JP3454451B2 - Method for producing ferrite using waste dry battery - 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 ferrite using a waste dry battery.

[0002]

2. Description of the Related Art Recently, electric appliances have become smaller and lighter,
As the number of portable batteries increases, the amount of dry batteries used increases. Most of the dry batteries used as primary batteries are manganese dry batteries and alkaline manganese batteries, and these are often discarded together with general waste after use. There are cases where these waste batteries are processed together with general waste by a local government or the like, or when they are collected as waste and then processed by a recovery company or the like.

Regarding the treatment of the waste dry battery after the recovery,
In recent years, there has been a demand for environmental protection, resource saving, waste volume reduction, and the like. Therefore, various methods such as a method of separating by type, a method of disassembling, and a method of separating and recovering valuable materials have been proposed.

Among these, in Japanese Examined Patent Publication No. 3-48624, waste dry batteries are separated to obtain a battery mainly composed of a manganese dry battery and an alkaline / manganese battery. After taking out only and crushing and mixing these battery bodies, roasting removes mercury etc., and at the same time, the slag obtained by roasting is separated into iron scrap and zinc slag to collect valuables. A method is disclosed. However, no specific use of iron scrap and zinc slag is presented.

On the other hand, Japanese Patent Laid-Open No. 7-85897 and Japanese Patent Laid-Open No. 7-81941 disclose a method of separating waste dry batteries to obtain manganese dry batteries, further sorting by grade, and collecting a mixture portion for each grade. Further, JP-A-7-
Japanese Patent No. 81941 discloses a method for producing ferrite using the recovered mixture portion. However, since it is a specific dry battery among the dry batteries and the specific portion thereof is used, it is insufficient from the viewpoint of effective resource utilization of the dry batteries.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a ferrite using a waste dry battery, which is capable of obtaining a practical level of ferrite from the waste dry battery and is preferable from the viewpoint of resource saving and environmental protection. It is to be.

[0007]

Such an object is achieved by the following constitutions (1) to (3). (1) Waste batteries are sorted according to their shape, and those that mainly consist of manganese batteries and alkaline / manganese batteries are selected, and these batteries are crushed and roasted to obtain slag, which is then magnetically separated by magnetic separation. To obtain a zinc slag, which is calcined to obtain almost the same amount of manganese oxide and zinc oxide in terms of weight, and a raw material mixture containing these oxides is fired to form ferrite. A method for producing ferrite using the obtained dry battery. (2) The method for producing ferrite using the waste dry battery according to (1) above, wherein the roasting is performed at a temperature of about 500 ° C to 700 ° C. (3) The method for producing ferrite using the waste dry battery according to (1) or (2), wherein the calcination is performed at a temperature of about 700 ° C to 950 ° C.

[0008]

In the present invention, the waste dry batteries are sorted according to their shapes, and the ones mainly composed of the manganese dry batteries and the alkaline / manganese batteries are obtained, crushed and roasted. By this roasting, combustible components are burned and NH ₄ Cl, Hg, ZnCl ₂ and a part of C are volatilized.

On the other hand, the slag obtained by roasting is cooled and then separated into iron and zinc slag by magnetic separation. This zinc slag mainly contains manganese and zinc. Next, this zinc slag is calcined. By this calcination, manganese and zinc are converted into manganese oxide and zinc oxide in a form suitable for ferrite raw materials. These mixtures contain almost the same amount of manganese oxide and zinc oxide in terms of weight, and are particularly suitable as raw materials for obtaining general-purpose ferrite. Also, due to this calcination, NH ₄ C, which remains even after the previous roasting,
1, ZnCl ₂ , C, etc. are removed.

Therefore, by performing the heat treatment steps of roasting and calcination twice, the substance unfavorable for the production of ferrite is completely removed. Although some of the constituent members of the dry battery are undesirable such as corrosion in the ferrite manufacturing process, this problem can be solved. Further, a substance that can be an impurity of ferrite can be removed and the recovery rate of zinc oxide can be improved.

If the roasting step is omitted and only the calcination step is used for the heat treatment, the amount of residual C is particularly large, so that the calcination takes a long time or it is necessary to select complicated conditions. By performing the heat treatment, the calcination time can be shortened and the conditions such as the atmosphere can be easily selected.

