CN110735154B - Method for producing electrolytic manganese metal and active manganese dioxide by anode mud produced by electrolytic manganese metal - Google Patents

Method for producing electrolytic manganese metal and active manganese dioxide by anode mud produced by electrolytic manganese metal Download PDF

Info

Publication number
CN110735154B
CN110735154B CN201811135594.1A CN201811135594A CN110735154B CN 110735154 B CN110735154 B CN 110735154B CN 201811135594 A CN201811135594 A CN 201811135594A CN 110735154 B CN110735154 B CN 110735154B
Authority
CN
China
Prior art keywords
manganese
filter
pressing block
manganese dioxide
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811135594.1A
Other languages
Chinese (zh)
Other versions
CN110735154A (en
Inventor
庞炼红
唐诗祝
张雪莲
庞列培
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201811135594.1A priority Critical patent/CN110735154B/en
Publication of CN110735154A publication Critical patent/CN110735154A/en
Application granted granted Critical
Publication of CN110735154B publication Critical patent/CN110735154B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B19/00—Selenium; Tellurium; Compounds thereof
    • C01B19/02—Elemental selenium or tellurium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/02—Oxides; Hydroxides
    • 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
    • C22B13/00—Obtaining lead
    • C22B13/04—Obtaining lead by wet processes
    • C22B13/045—Recovery from waste materials
    • 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Abstract

The invention belongs to the technical field of electrolytic production and manganese recovery by a solution electrolytic method, and particularly relates to a method for producing electrolytic manganese metal and active manganese dioxide by anode mud produced by electrolyzing manganese metal, which comprises the following steps: A. slurrying anode mud produced in the process of electrolyzing metal manganese, adding ammonia water to adjust the pH value of the solution to 9-10, carrying out solid-liquid separation after filter pressing, washing to obtain a filter pressing block and washing water, and recycling the washing water; B. calcining the filter-pressing block, leaching by using anolyte for electrolyzing metal manganese, and carrying out solid-liquid separation after filter-pressing to obtain a manganese dioxide filter-pressing block and a manganese sulfate solution; C. acid leaching and filter pressing the manganese dioxide filter pressing block to obtain a manganese dioxide filter pressing block and a lead water solution, washing the filter pressing block with water, drying and grinding to obtain active manganese dioxide; D. removing impurities from the manganese sulfate solution, standing to obtain electrolyte, and electrolyzing and post-treating the electrolyte to obtain electrolytic manganese metal. The method realizes the recycling of resources and improves the income; safe and environment-friendly, and has no pollution.

