5-2.0 times of the dry weight of the anode mud with low calcium and magnesium and low acid content, and the temperature is controlled at 20-70 ℃; when the reducing agent is glucose, the dosage of the glucose is 15-90 wt% of the dry weight of the anode mud with low calcium and magnesium and low acid content, and the temperature is controlled to be 70-100 ℃; when the reducing agent is hydrogen peroxide and glucose, the dosage of the hydrogen peroxide is 10-150 wt% of the dry weight of the anode mud with low calcium and magnesium and low acid content, the dosage of the glucose is 10-50 wt% of the dry weight of the anode mud with low calcium and magnesium and low acid content, hydrogen peroxide is firstly added, the temperature is controlled to be 20-70 ℃, after the reaction is finished, the glucose is added, and the temperature is controlled to be 70-100 ℃; when the reducing agent is hydrogen peroxide and molasses, the hydrogen peroxide accounts for 10-150 wt% of the dry weight of the anode mud with low calcium and magnesium and low acid content, the molasses accounts for 10-30 wt% of the dry weight of the anode mud with low calcium and magnesium and low acid content, hydrogen peroxide is firstly added, the temperature is controlled to be 20-70 ℃, and after the reaction is completed, the molasses is added, and the temperature is controlled to be 90-100 ℃.
Further, in step S5, ammonium sulfide or manganese sulfide is used to remove heavy metals. Furthermore, the amount of ammonium sulfide or manganese sulfide is 1-2.5 g/L.
Further, the anode slime final washing liquid obtained by filtering in the step S4 returns to the step S1 to replace water;
and/or
Returning to step S2 as a solvent for the carbonate solution;
and/or
And returning to the step S3 as a solvent of the acid solution.
Further, the carbonate solution is a sodium carbonate solution or a potassium carbonate solution.
Further, the acid solution is inorganic acid or acetic acid.
Further, in the step S1, the solid-to-liquid ratio of the electrolytic manganese metal anode mud to water is 1: 2-10 g/mL;
in the step S2, the carbonate solution is 1-40% by mass, and the solid-to-liquid ratio is 1: 2-10 g/mL;
in the step S3, the mass ratio of the acid ore is 0.005-0.1, and the solid-liquid ratio is 1: 2-10 g/mL;
in the step S4, the solid-to-liquid ratio of the electrolytic manganese metal anode mud to water is 1: 2-10 g/mL.
Further, in the step S5, the solid-to-liquid ratio of the anode slime with low calcium and magnesium and low acid content to water is 1: 2-10 g/ml, the mass ratio of acid ore is 1: 0.5-2.0, the dosage of iron powder is 0.1-20 g/L, and the temperature is controlled to be 85-98 ℃ when the reaction is close to the end point.
In step S5, the pH value during neutralization is adjusted to 4.9-5.5.
In the method for producing the high-purity manganese sulfate by adopting the metal manganese anode slime, clear water is added in step S1, and soluble divalent manganese and ammonium sulfate are cleaned; step S2, adding a sodium carbonate solution to precipitate calcium and magnesium, and converting calcium sulfate and magnesium sulfate bonded in the anode mud colloid into calcium carbonate and magnesium carbonate; step S3, adding acid solution to dissolve calcium carbonate and magnesium carbonate, and converting calcium and magnesium into soluble Ca2+And Mg2+After full reaction, solid-liquid separation is carried out to remove calcium and magnesium in the anode mud; washing the obtained product for 1-3 times by using clear water in the step S4 to remove acid radical ions, adding water, sulfuric acid and a reducing agent in the step S5, and removing K by using a jarosite precipitation method+Reducing the potassium content in the crystallization qualified liquid, finally neutralizing, and further removing heavy metals, mainly Fe2+Crystallizing to obtain manganese sulfate crystal MnSO4·H2The O% can reach 99.0-99.9%, and the index of battery grade high-purity manganese sulfate is reached.
Furthermore, the reducing agent can be one of hydrogen peroxide, hydrogen peroxide and glucose, hydrogen peroxide and molasses, and the glucose or the molasses can better improve the reduction effect and further improve the purity of the high-purity manganese sulfate. In addition, ammonium sulfide is preferred for removing heavy metals, such as Pb2+、Cu2+、Fe2+Can be precipitated to better improve the purity of manganese sulfate.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited to the following examples.
