JPS63222017A - Production of high-purity manganese compound - Google Patents

Abstract

PURPOSE:To readily obtain a high-purity Mn compound, by adding ferromanganese to an aqueous solution containing an electrolyte, adjusting to proper pH, dissolving iron, aging, separating and removing undissolved substances, precipitating Mn and iron and recovering. CONSTITUTION:An electrolyte-containing aqueous solution (e.g. aqueous solution of ammonium chloride) is blended with one or more of ferromanganese and metallic manganese, an acid is added to the solution while stirring, manganese and iron are dissolved by maintaining pH2-9. The solution is aged, undissolved substances are condensed, coarse particles are formed and the undissolved substances are separated and removed. Then manganese and iron in the solution are precipitated and recovered to give a high-purity manganese compound. The prepared manganese compound has low content of impurities such as Si and P and is preferably used as a raw material for ferrite of manganese type.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a high purity manganese compound, and particularly to a method for producing a manganese compound suitable as a raw material for manganese ferrite.

[Conventional technology]

Conventionally, high-purity manganese compounds are produced by dissolving manganese ore in sulfuric acid, impurity heavy metals are removed by the sulfide method, solvent extraction method, alcoholate method, etc., and iron is oxidized and separated and removed as hydroxide. Methods are being used to recover it as various salts.

Recently, in order to produce manganese compounds with even higher purity, ferromanganese or metallic manganese, which has fewer impurities than manganese ore, are used, and these are directly dissolved in acid, and heavy metals and iron are separated and removed as in the previous conventional method. There is a method of purifying high-purity manganese compounds by further combining recrystallization.

However, the above method requires several steps and a purification step using a multiplex recrystallization method, which not only has poor processing efficiency but also does not necessarily result in a product of high purity.

In order to improve the drawbacks of the conventional method described above, the present applicant added one or two of ferromanganese and metallic manganese to an aqueous solution containing an electrolyte, added acid while stirring, and maintained the pH at 2 to 9 to remove undissolved substances. (See Japanese Patent Application No. 60-197246) to propose a method for obtaining highly pure manganese compounds by separating, precipitating and recovering manganese and iron in solution.

[Problems to be solved by the present invention]

The invention described in the above-mentioned Japanese Patent Application No. 60-1.97246 (hereinafter referred to as the prior art) has a simple treatment process compared to the conventional method, and it can treat heavy metals such as Cr, Co, and Ni as well as P and Si. , AA, V, and other impurities can be removed.

However, although the above-mentioned prior art is effective in removing impurities, there is considerable variation in impurity removal efficiency, and therefore, it is necessary to sort by impurity content before use, and products of stable quality cannot be obtained. It is difficult to supply in large quantities.

As a result of research to improve the drawbacks of the prior art described above, the present invention provides a method for stably producing a high-purity manganese compound with extremely low impurity content and little variation in manganese compound used as a raw material for ferrite. It's about doing.

[Means for solving problems]

The first invention of the present application is to add ferromanganese, one type of metal manganese, or one type of Ha23 to an aqueous solution containing an electrolyte, add an acid while stirring, and adjust p+-1 to 2 to 9.
In the process of precipitating and recovering the manganese and iron in the solution, after dissolving the manganese and iron, the solution is aged and then the undissolved substances are separated and removed. This is a method for producing a high-purity manganese compound consisting of the following components.

In addition, the second invention is to add one or two of ferromanganese and metallic manganese to an aqueous solution containing an electrolyte, add acid while stirring, and maintain the pH at 2 to 9 to dissolve manganese and iron. After that, in the process of precipitating and recovering the manganese and iron in the solution, after dissolving the manganese and iron, undissolved substances are separated and removed, followed by adding a precipitant to the solution and subjecting it to aging treatment. This is a method for producing a high purity manganese compound consisting of:

[For production]

The present invention has the following configuration, and the electrolyte used in the art is one or more of ammonium chloride, ammonium nitrate, ammonium acetate, or alkali metal salts.
Two.

Furthermore, the manganese compound referred to in the present invention includes not only a manganese compound alone but also a mixture of a manganese compound and an iron compound.

Ferromanganese and metallic manganese (pulverized, preferably less than 60 mesh), which are the raw materials of the present invention, are added to an electrolyte solution.

When ferromanganese and metallic manganese as described above are added to water, some of the manganese and iron react with the water to produce hydroxide, and the pH of the liquid increases to around 9.7.

On the other hand, when the ferromanganese and metal manganese are added to a solution containing an electrolyte such as ammonium chloride, manganese and iron similarly produce hydroxides, but the buffering action of the electrolyte lowers the pH of the solution. The degree to which the pH decreases varies depending on the concentration of the electrolyte, but for example, in the case of a 2% solution of ammonium chloride, the pH is about 9.0, 20%
The solution value is about 7.8.

The pH at which manganese hydroxide (n) or iron hydroxide (I+) completely precipitates is approximately 9 or higher and 18 or higher, respectively, so the produced manganese hydroxide and iron hydroxide are partially dissolved.
Other parts remain in a precipitated state, while noble elements that tend to ionize more than manganese and iron, ie, heavy metal elements, remain unreacted. In addition, according to this method, Cao, SiO2 contained in ferromanganese and metal manganese
゜AI 203. Nonmetallic inclusions (slag components) mainly composed of oxides such as MgO are hardly dissolved and are almost completely separated.

Manganese hydroxide produced as described above.

When acid is added to iron hydroxide, manganese hydroxide and iron hydroxide become salts and dissolve, completely separating heavy metal elements. The acids used for cleaning are hydrochloric acid and sulfuric acid.

Either acetic acid or nitric acid may be used.

