阅读说明：本技术 生产电解金属锰联产二氧化锰的生产方法 (Method for producing electrolytic manganese metal and co-producing manganese dioxide ) 是由 庞炼红 唐诗祝 张雪莲 庞列培 于 2018-09-27 设计创作，主要内容包括：本发明属于由溶液电解法电解生产、回收锰技术领域,具体涉及生产电解金属锰联产二氧化锰的生产方法,包括以下步骤：A.将锰元素含量≥47%的氧化锰、氢氧化锰或碳酸锰置于电解金属锰的阳极液中,电解；B.将电解后得到的阳极液搅拌、浸出,然后pH调节至6.1-6.4,净化、压滤、去渣、静置得到电解液,将电解液进行电解,经进一步处理得到电解金属锰；C.将步骤B得到的滤渣置于水中搅拌水洗、压滤,然后焙烧,抽出废气,回收二氧化硒提纯；后进行酸洗、歧化活化、净化除杂、压滤、烘干、研磨。该方法降低了生产成本,提高了收益,安全环保、无污染,提高了锰的总回收率,浸出率、压滤率和锰离子的上板率。(The invention belongs to the technical field of electrolytic production and recovery of manganese by a solution electrolytic method, and particularly relates to a production method for producing electrolytic manganese metal and coproducing manganese dioxide, which comprises the following steps of A, placing manganese oxide, manganese hydroxide or manganese carbonate with the manganese element content of more than or equal to 47% in anolyte for electrolyzing manganese metal, B, stirring and leaching the anolyte obtained after electrolysis, regulating the pH to 6.1-6.4, purifying, filter-pressing, deslagging, standing to obtain electrolyte, electrolyzing the electrolyte, carrying out treatment to obtain electrolytic manganese metal, C, placing the filter residue obtained in the step B in water, stirring and washing, filter-pressing, roasting, extracting waste gas, recovering selenium dioxide, purifying, then carrying out acid washing, disproportionation activation, purification and impurity removal, filter-pressing, drying and grinding.)

1. The production method for producing the electrolytic manganese metal and co-producing manganese dioxide is characterized by comprising the following steps of:

A. putting manganese oxide, manganese hydroxide or manganese carbonate with the manganese element content of more than or equal to 47 percent into anolyte for electrolyzing metal manganese, and electrolyzing at the temperature of 40-50 ℃;

B. stirring and leaching the anolyte obtained after electrolysis to ensure that the content of divalent manganese ions in the qualified electrolyte of the electrolytic manganese metal is 30-40g/L, then adjusting the pH to 6.1-6.4, purifying, filter-pressing, removing residues, standing to obtain the electrolyte, electrolyzing the electrolyte, and processing by step to obtain the electrolytic manganese metal;

C. b, placing the filter residue obtained in the step B in water, stirring, washing with water, filter-pressing, roasting, extracting waste gas, recovering selenium dioxide, and purifying; then acid washing, disproportionation activation, purification and impurity removal, filter pressing, drying and grinding are carried out.

2. The method as claimed in claim 1, wherein the anolyte of step a has a sulfuric acid content of 40-50g/L, an ammonium sulfate content of 80-100g/L, and a divalent manganese ion content of 14-15 g/L.

3. The method as claimed in claim 2, wherein the anolyte of step a has a sulfuric acid content of 40-50g/L, an ammonium sulfate content of 80-100g/L, and a divalent manganese ion content of 14-15 g/L.

4. The method of claim 1, wherein the pH adjustment to 6.1-6.4 in step B is performed by adding 15-17% by weight of ammonia water to adjust the pH to 6.1-6.4.

5. The method as claimed in claim 1, wherein in step B, the anolyte obtained after electrolysis is stirred and leached, then the pH is adjusted to 6.1-6.4, and the anolyte is purified, filter-pressed, deslagged and stood to obtain electrolyte, and the electrolyte is electrolyzed and treated by step to obtain electrolytic manganese metal.

6. The method as claimed in claim 2, wherein in step B, the anolyte obtained after electrolysis is stirred and leached, then the pH is adjusted to 6.1-6.4, and the anolyte is purified, filter-pressed, deslagged and stood to obtain electrolyte, and the electrolyte is electrolyzed and treated by step to obtain electrolytic manganese metal.

