JPS63222016A - Production of high-purity manganese compound - Google Patents

Abstract

PURPOSE:To readily obtain a high-purity Mn compound, by adding ferromanganese and (or) metallic Mn to an aqueous solution containing an electrolyte, adding an acid, controlling pH, dissolving Mn and iron, 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 while stirring, manganese and iron are dissolved by maintaining temperature at 20-60 deg.C and at pH2-9. Then undissolved substances are separated and removed, manganese and iron in the solution are precipitated and recovered to give high-purity manganese compound. Consequently, since ferromanganese and metallic manganese are added to the electrolytic solution, the solution is adjusted to proper pH and maintained at given temperature, the impurities such as Co and Ca in the raw material can be simply removed.

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-based ferrite. It is.

[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 impurity elements than manganese ore, are used, which are directly dissolved in acid, and heavy metals and iron are separated and removed in the same way as in the conventional method. Furthermore, there is a method of purifying high-purity manganese compounds by combining a recrystallization method.

However, the above method requires several steps and a purification step using a complicated 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. He proposed a method for obtaining high-purity manganese compounds by separating, precipitating and recovering manganese and iron in solution (see Japanese Patent Application No. 1972-1972).

[Problems to be solved by the present invention]

The invention described in the above-mentioned Japanese Patent Application No. 1972-1988 (hereinafter referred to as the prior art) has a simpler treatment process compared to the conventional method, and furthermore, in addition to heavy metals such as Cr, Co, and Ni, P, Si, and A7 can be removed. ! , V, and the like 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 must be produced in large quantities. It is difficult to supply

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 used as a raw material for ferrite, which has an extremely low content of impurities and has little variation. It's about doing.

[Means for solving problems]

The first invention of the present application is to add one or two of ferromanganese and metallic manganese to an aqueous solution containing an electrolyte, add an acid while stirring, maintain the temperature at 20 to 60°C and pH 2 to 9, and then add manganese and manganese. After dissolving the iron, undissolved matter is separated and removed,
This is a method for producing a high-purity manganese compound, which consists of precipitating and recovering manganese and iron in a solution.

Further, the second invention adds one or two of ferromanganese and metallic manganese to an aqueous solution containing an electrolyte, and while stirring,
Add acid while blowing air, and maintain the temperature at 20-60°C.
, after dissolving manganese and iron by maintaining it at pH 2-9,
This is a method for producing a high-purity manganese compound, which consists of separating and removing undissolved substances, and precipitating and recovering manganese and iron in the solution.

[For production]

The present invention has the above structure, and the electrolyte used in the stamen is one or more of ammonium chloride, ammonium nitrate, ammonium acetate, or an alkali metal salt.

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, which are the raw materials of the present invention, are pulverized (preferably less than 60 mesh) and added to the 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 form hydroxides, and the pH of the liquid rises 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 depends on the concentration of the electrolyte, but for example, in the case of a 2% solution of ammonium chloride, p) (= 9.0 species, 2
In a 0% solution, it is about 7.8.

The pH at which manganese (II) hydroxide or iron hydroxide (LTL) completely precipitates in mushrooms is approximately 9 or higher and 8 or higher, respectively. The parts become precipitated, while the elements that are more likely to ionize than manganese and iron, ie, heavy metal elements, remain unreacted.

Also according to this method, ferromanganese.

CaO, SiO2, AJa contained in metal manganese
Nonmetallic inclusions (slag components) mainly composed of oxides such as 203+Mg○ are hardly dissolved and can be 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, making it possible to completely separate heavy metal elements. The acid used here may be any of hydrochloric acid, sulfuric acid, acetic acid, or nitric acid.

Therefore, in a solution containing an electrolyte, the pH change due to the addition of hydrochloric acid is reduced due to the buffering effect of the electrolyte. Then, in such a pH range (at least p + - (= 2 or more)
In this case, unreacted substances are not affected by the acid and therefore do not dissolve at all, allowing complete separation of impurities.