Therefore, in a solution containing an electrolyte, the pH change due to the addition of an acid is reduced due to the buffering effect of the electrolyte. and,
In such a pH range (at least pH=2 or higher), unreacted substances are not affected by the acid and are therefore not dissolved at all, allowing complete separation of impurities.

Although various elements such as P, i, and V can be removed to a considerable extent by the above method, there are variations in the removal rate.

In particular, materials such as Co and Ca, whose dissolution rate is highly dependent on temperature, P and Si.

This has a large effect on substances such as AI, in which unreacted substances in the reaction system are adsorbed to the precipitate and removed.

The present invention involves adding one or both of ferromanganese and metallic manganese to an aqueous solution containing an electrolyte, adding acid while stirring, and maintaining the pH at 2 to 9 to dissolve and recover manganese and iron. In the method, after dissolving the manganese and iron,
By adopting the aging process, the removal rate of impurities can be improved and a stable product with less variation can be obtained.

That is, in the first invention, manganese and iron are dissolved and then aged. As a result, the silicic acid component dissolved during dissolution gradually polymerizes and precipitates, and can be separated together with undissolved materials.

Furthermore, the first invention provides, by the aging treatment,
When undissolved substances are separated by filtration, the filtration rate can be greatly improved. This is thought to be due to the gradual condensation of undissolved substances to form coarse particles as the aqueous solution ages, and therefore the filtration process is facilitated, which is highly effective when carried out industrially.

Further, the time required for aging may be appropriately selected depending on the allowable amount of Si in the target product, but is desirably 3 hours or more and about 10 hours.

After completing the aging process, undissolved −8= Remove things in advance.

The second invention involves dissolving and extracting manganese and iron in an aqueous solution, separating and removing undissolved substances, and then adding a precipitant to the solution for ripening. As a result, the P eluted into the solution is adsorbed by the precipitant, precipitated, and easily separated and removed.

The precipitants used in the art are aluminum salts, iron(III)
Add a small amount of salt or other substances that will not be dissolved or extracted into the solution. In this case, not only the impurity Si but also the P can be almost completely removed.

In addition, also in the second invention, the precipitant added during ripening aggregates, improving the filtration rate.

Substantially only manganese and iron are dissolved and extracted in the aqueous solution by the above-mentioned means.

In order to recover manganese and iron from the aqueous solution, manganese and iron in the solution are precipitated, for example, as carbonates, and then the carbonates are recovered, thereby making it possible to recover manganese compounds with an extremely low content of impurities. can.

Furthermore, if necessary, the carbonate can be easily recovered as a high-purity oxide containing manganese and iron by calcining it at 800°C.

Note that when recovering the manganese compound from the solution, it is not necessarily necessary to recover it as a carbonate, as long as it can be easily precipitated and separated from the solution.

〔Example〕

The present invention will be specifically explained below with reference to Examples.

Example 1 To 500 liters of 10% ammonium chloride solution, 50 g of ferromanganese powder crushed to 6o mesh or less was added,
While stirring the solution, 1.2M hydrochloric acid was successively added to the solution to dissolve and extract manganese and iron in the ferromanganese.

], by addition of 2M hydrochloric acid, the pH of the solution was 8.5.
The pH gradually decreased, but when the pH reached 5, the addition of 12M hydrochloric acid was stopped and the reaction was terminated.

Then, the solution (containing undissolved materials) after the reaction was transferred to another container and aged for 10 hours.

In this case, collect appropriate solutions to observe changes over time.
The analysis of i is shown in Figure 1.

As is clear from FIG. 1, the Si content in the solution decreases as the aging time progresses, indicating that aging is effective in removing Si.

In addition, in this case, a comparison of the filtration rates between the first invention and the case without aging treatment is as shown in Table 1.

Table 1 (Note) Use a filter press for filtration.

That is, in the first invention, it is recognized that the filtration speed is improved to 11 compared to the case without aging treatment, and the filtration time can be shortened.

Example 2 After dissolving and extracting manganese and iron in a 10% ammonium chloride solution in the same manner as in Example 1, undissolved substances in the solution were separated by filtration, and then 5% of a 10% ferric chloride solution was added.
00 ml was added and mixed and aged for 10 hours, P in the solution,
The analysis of Si was as shown in Table 2. still,
For comparison, the results without aging treatment are also shown.

Table 2 [Effects of the Invention] As described above, the present invention involves adding ferromanganese metal manganese to an electrolyte aqueous solution, adjusting the pH to 2 to 9 while adding an acid, dissolving and extracting manganese and iron in the solution, and recovering them. In this process, it is possible to improve the removal rate of impurities, especially Si and P, by aging a solution in which manganese and iron are dissolved, and by separating and removing undissolved substances and then adding a precipitant and aging. can.

In addition, since the aging treatment allows undissolved precipitates to coagulate, the filtration process for undissolved matters can be improved.

[Brief explanation of the drawing]

The figure is a graph showing the relationship between the aging time and the Si content in the solution.

Claims (2)

[Claims] (1) Add one or both of ferromanganese and metal manganese to an aqueous solution containing an electrolyte, add acid while stirring, and p
After dissolving manganese and iron by maintaining H at 2 to 9, in the step of precipitating and recovering manganese and iron in the solution,
A method for producing a high-purity manganese compound, which comprises dissolving manganese and iron, subjecting them to aging treatment, and then separating and removing undissolved substances. (2) Add one or both of ferromanganese and metallic manganese to an aqueous solution containing an electrolyte, add acid while stirring, and p
After dissolving manganese and iron by maintaining H at 2 to 9, in the step of precipitating and recovering manganese and iron in the solution,
After dissolving manganese and iron, separating and removing undissolved materials,
A method for producing a high-purity manganese compound, which comprises then adding a precipitant to the compound and subjecting it to aging.