JP3170534B2 - Method for producing purified manganese or purified iron manganese solution - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a purified manganese or purified iron manganese solution used as a raw material of a composite ferrite used as a raw material of a magnetic material, for example.

[0002]

2. Description of the Related Art
As a method of synthesizing ferrite, a dry method of mixing a plurality of oxide powders and firing at a high temperature is generally adopted. However, this method has the drawbacks that it is difficult to mix the powder raw materials homogeneously, impurities are mixed during pulverization, and it takes a long time to synthesize a composite oxide by solid phase diffusion between oxide particles. There is. The Mn source is Mn ₃ O
_{4, MnO 2, γ-MnOOH} , high purity, such as MnCO ₃
The price is high because it requires a large amount of oxides or carbonates .

[0003] On the other hand, a co-precipitation method by wet processing has been adopted as a method for obtaining a homogeneous ferrite (for example, Japanese Patent Publication No. 59-21527, Japanese Patent Publication No. 52-36119), but the method is complicated and the production cost is high. There are disadvantages.

[0004] Also, a spray roasting method is known as a method for synthesizing a composite oxide for ferrite, that is, a composite ferrite (for example, Japanese Patent Publication No. 47-11550). In this method, a composite ferrite is synthesized by spraying and roasting a metal component constituting ferrite into, for example, a chloride mixed solution and spraying and roasting this solution. This method can obtain a relatively homogeneous composite ferrite.

[0005] However, this method has a disadvantage that the step of producing manganese chloride is complicated. Also,
The chloride mixed solution used here is required to have high purity, but manganese carbonate ore and manganese dioxide ore conventionally used as starting materials for Mn contain a lot of impurities, and the impurity removal step becomes complicated. On the other hand, it has been proposed to use a reagent such as MnCl ₂ .nH ₂ O as Mn chloride (for example, Japanese Patent Publication No. 55-14442).
1) There is a disadvantage that the production cost is increased when the production scale is industrial.

The present invention has been made in view of the above circumstances, and provides a purified manganese solution capable of producing a high-purity purified manganese solution or a purified iron manganese solution used as a raw material of a composite ferrite by a simple process at a low cost. Another object is to provide a method for producing a purified iron manganese solution.

[0007]

The method for producing a purified manganese or iron manganese solution according to the present invention comprises a step of dissolving any of metal manganese, ferromanganese, and manganese ore in an acid; Al, Cr, V,
Adding and dissolving one or more selected from B, Zn and an acid solution thereof;
Adjusting the H in the range of 3.5 to 6 to form a hydroxide of the additional element, and then adding one or both of an anionic flocculant and a nonionic flocculant to the hydroxide to form the hydroxide Aggregating and separating together with SiO ₂ and other impurities in the solution.

The inventors of the present invention have conducted various studies to produce a purified manganese or purified iron manganese solution at a low cost. As a result, the present applicant has previously proposed Japanese Patent Application Laid-Open No. 1-153532.
It has been found that a high-purity purified manganese solution can be produced in a simple process by using inexpensive metallic manganese, ferromanganese, and manganese ore as starting materials. The technique disclosed in Japanese Patent Application Laid-Open No. 1-153532 is a method for purifying an acid solution containing ferrous ions. However, in the case of a manganese solution, impurities, particularly S
_They found that iO ₂ could be removed, and completed the present invention.

[0009] Simply dissolving metallic manganese, ferromanganese, and manganese ore in an acid cannot be used to produce a purified manganese or purified iron manganese solution due to a large amount of impurities. Most of the impurities can be removed, and a high-purity purified manganese or purified iron manganese solution can be produced.

The principle of the present invention is as follows. That is, in a solution of manganese or iron manganese, a metal having a large change in solubility with respect to a change in pH and having a very low residual solubility or an acid solution thereof is added.
To coprecipitate and separate these hydroxides and SiO ₂ and other impurities in the solution.

In the present invention, first, one of metal manganese, ferromanganese, and manganese ore is dissolved in an acid. The acid used here is not particularly limited, but hydrochloric acid (HCl), which is usually used as a solution for producing ferrite by spray roasting, is preferable.
In this case, the cost can be further reduced by using a recovered acid obtained by recovering HCl gas generated during waste acid roasting or the like.

Next, one or more selected from Al, Cr, V, B, Zn and these acid solutions are added to the manganese or iron manganese acid solution thus obtained. Allow to dissolve. These acid solutions include AlC
l ₃ solution, and the like.

Thereafter, the pH of the solution is adjusted to adjust the hydroxide of the additional element (eg, Al (OH) ₃ , Cr (OH)
₃ etc.). PH adjustment at this time is performed by neutralizing the acid with an alkali such as ammonia,
Select a pH suitable for the additive element used. If the pH exceeds 6, a hydroxide of Mn will crystallize. Conversely, if it is less than 3.5, the hydroxide of the added element cannot be effectively crystallized. Is defined in the range of 3.5 to 6. The crystallization reaction of the hydroxide, the additive ions positive suspended or dissolved impurities microparticles are or oxide ions in solution because it has a charge ^{_{(e.g., SiO 2, (SiO 4 -}} ) _n , n = 1 to 5) as nuclei, and simultaneously these impurity fine particles or oxide ions are captured and polymerized by additive ions having a positive charge.