Description

Method for producing electrolytic manganese metal and active manganese dioxide by anode mud produced by electrolytic manganese metal
Technical Field
The invention belongs to the technical field of electrolytic production and manganese recovery by a solution electrolytic method, and particularly relates to a method for producing electrolytic manganese metal and manganese dioxide by anode mud produced by electrolyzing manganese metal.
Background
The anode slag generated in the production process of electrolytic manganese metal is also called anode mud, and the anode mud contains high-content substances such as manganese dioxide, ammonium sulfate, sulfuric acid, manganese sulfate, lead, selenium and the like. Through the investigation of the enterprises for producing electrolytic manganese metal in the current industry of China, the manganese content in the anode mud produced by the electrolytic manganese metal accounts for about 7-10% of the total manganese input.
In the existing electrolytic manganese metal production, anode mud is not recycled, but is sold to an intermediate merchant at a low price and then is sold to manganese alloy production enterprises to be used as a raw material for smelting alloys by a pyrogenic process, and discharged harmful gases such as ammonia, nitrogen, sulfur dioxide, selenium dioxide, lead-containing smoke and the like cause serious pollution to air and environment and loss of auxiliary materials.
There have been some researches on the treatment of anode slime, for example, jiatian, has developed a method for recycling electrolytic manganese anode slime, in which oxalic acid is used as a reducing agent, concentrated sulfuric acid and oxalic acid are used to reduce and leach manganese in the anode slime, and after filter pressing, the leachate is neutralized, oxidized and sulfurized (publication number CN 103436914A). However, the method has large consumption of auxiliary materials of concentrated sulfuric acid and oxalic acid and high cost, and can not solve the balance problem in the processes of sulfuric acid filter pressing and electrolysis.
Disclosure of Invention
In view of the above, the present invention provides a method for producing electrolytic manganese metal and manganese dioxide from anode mud produced by electrolyzing manganese metal.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the method for producing electrolytic manganese metal and manganese dioxide by using anode mud produced by electrolyzing the manganese metal comprises the following steps:
A. grinding anode mud produced in the process of electrolyzing metal manganese into powder and slurrying, adding ammonia water to adjust the pH of the solution to 9-10, performing solid-liquid separation after filter pressing, washing to obtain a filter pressing block and washing water, and recycling the washing water;
B. calcining the filter-pressing block, leaching by using anolyte for electrolyzing metal manganese, and carrying out solid-liquid separation after filter-pressing to obtain a manganese dioxide filter-pressing block and a manganese sulfate solution;
C. acid leaching the manganese dioxide filter pressing block by using acetic acid solution and ammonia water solution, filter-pressing to obtain a manganese dioxide filter pressing block and a lead water solution, washing the manganese dioxide filter pressing block with water, drying, and grinding to obtain active manganese dioxide;
D. removing impurities from the manganese sulfate solution, standing to obtain electrolyte, and electrolyzing and post-treating the electrolyte to obtain electrolytic manganese metal.
The slurrying refers to mixing anode mud and water, wherein the slurrying degree is that the content of divalent manganese ions in a slurried solution is 25-40 g/L.
The post-treatment refers to a series of operations for treating electrolytic manganese metal after electrolysis, and comprises the steps of purification, water washing, drying, stripping, plate treatment and the like.
The method solves the balance problem in the sulfuric acid filter pressing and electrolysis processes.
According to the method, a part of manganese dioxide in the anode mud is converted into active manganese dioxide, and a part of manganese dioxide is generated into manganese sulfate to be continuously electrolyzed, so that the recovery rate of manganese is improved; on the other hand, the production of waste slag is greatly reduced, thereby reducing the production cost.
The method does not generate NH in the production process3And the like, is safe and environment-friendly, and has no pollution.
Further, the temperature of the calcination is 540-.
Further, the dosage of the anolyte is such that the content of divalent manganese ions in the solution after reaction is 25-40 g/L.
Further, the drying temperature is 100-.
