JPH0455133B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] 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. [Prior art] Conventionally, high-purity manganese compounds are produced by dissolving manganese ore in sulfuric acid, impurity heavy metals are removed by sulfide method, solvent extraction method, alcoholate method, etc., and iron is oxidized and separated and removed as hydroxide. After that, methods are being used to recover manganese as various salts. Recently, in order to produce manganese compounds of even higher purity, ferromanganese or metallic manganese, which has fewer impurity elements than manganese ore, are used, which are directly dissolved in acid, heavy metals and iron are separated and removed in the same way as in the conventional method, and then recycled. There is a method for purifying high-purity manganese compounds by combining crystallization methods. 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 mentioned above, the applicant has
One or two types of ferromanganese and metal manganese are added to an aqueous solution containing an electrolyte, and an acid is added while stirring.
He proposed a method of obtaining a highly pure manganese compound by maintaining the pH at 2 to 9, separating undissolved substances, and precipitating and recovering manganese and iron in the solution (see Japanese Patent Application No. 197246/1983). [Problems to be solved by the invention] The invention described in the above-mentioned Japanese Patent Application No. 60-197246 (hereinafter referred to as the prior art) has a treatment process that is simpler than the conventional method, and moreover, It has the effect of removing impurities such as P, Si, Al, and V in addition to heavy metals such as P, Si, Al, and V. However, although the above-mentioned prior art is effective in removing impurities, there is considerable variation in impurity removal efficiency, and therefore, when used, it is necessary to sort according to the impurity content, 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 the 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, and heat the mixture at a temperature of 20 to 60°C. PH2
This is a method for producing a high-purity manganese compound, which consists of dissolving manganese and iron by maintaining the solution at a temperature of 9 to 9, then separating and removing undissolved substances, and precipitating and recovering the manganese and iron in the solution. In addition, the second invention is to add one or two of ferromanganese and metal manganese to an aqueous solution containing an electrolyte, add acid while stirring and blowing air, and raise the temperature to 20 to 60°C and pH 2 to 9. This is a method for producing a high-purity manganese compound, which consists of holding and dissolving manganese and iron, separating and removing undissolved substances, and precipitating and recovering manganese and iron in the solution. [Function] The present invention is constructed as described above, and the electrolyte used in the electrolyte 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 ground (preferably under 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 produce 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 effect 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, 2% of ammonium chloride
In the case of a solution, the pH is approximately 9.0, and in the case of a 20% solution, it is approximately 7.8. Manganese hydroxide () or iron hydroxide ()
Since the pH at which the hydroxide completely precipitates is about 9 or above and about 8 or above, respectively, the produced manganese hydroxide and iron hydroxide are partially dissolved and the other part is in a precipitated state.
On the other hand, noble elements that tend to ionize more than manganese and iron, ie, heavy metal elements, remain unreacted. Also, according to this method, CaO, SiO ₂ , Al ₂ O ₃ , which are contained in ferromanganese and metal manganese,
Nonmetallic inclusions (slag components) mainly composed of oxides such as MgO are hardly dissolved and can be almost completely separated. When an acid is added to the manganese hydroxide and iron hydroxide produced as described above, the manganese hydroxide and iron hydroxide become salts and dissolve, and the heavy metal elements can be completely separated. 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. And such a PH area (at least PH
= 2 or more), unreacted substances are not affected by the acid and therefore do not dissolve at all, allowing complete separation of impurities. Although various elements such as P, Al, and V can be removed to a considerable extent by the above-described method, there are variations in the removal rate. Especially for materials such as Co and Ca, whose dissolution rate is highly dependent on temperature, P, Si, and Al.
The influence of substances that are removed by adsorption to unreacted substances or precipitates in the reaction system is large. Therefore, the first invention improves the removal rate of impurities, especially the removal of Co and Ca, by maintaining the reaction temperature at 20 to 60°C when adding and dissolving acid while stirring in the reaction system. We were able to increase the ratio and reduce variation. On the other hand, if the temperature is less than 20°C, the dissolution reaction rate of manganese and iron is unfavorable, and if it exceeds 60°C, the dissolution rate of Co, Ca, etc. becomes high and the removal rate thereof becomes low. In addition, by setting the temperature to 20 to 60°C as described above, the removal rate of impurities such as P, Al, and V can also be reduced by Co,
It improves in the same way as Ca, etc., and there is little variation. Moreover, the second invention is to dissolve the mixture while blowing air into the reaction system of the first invention. That is, the first invention is to add ferromanganese or metal manganese to an aqueous solution containing an electrolyte,