The test process adopts the anode mud of a pilot plant as a raw material, and the analysis results of the raw material are as follows:
TABLE 1 anode slime analysis results
Example 1
A method for producing high-purity manganese sulfate by adopting metal manganese anode slime comprises the following steps:
s1, adding water into the electrolytic manganese metal anode mud for cleaning, wherein the solid-to-liquid ratio of the electrolytic manganese metal anode mud to the water is 1: 8g/mL, stirring for 30min, and filtering to obtain anode mud washing slag and anode mud washing liquid, wherein the step is to clean soluble divalent manganese and ammonium sulfate;
s2, adding a sodium carbonate solution into the anode mud first washing slag for cleaning, wherein the mass percent of the sodium carbonate solution is 2%, and the solid-to-liquid ratio is 1: 4g/mL, stirring for reaction for 120min, and filtering to obtain anode mud second washing slag and anode mud second washing liquid, wherein the step is to convert calcium sulfate and magnesium sulfate which are bonded in the anode mud colloid into calcium carbonate and magnesium carbonate;
s3, adding hydrochloric acid solution into the anode mud secondary washing slag for cleaning, wherein the solid-liquid ratio is 1: 3g/mL, the acid-ore mass ratio is 0.01, filtering to obtain anode mud tertiary washing slag and anode mud tertiary washing liquid, wherein the anode mud tertiary washing slag contains low calcium and magnesium impurities, and the step is to convert calcium and magnesium into soluble Ca2+And Mg2+And after full reaction, carrying out solid-liquid separation to remove calcium and magnesium in the anode mud.
And S4, washing residues of the anode slime for three times by using water, filtering, and washing sodium ions and chloride ions in the step to obtain the anode slime with low calcium, magnesium and acid contents, wherein the washing water for the 2 nd time of washing is returned to the step S2 for preparing the sodium carbonate solution, and the washing water for the 1 st time of washing is returned to the step S3 for preparing the hydrochloric acid solution.
S5, adding water into the anode mud with low calcium, magnesium and acid content according to the solid-to-liquid ratio of 1:2g/mL, adding sulfuric acid according to the acid-to-mineral mass ratio of 1:1 for reaction, adding iron powder according to the concentration of 7.5g/L for reaction for 0.5h, adding hydrogen peroxide for reaction, wherein the hydrogen peroxide is 1.3 times of the dry weight of the pretreated slag, slowly adding the hydrogen peroxide in the reaction process, if the hydrogen peroxide is added too fast, a groove overflow phenomenon occurs, the reaction time is 2.5h, when the reaction is close to the end point, controlling the pH value of the solution to be 1.2-2.5, and when the pH value of the solution is over 3.0, completely precipitating Fe in the solution3+Hydrolysis results in the formation of ferric hydroxide precipitate, and if the pH is lower than 1.2, the subsequent removal of K is difficult, so the pH of the solution is well controlled during leaching.
Adding metal manganese powder for neutralization, adding 2g/L ammonium sulfide for heavy metal removal, reacting for 0.5h, adjusting pH to 5.2, filtering to remove precipitate, and crystallizing to obtain the crystal yield of 71.22%.
Step S1 test data:
step S3 test data:
test data of Ca and Mg in the washing slag:
example 2
A method for producing high-purity manganese sulfate by adopting metal manganese anode slime comprises the following steps:
s1, adding water into the electrolytic manganese metal anode mud for cleaning, wherein the solid-to-liquid ratio of the electrolytic manganese metal anode mud to the water is 1:2g/mL, stirring for 30min, filtering, and repeating for 3 times to obtain anode mud washing slag and anode mud washing liquid, wherein the step is used for cleaning soluble bivalent manganese and ammonium sulfate;
s2, adding a sodium carbonate solution into the anode mud first washing slag for cleaning, wherein the mass percent of the sodium carbonate solution is 2%, and the solid-to-liquid ratio is 1: 4g/mL, stirring for reaction for 120min, and filtering to obtain anode mud second washing slag and anode mud second washing liquid, wherein the step is to convert calcium sulfate and magnesium sulfate which are bonded in the anode mud colloid into calcium carbonate and magnesium carbonate;
s3, adding hydrochloric acid solution into the anode mud secondary washing slag for cleaning, wherein the solid-liquid ratio is 1: 3g/mL, the acid-ore mass ratio is 0.01, filtering to obtain anode mud tertiary washing slag and anode mud tertiary washing liquid, wherein the anode mud tertiary washing slag contains low calcium and magnesium impurities, and the step is to convert calcium and magnesium into soluble Ca2+And Mg2+And after full reaction, carrying out solid-liquid separation to remove calcium and magnesium in the anode mud.
