JP2806984B2 - Production method of raw material oxide for ferrite - Google Patents

Description

The present invention relates to a method for producing a raw material oxide for ferrite. More specifically, through the chlorides of iron and manganese,
The present invention relates to an improvement technique in a method for producing a raw material mixed oxide for soft ferrite having few impurities.

[Conventional technology]

The industrial production method of ferrite is that after mixing each powder such as iron, manganese, zinc and other oxides or carbonates of the metal constituting ferrite at a predetermined molar ratio, calcinate, pulverize, and mold this. In general, firing is performed.

At this time, as the iron oxide raw material which accounts for the largest proportion of the soft ferrite composition, in most cases, iron oxide obtained by oxidizing and roasting a hydrochloric acid pickling waste liquid of a steel sheet is used. Manganese, which is a main constituent element of soft ferrite, is a fine powder obtained by grinding oxides, carbonates, and hydroxides. For zinc, oxide powder is used.

In the case of a normal ferrite production method using the above oxides or carbonates of the metals constituting the ferrite as a raw material, a wet mixing method using an apparatus such as an attritor or a ball mill in order to improve the uniformity of the composition. Alternatively, the composition of the raw materials is made uniform by the dry mixing method,
Further improve the uniformity in the pulverization process.

From the viewpoint of improving the uniformity of the composition, it is desirable to lengthen the mixing time and the pulverizing time. On the other hand, if the mixing time and the pulverizing time are long, the incorporation of unavoidable impurities during these steps increases, causing a problem. The magnetic properties of the final ferrite are
It is closely related to the macroscopic and microscopic uniformity of the composition,
From this point, the conventional method has limitations.

There have been many attempts to produce ferrite raw materials in place of the above-mentioned raw materials. One of them has been proposed using a chloride mixed solution of a metal constituting ferrite as a starting material (Japanese Patent Publication No. 47-11550 and Japanese Patent Publication No. 63-17776).

In the case of using a mixture of iron and manganese chloride as a raw material, for example, manganese chloride may be mixed in a steelmaking pickling waste solution or a solution containing iron chloride obtained by dissolving electrolytic iron or the like in hydrochloric acid, or electrolytically. A solution in which manganese or an iron-manganese alloy is dissolved in hydrochloric acid is mixed with the solution containing iron chloride, and the mixture is oxidized and roasted to obtain a raw material oxide for ferrite. The iron and manganese oxides generated by oxidizing roasting are uniformly mixed on a microscopic scale, and the uniformity of the composition is greatly improved in the ferrite manufacturing process, and the calcination process can be omitted. it can.

In obtaining a chloride mixed solution of the raw material, a large amount of steel plate pickling waste liquid can be industrially used as a source of iron chloride, but as a manganese chloride source, there is no similar resource,
For example, in the embodiment of JP-B-47-11550, a solution in which electrolytic manganese is dissolved in hydrochloric acid is used.
No. 6 describes the use of manganese chloride dissolved in water or metallic manganese dissolved in hydrochloric acid.

However, the use of manganese chloride is expensive and not economical. When metal manganese or a manganese iron alloy is used, the obtained form is usually a lump, and the dissolution efficiency in hydrochloric acid is very poor. Although it is possible to improve the dissolution efficiency by pulverization by pulverization, the pulverization is limited, and there are problems of impurity contamination and cost increase in the pulverization process.

On the other hand, in the steelmaking process of the steel industry, manganese iron alloys (ferromanganese), which are indispensable as deoxidizers, desulfurizers, and additives, convert oxygen or oxygen-containing gas into the molten metal of ferromanganese in the refining process of low carbonization. There are ways to spray or blow. At this time, manganese evaporates and comes into contact with oxygen because its vapor pressure is much higher than iron, and Mn ₃ O ₄
The main component is an oxide of fine particles having an average particle size of about 2 μm or less.

These fine oxides are collected by a bag filter or the like,
It was used as a raw material for glazes or recycled as a raw material for the production of manganese iron alloys. An example of the material of the manganese oxide fine particles generated in this way is as follows: the composition is Mn: 71.1% Fe: 1.5% SiO ₂ : 0.2% CaO: 0.01% and residual oxygen, and the average particle size is 1.89 μm is there. Although it is conceivable to use these directly as ferrite raw materials, SiO ₂ ,
Since the CaO content is high and its reduction is difficult, its application range is very narrow and limited.

[Problems to be solved by the invention]

In the method of oxidizing and roasting a chloride mixed solution of iron and manganese to obtain a raw material oxide for soft ferrite, conventionally,
Manganese chloride, metallic manganese, and manganese iron alloys were used as the Mn source, but there were problems such as the extremely high cost and the extremely long melting time required for the production of chlorides resulting in poor efficiency. Was.