Further, the method also comprises the following steps: and E, using the electrolyzed anolyte obtained in the step D in the leaching process in the step B, and using the anode mud in the step A.
The method recycles the anode mud and the anolyte, greatly reduces the production cost and recovers lead while eliminating pollution sources.
Further, the method also comprises the following steps: F. and (4) adding ammonia water into the washing water, and performing filter pressing to be used for the washing procedure in the step A.
The method of the invention recycles water, reduces production cost and improves resource utilization rate.
Further, the dosage of the ammonia water is such that the divalent manganese ions in the washing water can completely react.
Further, the method comprises the steps of:
A. grinding anode mud produced in the process of electrolyzing metal manganese into powder and slurrying, adding ammonia water to adjust the pH of the solution to 9-10, performing solid-liquid separation after filter pressing, washing to obtain a filter pressing block and washing water, and recycling the washing water;
B. calcining the filter pressing block at the temperature of 540-; the dosage of the anolyte is that the content of bivalent manganese ions in the solution after reaction is 25-40 g/L;
C. acid leaching and filter-pressing the manganese dioxide filter-pressing block to obtain a manganese dioxide filter-pressing block and a lead water solution, drying and grinding the manganese dioxide filter-pressing block to obtain active manganese dioxide, and recovering lead;
D. removing impurities from a manganese sulfate solution, standing to obtain an electrolyte, and electrolyzing and post-treating the electrolyte to obtain electrolytic manganese metal;
E. d, using the electrolyzed anolyte in the step B in the leaching procedure, and using anode mud in the step A;
F. and (3) adding ammonia water into the washing water, and performing filter pressing to be used in the washing procedure of the step A, wherein the dosage of the ammonia water can enable the divalent manganese ions in the washing water to completely react.
The lead recovery refers to the steps of putting active manganese dioxide into an ammonium acetate solution, then carrying out filter pressing and solid-liquid separation, adding a sulfuric acid solution into the liquid, and filtering to obtain a lead sulfate precipitate.
And the step of recovering the selenium is to introduce gas obtained by calcination into water, then introduce sulfur dioxide gas into the solution, and filter to obtain selenium precipitate.
Further, the leaching temperature is 30-80 ℃.
The method can produce two kinds of products simultaneously, thereby reducing unit power consumption of the products.
The electrolytic manganese metal is produced by utilizing the prior art, the main component of anode mud is manganese dioxide, and Mn (mainly MnO) accounting for 7-10% of the mass ratio of the input ore is taken away2Form exists), 3.5 to 5 percent of lead and 0.1 to 0.3 percent of selenium, and the anode mud is sold to other factories at the price of 400-600 yuan/ton. When the method is used for producing electrolytic manganese metal, part of manganese dioxide in anode mud is converted into active manganese dioxide, part of manganese dioxide is generated into manganese sulfate for recycling, and electrolysis is continued, so that the electrolytic manganese metal is extractedThe recovery rate of manganese is high. Meanwhile, the generated active manganese dioxide (about 10000 yuan/ton) also greatly improves the income, and the recycled lead and selenium also improve the income.
When the method of the invention is used for producing electrolytic manganese metal and active manganese dioxide, 1 ton of active manganese dioxide (about 10000 yuan/ton), 0.5 ton of electrolytic manganese metal (about 11000 yuan/ton), 0.117-0.168 ton of lead sulfate (about 770 yuan/ton) and 0.0023-0.0069 ton of selenium (about 2000 yuan/ton) can be prepared when 2.3 ton of anode mud (about 400 yuan/ton) and 2800 DEG electric quantity (about 0.41 yuan/ton) are consumed. Namely, every 2.3 tons of anode mud are consumed, the income is about 13067 yuan and 13631 yuan.
And other agents are not required to be added for treatment, new impurity ions are not introduced, and the additional treatment of the impurity ions is not required.
The invention has the beneficial effects that:
(1) the electrolytic manganese metal and the active manganese dioxide are produced by using the anode slime, so that the anode slime is treated, the electrolytic manganese metal is obtained, the resource is recycled, the income can be improved, and lead is recycled.
(2) The anode mud and the anolyte are recycled, and a pollution source is eliminated, so that the environment-friendly use of the anode mud is realized.
(3) When the method is used for producing the electrolytic manganese metal and the active manganese dioxide, the anode mud, the anolyte and the water can be recycled, so that the cost is reduced and the benefit is improved.