In the present invention, by using the raw material mixed powder containing these oxides, it is possible to obtain a general-purpose ferrite used for a deflection yoke core, a copying machine carrier and the like.

[0013]

[Specific Configuration] The specific configuration of the present invention will be described in detail below.

In the present invention, a manganese dry battery and an alkaline
Using a waste dry battery mainly composed of a manganese battery, MnO-Z
A general-purpose nO-MgO ferrite is obtained.

Such a MnO-ZnO-MgO-based general-purpose ferrite has a manganese oxide / zinc oxide molar ratio of usually about 0.01 to 0.5, for example 6/18, in terms of MnO and ZnO. Therefore, a general-purpose ferrite can be easily obtained by a dry method by directly using a zinc slag obtained from a manganese dry battery and an alkaline manganese battery.

Next, the method for producing the ferrite of the present invention will be described with reference to FIG.

(1) Sorting step This is a step of sorting a cylindrical dry battery from a variety of waste dry batteries with a shape sorter. As a result, a battery mainly composed of a manganese dry battery and an alkaline / manganese battery is obtained, and a nickel-cadmium battery, a lithium battery, a button battery having a different shape is removed. However, it is also possible that a battery of such a different shape is mixed in to some extent.

(2) Crushing process The manganese dry battery and the alkaline manganese battery mainly obtained in the above shape selecting process are crushed and disentangled by using a crushing mixer and wrapped in an iron crust. This is a step of separating and crushing a contained substance such as a mixture which is a positive electrode active substance in the cylindrical body from the outer cover and the cylinder. In this case, the crushing and the loosening may be carried out after the outer skin is previously removed by a disassembling machine or the like (see Japanese Patent Publication No. 3-48624). However, since the number of steps can be reduced, it is preferable to carry out this step without removing the outer skin for the purpose of the present invention.

(3) Roasting step In this step, the crushed material is put into a roasting furnace and roasted to obtain a slag. At the same time, this roasting produces NH ₄ C.
1, Hg, ZnCl ₂ and a part of C are volatilized and removed,
Paper, plastic, water, etc. are also burned out. Among these, the above volatile components are condensed and recovered. As such a system, specifically, a system having a combination of roasting equipment, condensation / exhaust gas treatment equipment, and wastewater treatment equipment described in Japanese Patent Publication No. 3-48624 can be used.

The roasting temperature in the roasting furnace is 500 to 700.
It is preferable to set the temperature to about 0 ° C., and for example, it may be heated by the combustion heat of the fuel by the burner. The roasting time may be, for example, about 0.5 to 1.5 hours after reaching the above temperature, with the amount of the waste dry battery being about 1 t. The atmosphere in the roasting furnace may be air or the like.

The slag obtained by roasting is discharged from the roasting furnace and cooled during transfer to reach room temperature (about 15 ° C to 35 ° C). The slag contains iron products and constituent substances such as zinc and manganese attached to the iron products.

(4) Crushing step This is a step of separating iron products and zinc, manganese, etc. adhering to the iron products from the slag obtained in the roasting step by a crusher. A crusher such as a cage mill type may be used.

(5) Magnetic Separation Step This is a step of collecting the iron scraps separated in the above crushing step by a magnetic separator such as a drum magnetic separator or a magnet magnetic separator. This iron scrap can be recovered as metallic iron by refining.

(6) Sieving step This is a step of sieving the slag after removing iron. As a result, oversized products and carbon rods can be removed, and zinc slag that is a slag after removing these can be obtained. The main components are zinc oxide and manganese oxide, and both oxides are contained in almost the same amount in terms of oxide, and the weight ratio of manganese / zinc is 0.5 to 1.5 in terms of oxide. It is a degree. The content of these oxides in the zinc slag is about 25 wt% to 45 wt% for both oxides. Here, the mesh size of the sieve used for sieving is about 3 to 5 mm.

(7) Calcining Step This is a step of calcining the zinc slag obtained in the above step to convert it into manganese oxide and zinc oxide in a form suitable for a ferrite raw material. At the same time, NH ₄ Cl, ZnCl ₂ , C, etc. still remaining in the previous roasting are removed. Calcination is performed using a calcination furnace, and the normal furnace temperature is 700
It is preferable to set the temperature to about 950 ° C, and the calcination time (70
The holding time at a temperature of about 0 to 950 ° C.) may be about 1 to 5 hours. The atmosphere in the furnace is not particularly limited, but C
It is preferable to use an oxidizing atmosphere in order to completely remove MnO and ZnO and to convert into MnO and ZnO. The oxidizing atmosphere is an atmosphere in which a higher oxide of manganese is produced.