Although P, AI, V and various other elements can be removed to a considerable extent by the above method, the removal rate varies. In particular, materials such as Co and Ca, whose dissolution rate is highly dependent on temperature, as well as P and Si.

The effect is large on substances such as A1 that are adsorbed and removed by unreacted substances or precipitates in the reaction system.

Therefore, in the first invention, when adding and dissolving an acid while stirring in the reaction system, the temperature of the reaction etc. is set to 20 to 60''.
By holding C, the removal rate of impurities, especially Co,
It was possible to increase the Ca removal rate and reduce variation.

On the other hand, if the temperature is less than 20°C, it is undesirable because the dissolution reaction rate of manganese and iron is slow, and if it exceeds 60°C, the dissolution rate of Co, Ca, etc. increases and the removal rate becomes small. .

Further, by setting the temperature to 20 to 60°C as described above, the removal rate of impurities such as P, Al, and V is improved similarly to that of Co, Ca, etc., and the variation thereof is also small.

Moreover, the second invention is one in which the reaction system of the invention in the cylinder 1 is dissolved while further air is blown thereinto. That is, the first
The invention was ferromanganese.

adding metallic manganese to an aqueous solution containing an electrolyte;
Add the acid with stirring, at a temperature of 20-60°C.
By adjusting the temperature and pH to 2 to 9, it is possible to obtain a manganese compound with extremely low impurities, but by combining the first invention with a means of blowing air into the reaction system, impurities can be further reduced. be able to.

When added to an aqueous solution containing solute, ferromanganese, and metal manganese laminate and adjusted to pH 2 to 9 by adding acid at 20 to 60'C with stirring, air is blown into the solution.
Iron hydroxide (n) is oxidized to produce iron hydroxide (lit). This iron hydroxide (Ill) precipitates more easily at low pH than iron (II) hydroxide, but in particular, it precipitates almost completely at pH 3 or higher.

Therefore, if it is necessary to reduce the Fe content as much as possible for the purpose of producing a high-purity manganese compound, the pH may be adjusted to 5 to 9. In addition, the precipitation of iron (III) hydroxide is due to the presence of trace amounts of P, Si, and Al in the solution.

Since impurities such as Cr are adsorbed, the impurity content can be significantly reduced by filtering and separating them, and therefore a product with even lower impurities than the first invention can be obtained.

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

To recover manganese and iron from the aqueous solution, the manganese and iron in the solution are precipitated, e.g. as carbonates.I-
By collecting the carbonate and recovering the carbonate, a manganese compound with extremely low impurity content can be recovered.

Further, if the carbonate is calcined at 800° C. if necessary, a high purity oxide containing mankanium and iron or a high purity manganese oxide can be easily obtained.

In recovering the manganese compound from the solution, it is not necessarily necessary to recover it as a carbonate, but any compound that can be easily precipitated and separated from the solution is sufficient.

〔Example〕

The present invention will be specifically explained below based on the following examples.

Example 1 To 150 ml of a 10% ammonium chloride solution was added 15 I of ferromanganese powder crushed to 60 mcs or less, and while stirring the solution, 6M hydrochloric acid was successively added to dissolve and extract manganese and iron in the ferromanganese.

The pH of the solution was gradually lowered from 8.5 by the addition of 6M hydrochloric acid, but when the predetermined pH was reached, the addition of 6M hydrochloric acid was stopped to terminate the reaction.

At this time, in order to investigate the effect of extraction temperature on the trace element content in the final product, the solution was heated at 10°C in a constant temperature bath.
Keep it at 90'C and let it react.

The reaction time was 2 to 5 hours, and the amount of 6M hydrochloric acid consumed was 76 to 8 hours.
The reaction rate (dissolution rate) of manganese and iron content in ferromanganese calculated from the consumption amount of hydrochloric acid was 88 to 92%.