And S4, washing residues of the anode slime for three times by using water, filtering, and washing sodium ions and chloride ions in the step to obtain the anode slime with low calcium, magnesium and acid contents, wherein the washing water for the 2 nd time of washing is returned to the step S2 for preparing the sodium carbonate solution, and the washing water for the 1 st time of washing is returned to the step S3 for preparing the hydrochloric acid solution.
S5, adding water into the anode mud with low calcium, magnesium and acid content according to the solid-to-liquid ratio of 1:2.5g/mL, adding sulfuric acid according to the acid-to-mineral mass ratio of 1:1 for reaction, adding iron powder according to the concentration of 8g/L for reaction for 0.5h, adding hydrogen peroxide for reaction, wherein the hydrogen peroxide is 1.3 times of the dry weight of the pretreated slag, slowly adding the hydrogen peroxide in the reaction process, if the hydrogen peroxide is added too fast, a groove overflow phenomenon occurs, the reaction time is 2.5h, when the reaction is close to the end point, controlling the pH value of the solution to be 1.2-2.5, and when the pH value of the solution exceeds 3.0, completely precipitating Fe in the solution3+Hydrolysis results in the formation of ferric hydroxide precipitate, and if the pH is lower than 1.2, the subsequent removal of K is difficult, so the pH of the solution is well controlled during leaching.
Adding metal manganese powder for neutralization, adding 1.5g/L ammonium sulfide for heavy metal removal, reacting for 0.5h, adjusting pH to 5.3, filtering to remove precipitate, and crystallizing to obtain 72.07% crystal yield.
Step S1 test data:
step S3 test data:
test data of Ca and Mg in the washing slag:
example 3
A method for producing high-purity manganese sulfate by adopting metal manganese anode slime comprises the following steps:
s1, adding water into the electrolytic manganese metal anode mud for cleaning, wherein the solid-to-liquid ratio of the electrolytic manganese metal anode mud to the water is 1: 8g/mL, stirring for 40min, and filtering to obtain anode mud washing slag and anode mud washing liquid, wherein the step is to clean soluble divalent manganese and ammonium sulfate;
s2, adding a sodium carbonate solution into the anode mud first washing slag for cleaning, wherein the mass percent of the sodium carbonate solution is 2%, and the solid-to-liquid ratio is 1: 4g/mL, stirring for reaction for 120min, and filtering to obtain anode mud second washing slag and anode mud second washing liquid, wherein the step is to convert calcium sulfate and magnesium sulfate which are bonded in the anode mud colloid into calcium carbonate and magnesium carbonate;
s3, adding nitric acid solution into the secondary washing slag of the anode mud for cleaning, wherein the solid-liquid ratio is 1: 3g/mL, and the mass ratio of acid ores is 0.009, obtaining the tertiary washing slag of the anode mud and the tertiary washing liquid of the anode mud, wherein the tertiary washing slag of the anode mud has low calcium and magnesium impurity content, and the step converts calcium and magnesium into soluble Ca2+And Mg2+And after full reaction, carrying out solid-liquid separation to remove calcium and magnesium in the anode mud.
And S4, washing the anode slime residue for three times by using water, filtering, and washing sodium ions and nitrate ions in the step to obtain the anode slime with low calcium, magnesium and acid contents, wherein the washing water for the 2 nd time of washing is returned to the step S2 for preparing the sodium carbonate solution, and the washing water for the 1 st time of washing is returned to the step S3 for preparing the nitric acid solution.
S5, adding water into the anode mud with low calcium, magnesium and acid content according to the solid-to-liquid ratio of 1:2.5g/mL, adding sulfuric acid according to the acid-to-mineral mass ratio of 0.9:1 for reaction, adding iron powder according to the concentration of 7.5g/L for reaction for 0.5h, adding hydrogen peroxide with the amount of 1.2 times of the dry weight of the pretreated slag for reaction, slowly dropwise adding the hydrogen peroxide in the reaction process, wherein the phenomenon of groove overflow can occur if the hydrogen peroxide is added too fast, the reaction time is 2.5h, when the reaction is close to the end point, controlling the pH value of the solution to be 1.2-2.5, and completely precipitating, and when the pH value of the solution exceeds 3.0, Fe in the solution3+Hydrolysis results in the formation of ferric hydroxide precipitate, and if the pH is lower than 1.2, the subsequent removal of K is difficult, so the pH of the solution is well controlled during leaching.