7. The method as claimed in claim 1, wherein the temperature of the calcination in step C is 540-800 ℃.

8. The method of claim 1, further comprising the steps of: D. and combining the washing water and the disproportionation activated acid solution to be used as a supplementary solution of the electrolytic manganese metal anode solution.

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 production method of co-products of electrolytic manganese metal and manganese dioxide.

Background

The method is mainly characterized in that firstly, the loss of electrolytic manganese anode mud produced by the existing process is utilized, part of anode mud enters an initialization combination tank along with anode liquid, manganese dioxide and dilute sulfuric acid do not chemically react, and part of manganese dioxide is brought into acid leaching loss and removed manganese sulfate, loss of manganese sulfate and ammonium sulfate loss are also removed, and the loss of iron sulfate and ammonium sulfate is caused by the fact that the existing process directly produces low-cost ammonia sludge containing sulfur dioxide and ammonium sulfate, and the loss of iron sulfate and ammonium sulfate is caused by the fact that the existing process produces the iron-making waste slag which contains low sulfide, low-phosphorus, low-calcium, magnesium and other low-harmful substances such as manganese carbonate and manganese oxide, and the iron-making waste slag directly produces iron-making waste.

CN104404244A chinese patent discloses methods for producing electrolytic manganese metal by using manganese oxide, which is to prepare electrolytic manganese by using low-valence manganese prepared by direct leaching after roasting reduction of pulverized coal, wherein, during roasting, manganese oxide ore with a particle size of is preferred, and conditions such as proper roasting temperature, acid-mineral ratio, solid-liquid ratio and the like are determined.

Disclosure of Invention

In view of the above, the present invention aims to provide methods for producing electrolytic manganese metal and co-producing manganese dioxide.

In order to achieve the purpose, the technical scheme of the invention is as follows:

the production method for producing the electrolytic manganese metal and co-producing the manganese dioxide comprises the following steps:

A. putting manganese oxide, manganese hydroxide or manganese carbonate with the manganese element content of more than or equal to 47 percent into anolyte for electrolyzing metal manganese, and electrolyzing at the temperature of 40-50 ℃;

B. stirring and leaching the anolyte obtained after electrolysis to ensure that the content of divalent manganese ions in the qualified electrolyte of the electrolytic manganese metal is 30-40g/L, then adjusting the pH to 6.1-6.4, purifying, filter-pressing, removing residues, standing to obtain the electrolyte, electrolyzing the electrolyte, and processing by step to obtain the electrolytic manganese metal;

C. b, placing the filter residue obtained in the step B in water, stirring, washing with water, filter-pressing, roasting, extracting waste gas, recovering selenium dioxide, and purifying; then acid washing, disproportionation activation, purification and impurity removal, filter pressing, drying and grinding are carried out.

The pickling is to remove an oxide layer and rusty materials on the surface by using an acid solution, and Mn is removed in the pickling process₂O₃And H₂SO₄Reaction to MnO₂And MnSO₄I.e. Mn₂O₃Disproportionation reaction is carried out to generate active MnO₂And MnSO₄。

In the qualified electrolyte, Mn²⁺The content is 30-40g/L, Zn is less than or equal to 5mg/L, Co is less than or equal to 0.5mg/L, Ni is less than or equal to 1.0mg/L, Pb is less than or equal to 1.0mg/L, Cu is less than or equal to 0.5mg/L, (NH)₄)₂SO₄The content is 80-95g/L, and the pH is 6.1-6.4.

The method has no special requirement on the particle size of the manganese ore, and does not generate extra cost.

The method enables part of manganese dioxide in the anode mud to be converted into active manganese dioxide, part of manganese dioxide generates manganese sulfate to be continuously electrolyzed, so that the recovery rate of manganese is improved, and in addition, , the generation of waste residues is reduced, so that the production cost is reduced.

In addition, the method treats the selenium in the manganese ore and recovers the selenium dioxide, thereby greatly reducing the production amount of waste residues and lowering the production cost, and in addition, , the recovered selenium dioxide can also improve the production yield.

The method does not generate NH in the production process₃And the like, is safe and environment-friendly, and has no pollution.