Further, one or both of an anionic flocculant and a nonionic flocculant are added to the liquid, and fine colloidal crystallized particles are aggregated and coarsened, and separated from the liquid by sedimentation, filtration and the like. Through the above steps , a purified iron manganese solution is produced. In addition, this refined iron
Air is blown into the gun solution to supply oxygen and produce iron.
Purified manganese solution by removing after oxidation precipitation
A liquid is produced.

[0015]

According to the present invention, any one of metal manganese, ferromanganese, and manganese ore is dissolved in an acid, and the crystallization reaction of the hydroxide is performed in the acid solution by adjusting the pH of the solution. fine colloidal silica and ion particles are suspended in an acid solution ^{_{((SiO 4 -) n,}} n
= 1 to 5) become the nucleus of this reaction or are adsorbed by the crystallized hydroxide and are trapped in the crystallized material. Therefore, under ideal conditions, S in manganese solution or iron manganese solution
The iO ₂ content can be significantly reduced to 3 to 4 ppm or less, and other impurities are also removed, so that a high-purity purified manganese solution can be obtained. In this case, since inexpensive metal manganese, ferromanganese, and manganese ore are used as starting materials, a highly pure purified manganese or purified iron manganese solution can be produced at low cost. In addition, since the crystallization reaction of the hydroxide is used, a highly purified purified manganese or iron manganese solution can be produced by a simple process without complicating the process.

[0016]

Embodiments of the present invention will be described below.
FIG. 1 is a schematic configuration diagram showing an example of an apparatus for carrying out the method of the present invention. Dissolved tank 1 contains recovered acid (18% H
Cl) 2 and a manganese source 3 such as ferromanganese are charged, and these are stirred by a stirrer 4. As a result, the manganese source 3 is dissolved in hydrochloric acid to form a solution. This solution is supplied to the pH adjusting tank 6 by the pump 5. In the pH adjusting tank 6, the solution is stirred by the stirrer 7 to adjust the pH of the solution to 2 to 4 so that the carbon in the solution is fixed, and is filtered by the filter 9 to remove the carbon from the solution.
The pH in the pH adjusting tank 6 is measured by a pH meter 8.

The solution after filtration is supplied to a reaction tank 1 by a pump 10.
1 is supplied. The reaction tank 11 is divided into two parts, a first chamber 11a and a second chamber 11b. A stirrer 16 is provided in the first chamber 11a, and a stirrer 17 is provided in the second chamber 11b. An additive 12 for removing impurities, such as an AlCl ₃ solution, is added to the solution in the first chamber 11a. Further, pH is added alkaline material 13, such as a solution in the second chamber 11b NH ₄ OH is adjusted to a predetermined value in the range of 3.5 to 6. The pH in the second chamber 11b
Is measured by the pH meter 15.

At this stage, a hydroxide crystallization reaction occurs, and impurities such as SiO ₂ are captured and polymerized. Further, a predetermined amount of an anionic or nonionic flocculant 14 is added to the solution in the second chamber 11b according to the amount of the additive and the amount of the solution, and the crystallized product is aggregated.

In the liquid discharged from the reaction tank 11, aggregates are settled and separated from the solution by the thickener 18, and the supernatant liquid is filtered by the filter 19. Thereby, a highly pure purified manganese or purified iron manganese solution is obtained.

In order to promote the crystallization reaction of the hydroxide efficiently, it is important to stir the liquid uniformly and to maintain the temperature of the liquid at 40 to 60 ° C. Next, a series of steps of producing a purified manganese or purified iron manganese solution by the method of the present invention and producing a composite ferrite powder using the solution will be described with reference to FIG.

First, the manganese raw material is pulverized as necessary to obtain a powder or a flake (5 mm or less), which is dissolved in hydrochloric acid (step 1). At this time, for example, a recovered acid (18% HCl) whose concentration has been adjusted is used as hydrochloric acid,
The raw material is gradually supplied into the recovered acid. Then, the manganese raw material is dissolved by heating and stirring. At this time, hydrogen gas is generated, and this hydrogen gas is separately collected and used as a combustion aid.

Next, this solution is filtered for decarbonization (step 2). In this case, the pH of the solution is adjusted to 2 to 4 for decarbonization. The removed carbon is reused as a carbon source.

An additive such as an AlCl ₃ solution is added to the filtered solution (step 3). Then, the pH of the solution is adjusted to 3.5 to 6 by adding an alkaline substance such as NH ₄ OH (Step 4). Thereby, hydroxides and impurities are crystallized. Further, an anionic or nonionic coagulant is added to coagulate the crystallized product (step 5).

The aggregate is separated from the solution by settling, and the supernatant is filtered (step 6). Thereby, SiO ₂
Such impurities are almost completely separated from the solution, resulting in a high-purity solution.