(8) Sieving Step This is a step of pulverizing the calcinated product obtained by calcination and sieving to obtain a predetermined particle size. For crushing, use a bantam mill etc.
The sieving may be performed using, for example, a sieve having an opening of about 200 mesh.

This pulverized product is a mixture of manganese oxide and zinc oxide, and these oxides are contained in substantially the same amount in terms of weight. Weight of manganese oxide / zinc oxide The ratio is about 0.8 to 1.4. The composition is, for example, MnO: 35-45 wt%, ZnO: 35
_{~45wt%, Fe 2 O 3:} 4~6wt%, C: 0.05~
0.15 wt%, Cl: 0.1-1 wt%, C, Cl
In addition to impurities such as SiO ₂ , CaO, MgO, P,
Impurities such as Na ₂ O and K ₂ O are 0.001 to 0.5, respectively.
Although it is included at a level of about wt%, it is a level that does not pose any problem for the purpose of use of the present invention. In addition, iron remains even after magnetic separation and exists in the form of Fe ₂ O ₃ after the calcination process, but in the present invention, it is a part of the ferrite raw material as it is, so it belongs to a valuable resource. Is preferable.

Using such a mixture as E material (FIG. 1) which is a regenerated raw material obtained from a waste dry battery, a general-purpose ferrite is manufactured.

In the production of ferrite, as shown in FIG. 1, in addition to the E material, raw materials A, B, C, D, etc. are mixed according to the intended ferrite composition to adjust the components.
These raw materials A, B, C, D, etc. are precursors of commercially available metal oxides or metal hydroxides that become metal oxides by calcination, for example, Fe ₂ O ₃ , MnO, ZnO, Mg.
(OH) ₂ and the like.

Ferrite is produced from such a ferrite raw material by a usual method, preferably a dry method as shown in FIG.

The ferrite raw material may be mixed by a wet mixer or a dry mixer, and a solvent such as water may be appropriately added. After this mixing, it is dried using a spray dryer and then calcined. The calcination is, for example, 1 to 4 at a temperature of 700 to 1100 ° C. in an air atmosphere.
Do about an hour.

The pre-baked product is pulverized to a predetermined particle size (average particle size 1.0 to 3.0 μm). The crushing is performed by using a coarse crusher and a fine crusher. Then, it is dried with a spray dryer or the like, granulated, and molded.

The molded body having a predetermined shape is then fired or sintered. Sintering may be performed using an electric furnace or the like, and the conditions such as sintering atmosphere, temperature, and time may be normal ones.

For the purpose of improving the magnetic properties of ferrite, a trace amount of additives may be added in addition to the impurities present in the oxide.

Generally, the sintering atmosphere may be air or a mixed atmosphere of air and nitrogen, and the sintering temperature is 1150 to 1.50.
The temperature is 1400 ° C. and the sintering time is about 1 to 5 hours.

In this way, MnO-ZnO-MgO
Ferrite products of series ferrite are obtained.

Such a ferrite is suitably used as a general-purpose ferrite in a core for a deflection yoke, a carrier for a copying machine, and the like.

[0038]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 1000 kg of a manganese dry battery and an alkaline manganese battery were mainly obtained by shape selection. The cylindrical waste dry battery obtained as described above was passed through a crushing mixer, and then placed in a roasting furnace and roasted at 600 ° C. for 1 hour in an air atmosphere. NH ₄ Cl, ZnCl ₂ , H by roasting
A part of g and C was condensed and recovered, and paper, plastic, moisture and the like were removed.

After the slag obtained by such roasting is returned to room temperature, a cage mill type crusher is used to separate iron products and zinc, manganese, etc. adhering to them, and iron scraps are recovered by a magnetic separator. did. After removing iron, the slag was screened to remove oversized products and carbon rods. The sieve used had a mesh size of 4 mm. The slag obtained in this way is called zinc slag, and the main components are zinc oxide and manganese oxide. 530 kg of the zinc slag was obtained. The zinc oxide content in this zinc slag was 37 wt% and the manganese oxide content was 30 wt%.