Adding metal manganese powder for neutralization, adding 1.8g/L ammonium sulfide for heavy metal removal, reacting for 0.5h, adjusting pH to 5.2, filtering to remove precipitate, and crystallizing to obtain 70.78% crystal yield.
Step S1 test data:
step S3 test data:
test data of Ca and Mg in the washing slag:
example 4
In this embodiment, steps S1 to S4 are the same as those in embodiment 1, and step S5 is the same as that in embodiment 1, but after the iron powder is added and reacted for 0.5 hour, glucose with low calcium and magnesium and low acid content is added, wherein the glucose accounts for 16wt% of the dry weight of the anode slime, and the amount of hydrogen peroxide is 15wt% of the dry weight of the pretreated slag.
The crystallization yield was 71.57%.
Example 5
This example is essentially the same as example 4, but with glucose replaced by molasses.
The crystallization yield was 70.79%.
Example 6
In this embodiment, steps S1 to S4 are the same as in embodiment 1, and step S5 is the same as in embodiment 1, except that the hydrogen peroxide is replaced by glucose, and the amount of glucose is 20wt% of the dry weight of the anode slime with low calcium, magnesium and acid content.
The crystallization yield was 70.46%.
The detection results of the residue leached residues after the anode pretreatment of the embodiments 1 to 6 are shown in the following table:
the detection results of the qualified liquid of slag crystallization after the anode pretreatment of the embodiments 1-6 are shown in the following table:
the detection results of manganese sulfate products crystallized from the residues after the anode pretreatment in the embodiments 1-6 are shown in the following table:
and (4) conclusion:
(1) after the washing slag is reacted with hydrogen peroxide in the leaching process, the slag leaching slag after anode pretreatment has about 3 percent of manganese slag, the minimum leaching rate of the total manganese is 98.57 percent and can reach 99.81 percent, the maximum enrichment rate of lead slag can reach 52.05 percent, and the lead slag can be recycled as a lead resource.
(2) The solution is directly taken from the neutralized solution in the crystallization process for crystallization, the crystallization yield can reach more than 70 percent, and the calcium, magnesium, heavy metal and main content of the crystallized product all meet the qualified requirements of high-purity manganese sulfate.
(3) After the jarosite method is adopted for precipitation, the content of K can be greatly reduced, after potassium is removed, Ca, Mg, K and Na of a crystallized product after potassium removal are all qualified, and the heavy metal content of the product reaches the qualified requirement.
Claims (10)
1. A method for producing high-purity manganese sulfate by adopting metal manganese anode slime is characterized by comprising the following steps:
s1, adding water into the electrolytic manganese metal anode slime for cleaning and filtering, wherein the cleaning and filtering operations are not repeated or are repeated for 1-3 times to obtain anode slime washing slag and anode slime washing liquid;
s2, adding carbonate solution into the anode mud first washing slag for cleaning, and filtering to obtain anode mud second washing slag and anode mud second washing liquid;
s3, adding an acid solution into the second washing residue of the anode mud for cleaning, and filtering to obtain third washing residue of the anode mud and third washing liquid of the anode mud, wherein the third washing residue of the anode mud contains low calcium and magnesium impurities;
s4, washing the three anode mud washing residues with water for 1-3 times, and filtering to obtain anode mud with low calcium and magnesium and low acid content;
and S5, adding water, sulfuric acid and iron powder into the anode mud with low calcium, magnesium and acid content, adding a reducing agent, controlling the pH value of the solution to be 1.2-2.5 when the reaction is close to the end point, neutralizing after the precipitation is complete, removing heavy metals, filtering the precipitation, and crystallizing to obtain the high-purity manganese sulfate.
2. The method for producing high-purity manganese sulfate by using anode slime of manganese metal according to claim 1, wherein the method comprises the following steps:
in the step S5, the reducing agent is one of hydrogen peroxide, glucose, hydrogen peroxide and molasses.