The method can produce two kinds of products simultaneously, thereby reducing unit power consumption of the products.

And step , in order to ensure the smooth proceeding of the electrolytic reaction, the content of sulfuric acid in the anolyte in the step A is 40-50g/L, the content of ammonium sulfate is 80-100g/L, and the content of divalent manganese ions is 14-15 g/L.

The sulfuric acid and the ammonium sulfate can be recycled, thereby greatly reducing the production cost.

And step , wherein the pH value adjusted to 6.1-6.4 in the step B is adjusted to 6.1-6.4 by adding ammonia water with the mass fraction of 15-17%.

And step , in the step B, stirring and leaching the anolyte obtained after electrolysis to ensure that the content of divalent manganese ions in the qualified electrolytic manganese metal solution is 30-38g/L, then adjusting the pH value to 6.1-6.4, purifying, press filtering, removing residues, standing to obtain electrolyte, electrolyzing the electrolyte, and processing in the step to obtain the electrolytic manganese metal.

The heavy metal obtained by the treatment in the step is recycled, so that the generation amount of waste residues is reduced, and the production cost is reduced; meanwhile, the recovery of heavy metals can improve the yield.

And step , the temperature of the roasting in step C is 540-800 ℃.

And step , combining the washing water and the disproportionation activated acid solution to be used as a supplementary solution of the electrolytic manganese metal anode solution.

Recycling the anolyte and water (the main chemical equation in the step is MnSO)₄+H₂O＝2Mn+O₂+2H₂SO₄)。

The method has the advantages of no waste water discharge, recycling of anolyte, reduction of production cost, safety and environmental protection.

The method for producing the electrolytic manganese metal does not need to rebuild or newly build a large waste residue warehouse, fully utilizes heat energy, reduces the conveying distance of the anode mud and the anolyte, the stacking place and the labor cost of the anode mud, enriches and recovers the selenium dioxide, reduces the production cost and improves the benefit.

The electrolytic manganese metal produced by the prior art consumes 2 tons of sulfuric acid (about 620 yuan/ton), 0.001kg of selenium dioxide (about 20-80 ten thousand yuan/ton) and 100kg of liquid ammonia (about 3300 yuan/ton) for each 1 ton of manganese metal. When the method is used for producing the electrolytic manganese metal, the sulfuric acid, the ammonium sulfate and the selenium dioxide can be recycled, so that the production cost is greatly reduced, and the 1570.2-1570.8 yuan cost is saved when 1 ton of electrolytic manganese metal is produced.

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 away₂The anode mud is sold to other manufacturers at the price of 400-600 yuan/ton, the manganese dioxide in the anode mud is partially converted into active manganese dioxide by the method for producing the electrolytic manganese metal, part of the manganese dioxide generates manganese sulfate for recycling and continuous electrolysis, so that the recovery rate of manganese is improved, and meanwhile, the generated active manganese dioxide (about 10000 yuan/ton) also greatly improves the benefit.

The invention has the beneficial effects that:

(1) the method has no special requirement on the particle size of the manganese ore, and does not generate extra cost.

(2) The method for producing the electrolytic manganese metal has the advantages that the sulfuric acid, the ammonium sulfate and the selenium dioxide can be recycled, so that the production cost is greatly reduced, 1570.2-1570.8 yuan is saved when 1 ton of the electrolytic manganese metal is produced, part of manganese dioxide in anode mud is converted into active manganese dioxide, part of manganese dioxide generates manganese sulfate for recycling, the electrolyte is supplemented for continuous electrolysis, so that the recovery rate of manganese is improved, and meanwhile, the generated active manganese dioxide (about 10000 yuan/ton) is greatly increased in income.

(3) The original main production process equipment of electrolytic manganese is not required to be changed, and the process is simple and mature.

(4) 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.

(5) Does not generate NH₃And the like, is safe and environment-friendly, and has no pollution.

(6) The total recovery rate (more than 98%) of manganese, the leaching rate, the press filtration rate and the plate loading rate of manganese ions are improved.

(7) 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.

Drawings

FIG. 1 is a flow chart of a process for producing electrolytic manganese metal with co-production of manganese dioxide.

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.