(4) When the method is used for producing the electrolytic manganese metal, part of manganese dioxide in the anode mud is converted into active manganese dioxide, and part of manganese dioxide is generated into manganese sulfate for recycling and continuous electrolysis, so that the recovery rate of manganese is improved; meanwhile, the generated active manganese dioxide (about 10000 yuan/ton) also greatly improves the income, and the recycled lead and selenium also improve the income.
(5) When the method of the invention is used for producing electrolytic manganese metal and active manganese dioxide, 1 ton of active manganese dioxide (about 10000 yuan/ton), 0.5 ton of electrolytic manganese metal (about 11000 yuan/ton), 0.117-0.168 ton of lead sulfate (about 770 yuan/ton) and 0.0023-0.0069 ton of selenium (about 100000 yuan/ton) can be prepared when 2.3 ton of anode mud (about 400 yuan/ton) and 2800 DEG electric quantity (about 0.41 yuan/ton) are consumed. That is, each ton of anode mud is consumed by 2.3 tons, the yield is about 13292.4-14307.2 yuan.
(6) And other agents are not required to be added for treatment, new impurity ions are not introduced, and the additional treatment of the impurity ions is not required.
(7) The method produces two products simultaneously, thereby reducing the unit power consumption of the products, leading the production to be more stable and leading the operation to be simpler.
(8) Does not generate NH3And the like, is safe and environment-friendly, and has no pollution.
(9) The obtained electrolytic manganese metal and active manganese dioxide have high purity, the manganese content in the electrolytic manganese metal is more than or equal to 99.8 percent, and the manganese dioxide content in the active manganese dioxide is more than or equal to 90 percent.
(10) The method solves the balance problem in the sulfuric acid filter pressing and electrolysis processes.
Detailed Description
The examples are provided for better illustration of the present invention, but the present invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
Example 1
The method for producing electrolytic manganese metal and manganese dioxide by using anode mud produced by electrolyzing the manganese metal comprises the following specific steps:
A. grinding anode mud produced in the process of electrolyzing metal manganese into 80-mesh powder, slurrying (the slurrying degree is that the content of divalent manganese ions in the slurried solution is 25g/L), adding ammonia water to adjust the pH value of the solution to 9, carrying out solid-liquid separation after filter pressing, washing to obtain a filter pressing block and washing water, and recycling the washing water;
B. calcining the filter pressing block at 800 ℃, extracting gas to recover selenium, leaching the calcined solid by using anode liquor of electrolytic manganese metal at 55 ℃ (the dosage is 25g/L of divalent manganese ions in the solution after reaction), and performing solid-liquid separation after filter pressing to obtain a manganese dioxide filter pressing block and a manganese sulfate solution;
C. acid leaching and filter-pressing the manganese dioxide filter-pressing block with acetic acid solution and ammonia water solution to obtain a manganese dioxide filter-pressing block and a lead water solution, recovering lead, washing the manganese dioxide filter-pressing block with water, drying at the temperature of 100 ℃, and grinding to obtain powdery active manganese dioxide (the content of manganese dioxide in the active manganese dioxide is detected according to GB/T1507-2006 potassium dichromate titration method for determining the effective oxygen content of manganese ore, and the content of the manganese dioxide is measured to be 90%); the powdery manganese dioxide has large surface area, then active manganese dioxide is placed in an ammonium acetate solution, filter pressing and solid-liquid separation are carried out, a sulfuric acid solution is added into the liquid, and lead sulfate precipitation is obtained by filtration;
D. removing impurities from a manganese sulfate solution, standing to obtain an electrolyte, electrolyzing the electrolyte, and performing post-treatment to obtain electrolytic manganese metal (detecting the manganese content in the electrolytic manganese metal according to GB/T8654.7-1988 manganese metal chemical analysis method potentiometric titration method for determining manganese content, and detecting that the manganese content is 99.8%);
E. d, using the electrolyzed anolyte in the step D in the leaching process in the step B, and using the anode mud in the step A.
F. And (3) adding ammonia water (the dosage is enough to enable the divalent manganese ions in the washing water to completely react) into the washing water, and performing filter pressing to be used for the washing procedure of the step A.