As a result of searching for various substances and conducting experiments, the present inventors have found that, by using manganese oxide fine particles generated during refining of a manganese iron alloy using oxygen, (a) a manganese chloride solution can be easily produced. that can be, but is difficult to remove the SiO ₂ from (b) manganese oxide, the manganese chloride to remove the SiO ₂ easily by applying the de-SiO ₂ method conventional pickling waste The present inventors have found that a raw material oxide for soft ferrite having high purity can be easily and economically produced, and completed the present invention.

The present invention utilizes the above-mentioned manganese oxide microparticles, (a) eliminates the need for grinding power, and (ii) simplifies and facilitates the process using microparticles which are very easily melted in hydrochloric acid. An object of the present invention is to establish a technique for easily removing SiO _{2 and the} like, which is a problem in this case, and to provide a method for obtaining an inexpensive raw material oxide for ferrite.

[Means for solving the problem]

As a result of repeated experiments on the production of manganese chloride solution, which was a problem of the conventional method, from the viewpoint of simplification of the treatment process and improvement of economic efficiency, oxygen or oxygen was added to molten metal manganese or manganese iron alloy. Generating manganese oxide microparticles by blowing or blowing a gas containing: a step of dissolving the manganese oxide microparticles in hydrochloric acid to easily obtain a chloride solution; purifying the manganese chloride to form SiO ₂ The step of removing, the step of producing a mixed solution of manganese chloride and iron chloride, and the step of oxidizing and roasting the mixed solution are economical to produce a raw material mixed oxide for ferrite with excellent composition uniformity. It can be easily manufactured.

The step of purifying manganese chloride to remove SiO ₂ may be performed after mixing manganese chloride with iron chloride.

[Action]

The present invention utilizes the fact Mn of high vapor pressure, grinding process to produce a more soluble fine manganese oxide for fines in hydrochloric acid without a while, SiO ₂ is problematic in this case
As for the removal of manganese, it was found that the removal of SiO ₂ was easy if it was made of manganese chloride, thereby producing a raw mixed oxide for soft ferrite having few impurities.

The present inventors have repeated many experiments on a method of adjusting a mixed solution of iron and manganese chloride as a raw material for producing a raw material oxide for ferrite by oxidative roasting using the above manganese oxide fine particles. As described below, it was found that a great effect was obtained as compared with the conventional method.

(1) Manganese oxide fine particles obtained by the step of blowing or blowing oxygen or a gas containing oxygen onto molten metal manganese or manganese iron alloy to form manganese oxide fine particles have an average particle size of about 2 μm or less. Despite being an oxide, its reactivity with hydrochloric acid is very high, and the dissolution time is about 1 time compared to powder grinding of metal manganese or manganese iron alloy (-3 mm mesh powder).
Can be reduced to / 10 to 1/30.

(2) It is very difficult to reduce SiO ₂ and CaO in the state of manganese oxide, but this is dissolved in hydrochloric acid,
When a chloride solution is used, it is oxidized and roasted by a method conventionally known as a method for reducing SiO _{2 in an} iron chloride solution, for example, by adding a flocculant and using a filter using diatomaceous earth (Japanese Patent Laid-Open No. 58-151335). Can reduce the SiO ₂ in the oxide obtained to a sufficiently low level suitable as a raw material for ferrite. CaO can also be reduced by a purification method such as washing the generated oxide with water.

〔Example〕

Example-1 Manganese oxide fine particles containing Mn ₃ O ₄ as a main component generated by blowing oxygen into a molten manganese iron alloy at the time of refining a manganese iron alloy have the following composition: Mn: 71.1% by weight, SiO ₂ : 0.2 % By weight, CaO: 0.01% by weight, average particle size 1.89 μm. This manganese oxide fine particle is 35%
It was dissolved in hydrochloric acid at 70 ° C. with stirring. Hydrogen gas generated during the dissolution was continuously sucked and exhausted. 80 pure manganese
The time required to completely dissolve 0 kg of the manganese oxide fine particles was 3 hours.

After adding a surfactant to the manganese chloride solution thus produced, the solution was allowed to stand for 20 hours to promote aggregation of SiO ₂ , followed by filtration and separation. The contents of SiO ₂ and CaO in the solution after this treatment were 69 ppm and 87 ppm, respectively, in terms of the amount of Mn ₂ O ₃ after roasting.

Next, a concentrated solution of the purified acid pickling waste liquid was mixed at a predetermined ratio, a cationic coagulant was added thereto, and the mixture was allowed to stand for about 1 hour and filtered. Next, this solution was spray-roasted using an oxidation roasting furnace to produce a raw material oxide for ferrite, and further washed with pure water.