Add the acid while stirring, at a temperature of 20~20°C.
By adjusting the temperature to 60°C and pH 2 to 9, it is possible to obtain a manganese compound with extremely low impurities.However, by combining the first invention with means for blowing air into the reaction system, impurities can be reduced. can be further reduced. That is, ferromanganese and metallic manganese are added to an aqueous solution containing an electrolyte, and heated at 20 to 60°C while stirring.
When acid is added to adjust the pH to 2 to 9, when air is blown into this, iron hydroxide () is oxidized to produce iron hydroxide (). This iron hydroxide (2) precipitates more easily at low pH than iron hydroxide (2), but in particular, it precipitates almost completely at pH 3 or higher. Therefore, for the purpose of high-purity manganese compounds, Fe
If it is necessary to reduce the content as much as possible, PH5 ~
It should be 9. In addition, the precipitation of iron hydroxide () is caused by the presence of trace amounts of P, Si, Al, and
Since impurities such as Cr are adsorbed, the impurity content can be significantly reduced by filtering and separating them, and therefore, it is possible to obtain products with even lower impurities than in the first invention. can. By the above-mentioned means, substantially only manganese and iron are dissolved and extracted in the aqueous solution. 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. In addition, the carbonate may be heated to 800°C if necessary.
A high purity oxide containing manganese and iron or a high purity manganese oxide can be easily obtained by firing. Note that when 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 may be used. [Examples] The present invention will be specifically described below based on the following examples. Example 1 15 g of ferromanganese powder pulverized to 60 mesh or less was added to 150 ml of a 10% ammonium chloride solution, and while stirring the solution, 6M hydrochloric acid was successively added to dissolve and extract the 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 and the reaction was terminated. On this occasion,
In order to investigate the effect of extraction temperature on the trace element content in the final product, the solution was
The reaction was carried out while maintaining the temperature between 90°C and 90°C. The reaction time is 2 to 5 hours, and the amount of 6M hydrochloric acid consumed is
The reaction rate (dissolution rate) of the total amount of manganese and iron in the ferromanganese was 88 to 92%, calculated from the amount of hydrochloric acid consumed. Next, the reaction-completed solution was filtered to separate and remove undissolved substances, and then 22 g of ammonium carbonate was added.
was added, and the pH of the solution was adjusted to 7.8 with aqueous ammonia to precipitate the manganese in the solution as carbonate.
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 ₂ O ₃ ). The analysis of Co and Ca is as shown in Figures 1 and 2, respectively.
It is observed that when the temperature exceeds 60°C, the elution amount of both Co and Ca increases and the purification effect decreases. Furthermore, when the temperature is 60°C or lower, the removal rate of Co and Ca has little variation and is stable. Example 2 15 g of ferromanganese powder crushed to 60 mesh or less was added to 150 ml of 10% ammonium chloride solution, and while stirring the solution, the mixture was heated at approximately 1 minute per minute using a Teflon tube inserted into the solution.
of air was blown into the reactor, and 6M hydrochloric acid was successively added to dissolve and extract manganese and iron in the ferromanganese. The temperature at this time is maintained within the range of 20 to 60°C. By adding 6M hydrochloric acid, the pH of the solution gradually decreased from 8.5, but when the pH reached 5, the addition of 6M hydrochloric acid was stopped to terminate the reaction. At this time, iron is extracted and dissolved, and oxidized by air to produce iron hydroxide (), which is precipitated. The reaction time was about 2 hours, the consumption of 6M hydrochloric acid was 72 ml, and the reaction rate (dissolution rate) of manganese in ferromanganese calculated from the consumption of hydrochloric acid was 99%. Next, the reaction-completed solution was filtered to separate and remove undissolved substances, iron hydroxide, etc., and then 22 g of ammonium carbonate was added, and the pH of the solution was adjusted to 7.8 with aqueous ammonia. was precipitated as a carbonate, and 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 composed of Mn ₂ O ₃ ).
Where Si, Cr, Al, V and Fe were analyzed, Table-
1. For comparison, Table 1 also shows the results obtained when dissolving without blowing air.

【table】

〔Effect of the invention〕

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

[Brief explanation of drawings]

FIG. 1 is a graph showing the relationship between Co content and temperature, and FIG. 2 is a graph showing the relationship between Ca content and temperature.

Claims (1)

[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 to 60°C and pH 2 to 9 to dissolve manganese and iron. A method for producing a high-purity manganese compound, which comprises dissolving, separating and removing undissolved substances, and precipitating and recovering manganese and iron in the solution. 2 Add one or both of ferromanganese and metal manganese to an aqueous solution containing an electrolyte, add acid while stirring and blowing air, and raise the temperature to 20-60°C.
A method for producing a high-purity manganese compound, which comprises dissolving manganese and iron by maintaining the temperature at a temperature of 0.degree.