After that, calcination was performed in an oxidizing atmosphere at a temperature of 800 ° C. for 4 hours using a calcination furnace. This calcined product is crushed with a bantam mill and sieved with a 200 mesh,
0 kg of calcinated and ground product was obtained. When the composition of this pulverized product was examined, MnO: 39.6 wt%, ZnO: 42.0 wt%,
_{Fe 2 O 3: 5.2wt%,} C: 0.12wt%, Cl:
It was 0.4 wt%. Although Fe ₂ O ₃ is contained in an amount of about 5 wt%, it is useful for making ferrite and does not become an obstacle.

Using 6 kg of the above calcined product, Fe ₂ O
_{3: 35kg, Mg (OH)} 2: 9kg, ZnO: was 4kg by adding as a predetermined ferrite composition. In addition,
The average particle size of the raw material powder is about 3 μm. This was mixed by a wet mixer, and the mixed powder was granulated by a pan granulator, and then calcined at 950 ° C. for 2 hours. The obtained calcined powder was pulverized by a coarse pulverizer and a fine pulverizer to an average particle size of about 1 μm, granulated by a spray dryer and then molded into an annular sample by an automatic powder molding machine to obtain a molded body. . The compact was sintered. Sintering was performed in air at 1350 ° C. for 3 hours. In this way, a magnetic core of an annular sample composed of Mn-Zn-Mg system ferrite was obtained. Outer diameter: 3
1 mm, inner diameter: 19 mm, thickness: 7 mm. In this case, the shrinkage ratio during sintering was 16%.

The composition of the ferrite core thus obtained is as follows: Fe ₂ O ₃ : 46 mol%, MnO: 6 mol%,
It was ZnO: 18 mol% and MgO: 30 mol%.

The magnetic characteristics of the obtained ferrite magnetic core were measured. As a result, the saturation magnetic flux density was 255 mT, the initial magnetic permeability was 378, and the core loss was 153 kW / m ³ , which was in a practical level as a magnetic core for a deflection yoke or the like. confirmed.
The mixing was performed by the dry method from the wet method described above, but the same effect was obtained by the dry method.

On the other hand, the iron scraps separated by magnetic separation and the like were recovered as metallic iron.

When the roasting step was omitted in the above-mentioned ferrite manufacturing process, the amount of impurities in the zinc slag was large and the performance was inferior when used as a magnetic core, as compared with the above. Moreover, when only the roasting step was performed and the calcination was not performed, an oxide suitable for the ferrite raw material could not be obtained.

[0047]

According to the present invention, it is possible to obtain a practical level of ferrite from a waste dry battery.

[Brief description of drawings]

FIG. 1 is a process diagram showing a process for producing ferrite from a waste dry battery.

─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Hiroshi Sato 1-7-2 Otemachi, Chiyoda-ku, Tokyo Nomura Kosan Co., Ltd. (72) Inventor Shigeaki Suda 1-13-1 Nihonbashi, Chuo-ku, Tokyo TDK Corporation (72) Inventor Takeo Kitagawa 1-31-1 Nihonbashi, Chuo-ku, Tokyo TDK Corporation (56) Reference JP-A-6-260174 (JP, A) JP-A-7-81941 (JP, A) JP 7-85897 (JP, A) JP 6-260175 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) H01M 6/52 B09B 5 / 00 ZAB

Claims (3)

(57) [Claims] 1. A waste dry battery is sorted according to its shape, a manganese dry battery and an alkaline / manganese battery are mainly selected, and these dry batteries are crushed and roasted to obtain a slag, which is magnetically separated. To separate zinc from iron to obtain a zinc slag, which is calcined to obtain almost the same amount of manganese oxide and zinc oxide in terms of weight, and the raw material mixture using these oxides is fired. A method for producing ferrite using a waste dry battery for obtaining ferrite. 2. The method for producing ferrite using a waste dry battery according to claim 1, wherein the roasting is performed at a temperature of about 500 ° C. to 700 ° C. 3. The method for producing ferrite using a waste dry battery according to claim 1, wherein the calcination is performed at a temperature of about 700 ° C. to 950 ° C.