When the method is used for producing electrolytic manganese metal and active manganese dioxide, 1 ton of active manganese dioxide, 0.5 ton of electrolytic manganese metal, 0.117-0.168 ton of lead sulfate and 0.0023-0.0069 ton of selenium can be prepared when 2.3 tons of anode mud are consumed and 2800 DEG electric quantity is consumed.
Example 2
The method for producing electrolytic manganese metal and manganese dioxide by using anode mud produced by electrolyzing the manganese metal comprises the following specific steps:
A. grinding anode mud produced in the process of electrolyzing metal manganese into 100-mesh powder, slurrying (the slurrying degree is that the content of divalent manganese ions in the slurried solution is 30g/L), adding ammonia water to adjust the pH value of the solution to 10, carrying out solid-liquid separation after filter pressing, washing with water to obtain a filter pressing block and washing water, and recycling the washing water;
B. calcining the filter pressing block at 750 ℃, extracting gas to recover selenium, leaching the calcined solid by using 60-DEG C anolyte for electrolyzing metal manganese (the dosage is that the content of bivalent manganese ions in the solution after reaction is 40g/L), and performing solid-liquid separation after filter pressing to obtain a manganese dioxide filter pressing block and a manganese sulfate solution;
C. acid leaching and filter-pressing the manganese dioxide filter-pressing block with acetic acid solution and ammonia water solution to obtain a manganese dioxide filter-pressing block and a lead water solution, recovering lead, washing the manganese dioxide filter-pressing block with water, drying at the temperature of 200 ℃, and grinding to obtain powdery active manganese dioxide (the content of manganese dioxide in the active manganese dioxide is detected according to GB/T1507-2006 potassium dichromate titration method for determining the effective oxygen content of manganese ore, and the content of the manganese dioxide is measured to be 90%); the powdery manganese dioxide has large surface area, then active manganese dioxide is placed in an ammonium acetate solution, filter pressing and solid-liquid separation are carried out, a sulfuric acid solution is added into the liquid, and lead sulfate precipitation is obtained by filtration;
D. removing impurities from a manganese sulfate solution, standing to obtain an electrolyte, electrolyzing the electrolyte, and performing post-treatment to obtain electrolytic manganese metal (detecting the manganese content in the electrolytic manganese metal according to GB/T8654.7-1988 manganese metal chemical analysis method potentiometric titration method for determining manganese content, and detecting that the manganese content is 99.8%);
E. d, using the electrolyzed anolyte in the step D in the leaching process in the step B, and using the anode mud in the step A.
F. And (3) adding ammonia water (the dosage is enough to enable the divalent manganese ions in the washing water to completely react) into the washing water, and performing filter pressing to be used in the washing procedure of the step A.
When the method is used for producing electrolytic manganese metal and active manganese dioxide, 1 ton of active manganese dioxide, 0.5 ton of electrolytic manganese metal, 0.117-0.168 ton of lead sulfate and 0.0023-0.0069 ton of selenium can be prepared when 2.3 tons of anode mud are consumed and 2800 DEG electric quantity is consumed.
Example 3
The method for producing electrolytic manganese metal and manganese dioxide by using anode mud produced by electrolyzing the manganese metal comprises the following specific steps:
A. grinding anode mud produced in the process of electrolyzing metal manganese into 90-mesh powder, slurrying (the slurrying degree is that the content of divalent manganese ions in the slurried solution is 40g/L), adding ammonia water to adjust the pH value of the solution to 9.5, carrying out solid-liquid separation after filter pressing, washing with water to obtain a filter pressing block and washing water, and recycling the washing water;
B. calcining the filter pressing block at 540 ℃, extracting gas to recover selenium, leaching the calcined solid by using 80 ℃ anolyte for electrolyzing metal manganese (the dosage is that the content of bivalent manganese ions in the solution after reaction is 32g/L), and performing solid-liquid separation after filter pressing to obtain a manganese dioxide filter pressing block and a manganese sulfate solution;