The composition of the obtained oxide was α: Fe ₂ O ₃ : 75.1% by weight Mn ₂ O ₃ : 24.9% by weight SiO ₂ : 58ppm CaO: 38ppm.

After adding 7.8% by weight of zinc white to the obtained mixed oxide of iron and manganese, mixing, granulation, toroidal core press molding, and firing at 1350 ° C. The magnetic properties of the obtained ferrite
100kHz, 200mT, 80 ℃ of iron loss is 352mW / cm ^3, the initial permeability μ
_iac = 4450.

On the other hand, for comparison, 800 kg of pure manganese equivalent of high carbon manganese iron alloy powder (Mn content: 74.6% by weight) ground to −3 mm mesh was completely dissolved under the same conditions. This operation is 4
Needed 5 hours.

As a comparative material, a sintering core was prepared by processing under the same conditions as the above-described example of the present invention using this manganese chloride solution.
The frequency of abnormal growth of crystal grains was high, and the core loss was 824 mW / cm ³ and μ _iac = 3560 with the best magnetic properties.

Example 2 A manganese chloride solution produced in the same manner as in Example 1 was mixed with a concentrated solution of a purified steel plate pickling waste liquid, a cationic coagulant was added, and the mixture was allowed to stand for about 1 hour, and then filtered. hand
SiO ₂ was removed. Next, this solution was spray-roasted using an oxidation roasting furnace to produce a raw material oxide for ferrite.

The obtained oxide is in a state where α · Fe ₂ O ₃ and Mn ₂ O ₃ are microscopically and uniformly mixed, and the composition is αFe ₂ O ₃ : 75.3% by weight, Mn ₂ O ₃ : 24.7% by weight , SiO ₂ : 75 ppm and CaO: 93 ppm. These were washed with pure water to obtain 73 ppm of SiO _{2 and} 46 ppm of CaO.

Zinc white (ZnO) in the obtained mixed oxide of iron and manganese
Was added, followed by mixing, granulation, toroidal core press molding, and firing at 1350 ° C.

The magnetic properties of the obtained ferrite are 100KHz, 200mT, 8
The iron loss at 0 ° C. was 384 mW / cm ³ , and the initial magnetic permeability μ _iac was 4620.

In the second embodiment, the manganese chloride purification step of the first embodiment is performed after mixing with the iron chloride, and almost the same purification result can be obtained. Therefore, one step can be omitted.

〔The invention's effect〕

According to the present invention, (a) oxygen or a gas containing oxygen is blown into a molten metal manganese or manganese iron alloy to generate fine manganese oxide, so that a fine pulverizing step is not required and the raw material cost is low.

(B) Dissolution of manganese is extremely short and easy.

(C) the SiO ₂ from such manganese chloride can be easily removed.

(D) Further, SiO ₂ present in the raw material can be easily removed also by purification in the coexistence of iron chloride and manganese chloride. Therefore, the process is further simplified, the cost can be reduced by using an inexpensive raw material, and an excellent ferrite production raw material can be obtained.

It has excellent effects such as.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Fumiaki Yoshikawa 1-chome, Mizushima Kawasaki-dori, Kurashiki-shi, Okayama Pref. (Without address) Inside the Mizushima Works, Kawasaki Steel Corporation (72) Inventor Masao Tsuzaki 1, Mizushima-Kawasaki-dori 1 Chome (without address) Kawasaki Steel Corporation Mizushima Works (72) Inventor Kenshi Takagi 1-chome, Mizushima Kawasaki-dori Kurashiki-shi, Okayama Prefecture (without address house) Kawasaki Steel Corporation Mizushima Works (72) Inventor Hideyoshi Yoshimatsu 1 Kawasaki-cho, Chiba-shi, Chiba Kawasaki Steel Corporation Research and Development Headquarters (72) Inventor Yoshitaka Fujiwara 1-1 1-1 Mizushima Kawasaki-dori, Kurashiki-shi, Okayama Mizushima Alloy Iron Co., Ltd. (72) Inventor Kenichi Kaneko Okayama 1-1, Mizushima-Kawasaki-dori, Kurashiki-shi, Mizushima Alloy Iron Co., Ltd. 4 (JP, A)

Claims (2)

(57) [Claims] An oxygen or oxygen-containing gas is blown into molten metal manganese or manganese iron alloy to generate manganese oxide fine particles, and the manganese oxide fine particles are dissolved in hydrochloric acid to form a manganese chloride. To purify
A method for producing a raw material oxide for ferrite, comprising removing SiO ₂ , mixing the purified manganese chloride with iron chloride to form a chloride mixed solution, and oxidizing and roasting the mixed solution. 2. The ferrite raw material oxide according to claim 1, wherein said manganese chloride is purified before mixing with iron chloride, but is purified after mixing with iron chloride. Production method.