3. The method for producing high-purity manganese sulfate by using anode slime of manganese metal according to claim 1, wherein the method comprises the following steps:
in step S5, ammonium sulfide or manganese sulfide is used to remove heavy metals.
4. The method for producing high-purity manganese sulfate by using anode slime of manganese metal according to claim 2, wherein the method comprises the following steps:
when the reducing agent is hydrogen peroxide, the dosage of the hydrogen peroxide is 0.5-2.0 times of the dry weight of the anode mud with low calcium and magnesium and low acid content, and the temperature is controlled at 20-70 ℃;
when the reducing agent is glucose, the dosage of the glucose is 15-90 wt% of the dry weight of the anode mud with low calcium and magnesium and low acid content, and the temperature is controlled to be 70-100 ℃;
when the reducing agent is hydrogen peroxide and glucose, the dosage of the hydrogen peroxide is 10-150 wt% of the dry weight of the anode mud with low calcium and magnesium and low acid content, the dosage of the glucose is 10-50 wt% of the dry weight of the anode mud with low calcium and magnesium and low acid content, hydrogen peroxide is firstly added, the temperature is controlled to be 20-70 ℃, after the reaction is finished, the glucose is added, and the temperature is controlled to be 70-100 ℃;
when the reducing agent is hydrogen peroxide and molasses, the hydrogen peroxide accounts for 10-150 wt% of the dry weight of the anode mud with low calcium and magnesium and low acid content, the molasses accounts for 10-30 wt% of the dry weight of the anode mud with low calcium and magnesium and low acid content, hydrogen peroxide is firstly added, the temperature is controlled to be 20-70 ℃, and after the reaction is completed, the molasses is added, and the temperature is controlled to be 90-100 ℃.
5. The method for producing high-purity manganese sulfate by using anode slime containing manganese metal as claimed in claim 3, wherein the method comprises the following steps:
the dosage of the ammonium sulfide or the manganese sulfide is 1-2.5 g/L.
6. The method for producing high-purity manganese sulfate by using anode slime of manganese metal according to claim 1, wherein the method comprises the following steps:
the anode mud final washing liquid obtained by filtering in the step S4 returns to the step S1 to replace water;
and/or
Returning to step S2 as a solvent for the carbonate solution;
and/or
And returning to the step S3 as a solvent of the acid solution.
7. The method for producing high-purity manganese sulfate by using anode slime of manganese metal according to claim 1, wherein the method comprises the following steps:
the carbonate solution is a sodium carbonate solution or a potassium carbonate solution.
8. The method for producing high-purity manganese sulfate by using anode slime of manganese metal according to claim 1, wherein the method comprises the following steps:
the acid solution is inorganic acid or acetic acid.
9. The method for producing high-purity manganese sulfate by using anode slime of manganese metal according to claim 1, wherein the method comprises the following steps:
in the step S1, the solid-to-liquid ratio of the electrolytic manganese metal anode mud to water is 1: 2-10 g/mL;
in the step S2, the carbonate solution is 1-40% by mass, and the solid-to-liquid ratio is 1: 2-10 g/mL;
in the step S3, the mass ratio of the acid ore is 0.005-0.1, and the solid-liquid ratio is 1: 2-10 g/mL.
10. The method for producing high-purity manganese sulfate by using manganese metal anode slime as set forth in any one of claims 1 to 9, wherein:
in the step S5, the solid-to-liquid ratio of the anode mud with low calcium and magnesium and low acid content to water is 1: 2-10 g/ml, the mass ratio of acid ore is 1: 0.5-2.0, the dosage of iron powder is 0.1-20 g/L, and the temperature is controlled at 85-98 ℃ when the reaction is close to the end point.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113234941A (en) * | 2021-05-18 | 2021-08-10 | 西南科技大学 | High-value utilization method of electrolytic manganese anode slime |
| CN115261631A (en) * | 2022-08-10 | 2022-11-01 | 贵州大学 | Electrolytic manganese metal anode slag recovery treatment method |
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| CN113234941B (en) * | 2021-05-18 | 2022-07-19 | 西南科技大学 | High-value utilization method of electrolytic manganese anode slime |
| CN115261631A (en) * | 2022-08-10 | 2022-11-01 | 贵州大学 | Electrolytic manganese metal anode slag recovery treatment method |
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