C. acid leaching and filter-pressing the manganese dioxide filter-pressing block with acetic acid solution and ammonia water solution to obtain a manganese dioxide filter-pressing block and a lead water solution, recovering lead, washing the manganese dioxide filter-pressing block with water, drying at the temperature of 150 ℃, and grinding to obtain powdery active manganese dioxide (the content of manganese dioxide in the active manganese dioxide is detected according to GB/T1507-2006 determination of manganese ore effective oxygen content, and the content of manganese dioxide is measured to be 90%); the powdery manganese dioxide has large surface area, then active manganese dioxide is placed in an ammonium acetate solution, filter pressing and solid-liquid separation are carried out, a sulfuric acid solution is added into the liquid, and lead sulfate precipitation is obtained by filtration;
D. removing impurities from a manganese sulfate solution, standing to obtain an electrolyte, electrolyzing the electrolyte, and performing post-treatment to obtain electrolytic manganese metal (detecting the manganese content in the electrolytic manganese metal according to GB/T8654.7-1988 manganese metal chemical analysis method potentiometric titration method for determining manganese content, and detecting that the manganese content is 99.9%);
E. d, using the electrolyzed anolyte in the step D in the leaching process in the step B, and using the anode mud in the step A.
F. And (3) adding ammonia water (the dosage is enough to enable the divalent manganese ions in the washing water to completely react) into the washing water, and performing filter pressing to be used for the washing procedure of the step A.
When the method is used for producing electrolytic manganese metal and active manganese dioxide, 1 ton of active manganese dioxide, 0.5 ton of electrolytic manganese metal, 0.117-0.168 ton of lead sulfate and 0.0023-0.0069 ton of selenium can be prepared when 2.3 tons of anode mud are consumed and 2800 DEG electric quantity is consumed.
Example 4
The method for producing electrolytic manganese metal and manganese dioxide by using anode mud produced by electrolyzing the manganese metal comprises the following specific steps:
A. grinding anode mud produced in the process of electrolyzing metal manganese into 100-mesh powder, slurrying (the slurrying degree is that the content of divalent manganese ions in the slurried solution is 35g/L), adding ammonia water to adjust the pH value of the solution to 9.8, carrying out solid-liquid separation after filter pressing, washing with water to obtain a filter pressing block and washing water, and recycling the washing water;
B. calcining the filter pressing block at 630 ℃, extracting gas to recover selenium, leaching the calcined solid by 30 ℃ anolyte of electrolytic manganese metal (the dosage is that the content of bivalent manganese ions in the solution after reaction is 35g/L), and performing solid-liquid separation after filter pressing to obtain a manganese dioxide filter pressing block and a manganese sulfate solution;
C. acid leaching and filter-pressing the manganese dioxide filter-pressing block with acetic acid solution and ammonia water solution to obtain a manganese dioxide filter-pressing block and a lead water solution, recovering lead, washing the manganese dioxide filter-pressing block with water, drying at the temperature of 120 ℃, and grinding to obtain powdery active manganese dioxide (the content of manganese dioxide in the active manganese dioxide is detected according to GB/T1507-2006 potassium dichromate titration method for determining the effective oxygen content of manganese ore, and the content of the manganese dioxide is 90 percent); the powdery manganese dioxide has large surface area, then active manganese dioxide is placed in an ammonium acetate solution, filter pressing and solid-liquid separation are carried out, a sulfuric acid solution is added into the liquid, and lead sulfate precipitation is obtained by filtration;
D. removing impurities from a manganese sulfate solution, standing to obtain an electrolyte, electrolyzing the electrolyte, and performing post-treatment to obtain electrolytic manganese metal (detecting the manganese content in the electrolytic manganese metal according to GB/T8654.7-1988 manganese metal chemical analysis method potentiometric titration method for determining manganese content, and detecting that the manganese content is 99.8%);
E. d, using the electrolyzed anolyte in the step D in the leaching process in the step B, and using the anode mud in the step A.
F. And (3) adding ammonia water (the dosage is enough to enable the divalent manganese ions in the washing water to completely react) into the washing water, and performing filter pressing to be used for the washing procedure of the step A.
When the method is used for producing electrolytic manganese metal and active manganese dioxide, 1 ton of active manganese dioxide, 0.5 ton of electrolytic manganese metal, 0.117-0.168 ton of lead sulfate and 0.0023-0.0069 ton of selenium can be prepared when 2.3 tons of anode mud are consumed and 2800 DEG electric quantity is consumed.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.