When ferromanganese or manganese ore is used as a starting material, iron ions are also contained in the purified solution, but since iron is a raw material of ferrite, there is basically no need to remove iron. . However, when it is necessary to obtain a solution containing only Mn, only the iron is selectively oxidized by an oxidizing device and removed by a filter (step 7). Then, the obtained high-purity purified manganese solution is stocked in a stock tank.

Usually, a manganese solution containing iron filtered in step 6 is charged into a mixing tank, mixed with another metal solution (step 8), and the mixed solution is spray-roasted in a roasting furnace (step 8). 9). The composite ferrite powder generated by roasting is stocked in a product tank.

The exhaust gas from the roasting furnace is washed with water in a washing tower (Step 10), and HCl in the gas is recovered as an HCl solution. This HCl solution is supplied to a recovery acid container for dissolution.

Next, a specific embodiment will be described. (Example 1) 200 g of ferromanganese powder (hereinafter, referred to as FMn-P) having a particle size of 0 to 3 mm was supplied and dissolved in 1000 cc of hydrochloric acid adjusted to 18%. Table 1 shows the results of chemical analysis of FMn-P used at this time.

[0029]

[Table 1]

After dissolution, the pH of the solution was adjusted to 3.0, and the solution was filtered by decarburization. An AlCl ₃ solution having a concentration of 4.3% was added to 1000 cc of the filtered solution, and NH ₄ OH was added to adjust the pH.
Was adjusted to 4.0. Then, 25 pp of a nonionic flocculant was further added, and the flocculant was settled and separated, and then the solution was filtered. In this case, it took about one hour for the aggregate to settle.

After the furnace liquid was evaporated and dried at 100 ± 5 ° C., it was molded and analyzed for impurities by X-ray fluorescence. For comparison, a solution obtained by evaporating and drying the solution in a dissolved state was similarly analyzed. Table 2 shows the results of the analysis .

[0032]

[Table 2]

As shown in Table 2, by removing impurities according to the present invention, SiO ₂ became 45 ppm and 9 ppm
It was confirmed that 9.9% was removed . Also, problem occurring Ca as impurities, are P, etc. also effectively removed,
It was confirmed that a highly pure purified iron manganese solution was obtained. (Example 2) 13.6 kg of high-carbon ferromanganese pulverized to 60 mesh (0.25 mm) or less was collected with an acid (18% HCl) 6
It was fed via a feeder into 1.3 liters. Dissolution was carried out with a target of pH: 3 or less and a temperature: 80 ° C.
The liquid pump was set so that the liquid supply from the dissolving tank was started when the pH became 3.0 or more, and the pH was adjusted in the pH adjusting tank, followed by filtration and decarbonization. Further, a step of removing SiO ₂ and the like was performed in the same manner as in the example. Air is blown into the obtained liquid to selectively oxidize only Fe to convert Fe into Fe.
The precipitate was separated by precipitation as (OH) ₂ to obtain a purified manganese solution.

The solution was evaporated and dried, and analyzed by fluorescent X-ray. As a result, a reagent equivalent to a commercially available special-grade reagent was obtained .

[0035]

As described above, according to the present invention, there is provided a method for producing a purified manganese solution which can produce a high-purity purified manganese solution used as a raw material of a composite ferrite in a simple process at a low cost. Is done. In the present invention, since inexpensive starting materials are used, product costs can be reduced. Can be.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing an example of an apparatus for carrying out a method of the present invention.

FIG. 2 is a process chart for explaining a series of steps for producing a purified iron manganese solution or a purified manganese solution by the method of the present invention and producing a composite ferrite powder using the solution.

[Explanation of symbols]

1; dissolving tank, 2; recovered acid, 3; manganese source, 6; pH adjusting tank, 8, 15; pH meter, 9, 19;
1; reaction tank, 12; additive, 13; alkaline substance, 1
4; flocculant, 18; thickener.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Tomihiro Hara 2-11-11 Kandanishikicho, Chiyoda-ku, Tokyo Inside I-Rocks NK Co., Ltd. (72) Inventor Tomoo Maeda 1-2-1, Marunouchi, Chiyoda-ku, Tokyo (56) References JP-A-2-107529 (JP, A) JP-A-63-222017 (JP, A) JP-A-58-199721 (JP, A) JP-A-2-141431 ( JP, A) JP-A-1-153532 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C01G 45/00

Claims (1)

(57) [Claims] 1. A step of dissolving any of metal manganese, ferromanganese, and manganese ore in an acid, and obtaining a solution selected from Al, Cr, V, B, Zn, and an acid solution thereof. Adding and dissolving one or more of them, adjusting the pH of the solution to a range of 3.5 to 6 to generate a hydroxide of the added element,
Adding one or both of an anionic flocculant and a nonionic flocculant thereto to flocculate the hydroxide together with SiO ₂ and other impurities in the solution to separate the hydroxide. A method for producing a purified iron manganese solution.