Next, the reaction-completed solution was filtered to separate and remove undissolved substances, and then 22 g of ammonium carbonate was added, and the pH of the solution was adjusted to 7.8 with aqueous ammonia to remove the manganese in the solution as carbonate. After precipitation, the carbonate was collected by filtration.

In order to confirm the purification effect of the carbonate, the recovered carbonate was dried at 110°C and then calcined at 800°C for 90 minutes to form manganese oxide (mainly Mn 203). The analysis of Co and Ca was as shown in Figures 1 and 2, respectively, and the temperature was 60''C.
It is observed that when the amount exceeds 100%, the elution amount of both Co and O increases, and the purification effect decreases. Also, the temperature is 60°
Below C is Co.

There is little variation in the Ca removal rate and it is stable.

Example 2 Into 150 ml of 10% ammonium chloride solution, 15 ml of ferromanganese powder ground to 60 mesh or less was added. While stirring the solution, about 11 air per minute was blown through the Teflon tube inserted into the solution, and 6M hydrochloric acid was sequentially added to dissolve and extract the manganese and iron in the ferromanganese. . The temperature at this time is 20-60
Keep within 6C range.

The pH of the solution gradually decreased from 8.5 by adding 6M hydrochloric acid, but when the pH reached 5, the addition of 6M hydrochloric acid was stopped to terminate the reaction. This removed iron is once extracted and dissolved, and oxidized by air to form iron hydroxide (III).
) and precipitate. The reaction time was about 2 hours, the consumption of 6M hydrochloric acid was 72 m/h, and the reaction rate (dissolution rate) of manganese in ferromanganese calculated from the consumption of hydrochloric acid was 9.
It was 9%.

Next, the reaction-completed solution was filtered to separate and remove undissolved substances, iron hydroxide (1), etc., and then 22 g of aqueous ammonia carbonate was added, and the pH of the solution was adjusted to 7.
8, the manganese in the solution was precipitated as a carbonate, and the carbonate was immediately collected by filtration.

In order to confirm the purification effect of the carbonate, the recovered carbonate was dried at 110"C and then calcined for 90 minutes to form manganese oxide (mainly Mn 203).
P, Si, Cr, A7! , V and Fe were analyzed as shown in Table 1. For comparison, Table 1
The results are also shown when the sample was dissolved without blowing air into it.

〔Effect of the invention〕

-16= As described above, the first invention can easily remove various impurities in raw materials by adding ferromanganese or metal manganese to an electrolyte solution, adjusting the pH and maintaining the temperature. , it is possible to stably reduce elements such as Ca.

In addition, the second invention can remove various impurities and iron by combining the first invention with a simple method of further blowing air, so a wider range of raw materials can be used for ferrite. can be provided.

[Brief explanation of the drawing]

Figure 1 is a graph showing the relationship between Co content and temperature;
FIG. 2 is a graph showing the relationship between Ca content and temperature. Patent applicant: Japan Heavy and Chemical Industry Co., Ltd. Representative: Osamu Ichikawa 3. Relationship with the case of the person making the amendment Patent applicant Japan Heavy and Chemical Industry Co., Ltd. 4, Agent 5, Date of amendment order 7, Contents of the amendment As per the engraving and attached sheet of the specification originally attached to the application (contents not included) (no change)

Claims (2)

[Claims] (1) Add one or both of ferromanganese and metallic manganese to an aqueous solution containing an electrolyte, add acid while stirring, and maintain the temperature at 20-60°C and pH 2-9 to dissolve manganese and iron. A method for producing a high-purity manganese compound, which comprises separating and removing undissolved substances, and precipitating and recovering manganese and iron in a solution. (2) Add one or two of ferromanganese and metallic manganese to an aqueous solution containing an electrolyte, add acid while stirring and blowing air, and then add acid at a temperature of 20 to 60°C and a pH of 2 to 9.
1. A method for producing a high-purity manganese compound, which comprises dissolving manganese and iron by holding the solution in water, separating and removing undissolved substances, and precipitating and recovering manganese and iron in the solution.