Claims (9)

1. The method for producing electrolytic manganese metal and active manganese dioxide by using anode mud produced by electrolyzing the manganese metal is characterized by comprising the following steps of:
A. grinding anode mud produced in the process of electrolyzing metal manganese into powder and slurrying, adding ammonia water to adjust the pH of the solution to 9-10, performing solid-liquid separation after filter pressing, washing to obtain a filter pressing block and washing water, and recycling the washing water;
B. calcining the filter pressing block at the temperature of 540-;
C. acid leaching and filter-pressing the manganese dioxide filter pressing block by using acetic acid solution and ammonia water solution to obtain a manganese dioxide filter pressing block and a lead water solution, washing the manganese dioxide filter pressing block with water, drying at the temperature of 100-200 ℃, and grinding to obtain active manganese dioxide;
D. removing impurities from the manganese sulfate solution, standing to obtain electrolyte, and electrolyzing and post-treating the electrolyte to obtain electrolytic manganese metal.
2. The method of claim 1 further comprising the step of using the anolyte after electrolysis in step e.
3. The method according to claim 1 or 2, further comprising a step f. adding ammonia water to the washing water, and using the mixture after pressure filtration in the step a washing process.
4. The method of claim 3, wherein the aqueous ammonia is used in an amount to completely react the divalent manganese ions in the wash water.
5. Method according to claim 1, 2 or 4, characterized in that it comprises the following steps:
A. grinding anode mud produced in the process of electrolyzing metal manganese into powder and slurrying, adding ammonia water to adjust the pH of the solution to 9-10, performing solid-liquid separation after filter pressing, washing to obtain a filter pressing block and washing water, and recycling the washing water;
B. calcining the filter pressing block at the temperature of 540-; the dosage of the anolyte is that the content of bivalent manganese ions in the solution after reaction is 25-40 g/L;
C. acid leaching and filter-pressing the manganese dioxide filter-pressing block to obtain a manganese dioxide filter-pressing block and a lead water solution, drying and grinding the manganese dioxide filter-pressing block to obtain active manganese dioxide, and recovering lead;
D. removing impurities from a manganese sulfate solution, standing to obtain an electrolyte, and electrolyzing and post-treating the electrolyte to obtain electrolytic manganese metal;
E. d, using the electrolyzed anolyte in the step B in the leaching procedure, and using anode mud in the step A;
F. and (3) adding ammonia water into the washing water, and performing filter pressing to be used in the washing procedure of the step A, wherein the dosage of the ammonia water can enable the divalent manganese ions in the washing water to completely react.
6. A method according to claim 3, characterized by the steps of:
A. grinding anode mud produced in the process of electrolyzing metal manganese into powder and slurrying, adding ammonia water to adjust the pH of the solution to 9-10, performing solid-liquid separation after filter pressing, washing to obtain a filter pressing block and washing water, and recycling the washing water;
B. calcining the filter pressing block at the temperature of 540-; the dosage of the anolyte is that the content of bivalent manganese ions in the solution after reaction is 25-40 g/L;
C. acid leaching and filter-pressing the manganese dioxide filter-pressing block to obtain a manganese dioxide filter-pressing block and a lead water solution, drying and grinding the manganese dioxide filter-pressing block to obtain active manganese dioxide, and recovering lead;
D. removing impurities from a manganese sulfate solution, standing to obtain an electrolyte, and electrolyzing and post-treating the electrolyte to obtain electrolytic manganese metal;
E. d, using the electrolyzed anolyte in the step B in the leaching procedure, and using anode mud in the step A;
F. and (3) adding ammonia water into the washing water, and performing filter pressing to be used in the washing procedure of the step A, wherein the dosage of the ammonia water can enable the divalent manganese ions in the washing water to completely react.
7. A method as claimed in claim 1, 2, 4 or 6, characterised in that the leaching temperature is 30-80 ℃.
8. A method according to claim 3, characterized in that the leaching temperature is 30-80 ℃.
9. A method according to claim 5, characterized in that the leaching temperature is 30-80 ℃.
CN201811135594.1A 2018-09-27 2018-09-27 Method for producing electrolytic manganese metal and active manganese dioxide by anode mud produced by electrolytic manganese metal Active CN110735154B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811135594.1A CN110735154B (en) 2018-09-27 2018-09-27 Method for producing electrolytic manganese metal and active manganese dioxide by anode mud produced by electrolytic manganese metal

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811135594.1A CN110735154B (en) 2018-09-27 2018-09-27 Method for producing electrolytic manganese metal and active manganese dioxide by anode mud produced by electrolytic manganese metal

Publications (2)

Publication Number Publication Date
CN110735154A CN110735154A (en) 2020-01-31
CN110735154B true CN110735154B (en) 2021-09-24

Family

ID=69236612

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811135594.1A Active CN110735154B (en) 2018-09-27 2018-09-27 Method for producing electrolytic manganese metal and active manganese dioxide by anode mud produced by electrolytic manganese metal

Country Status (1)

Country Link
CN (1) CN110735154B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111961862B (en) * 2020-08-27 2021-11-19 江西理工大学 Method for deeply removing lead, selenium and arsenic from manganese electrolysis anode mud and preparing manganese dioxide

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103074496A (en) * 2013-01-21 2013-05-01 昆明理工大学 Method for separating and purifying magnesium dioxide from anode mud
CN104004919A (en) * 2014-06-11 2014-08-27 张安良 Environment-friendly recycling process of waste residues in electrolytic manganese production
CN104131167A (en) * 2014-07-11 2014-11-05 广西大学 Method for recovering selenium and manganese in manganese anode slime by using microwaves
CN104789755A (en) * 2015-04-23 2015-07-22 中南大学 Method and device of utilizing high-sulfur manganese mine to cleanly and efficiently produce manganese metal
CN105506294A (en) * 2016-02-23 2016-04-20 长沙矿冶研究院有限责任公司 Method for comprehensively recovering manganese and lead from electrolytic manganese anode slime
CN105695751A (en) * 2016-03-11 2016-06-22 武汉工程大学 Purification process of manganese anode slime
CN107574308A (en) * 2017-09-11 2018-01-12 中南大学 A kind of method of Manganese anode slime manganese lead separation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103074496A (en) * 2013-01-21 2013-05-01 昆明理工大学 Method for separating and purifying magnesium dioxide from anode mud
CN104004919A (en) * 2014-06-11 2014-08-27 张安良 Environment-friendly recycling process of waste residues in electrolytic manganese production
CN104131167A (en) * 2014-07-11 2014-11-05 广西大学 Method for recovering selenium and manganese in manganese anode slime by using microwaves
CN104789755A (en) * 2015-04-23 2015-07-22 中南大学 Method and device of utilizing high-sulfur manganese mine to cleanly and efficiently produce manganese metal
CN105506294A (en) * 2016-02-23 2016-04-20 长沙矿冶研究院有限责任公司 Method for comprehensively recovering manganese and lead from electrolytic manganese anode slime
CN105695751A (en) * 2016-03-11 2016-06-22 武汉工程大学 Purification process of manganese anode slime
CN107574308A (en) * 2017-09-11 2018-01-12 中南大学 A kind of method of Manganese anode slime manganese lead separation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
从电解锰阳极泥中去除铅的试验研究;郭颂等;《湿法冶金》;20180430;第37卷(第2期);138-142 *

Also Published As

Publication number Publication date
CN110735154A (en) 2020-01-31

Similar Documents

Publication Publication Date Title
CN101845562B (en) Improved device and method for producing electrolytic manganese metal by two-ore method
CN103526016B (en) A kind of method of raw material containing lead hydrometallurgic recovery
CN107058731B (en) A kind of technique that platinum palladium product is produced as raw material using Pt Pd concentrate
CN106129511A (en) A kind of method of comprehensively recovering valuable metal from waste and old lithium ion battery material
CN102828025B (en) Method for extracting V2O5 from stone coal navajoite
CN108118156B (en) A kind of method that electrolytic manganese anode mud separation produces electrolytic manganese metal and recycles lead
CN109055757B (en) Method for recovering manganese dioxide and lead in anode slag of electrolytic manganese or electrolytic zinc
CN101838736A (en) Wet separation method for valuable metals in purified liquid cobalt slags of wet zinc smelting system
CN103937973B (en) A kind of method of Organic-inorganic composite reducing pyrolusite
CN104178632A (en) Method for comprehensively utilizing titanium white waste acid
CN106399688B (en) The removal methods of iron ion in a kind of trivalent chromium acid solution
CN112760487A (en) Method for recovering manganese and lead from electrolytic manganese anode slag
CN108531718A (en) A method of producing chrome green using tailings in vanadium extraction
CN101307463B (en) Method for producing electrolytic manganese metal by replacing partial ammonia water with manganese dregs for neutralization deironing
CN104120269A (en) Method for comprehensively utilizing vanadium slag
CN103074496B (en) Method for separating and purifying magnesium dioxide from anode mud
CN110735039A (en) Electrolytic manganese metal anode mud treatment method
CN103451673A (en) Production method of electrolytic manganese metal
CN110735154B (en) Method for producing electrolytic manganese metal and active manganese dioxide by anode mud produced by electrolytic manganese metal
CN104164571B (en) The recovery method of valuable metal element in a kind of Converter Vanadium-bearing Slag
CN110732543B (en) Method for jointly producing cement clinker and ammonia water by electrolyzing metal manganese waste residue and gypsum
CN110735155B (en) Method for producing electrolytic manganese metal and co-producing manganese dioxide
CN101172647A (en) Method for producing gtitanium dioxide with sulphuric acid method
CN110734093B (en) Method for co-producing manganese hydroxide and sulfuric acid or ammonium sulfite by electrolyzing metal manganese waste residue
CN102660756B (en) High-purity manganese metal and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant