JP5444821B2 - Method for recovering manganese oxide from dry cells - Google Patents

Description

  The present invention relates to a method for recovering manganese oxide from a dry battery.

Since a dry battery, which is a primary battery, cannot be used repeatedly unlike a secondary battery, it has conventionally been proposed to collect a discarded dry battery (waste dry battery) and collect a reusable metal material.
In Patent Document 1 below, waste dry batteries are crushed with a uniaxial shear type crusher, the crushed material is sieved and the material on the sieve is magnetically sorted, and the iron component-containing particles, zinc component and copper component are contained. It is described that it is classified into particle pieces. The under-sieving material is classified as it is into pieces containing zinc and copper components. And the obtained iron component containing particle piece is made into an iron source raw material, and the zinc component and copper component containing particle piece are made into the zinc and copper source material for non-ferrous refining processes. In this method, manganese dioxide is made into a sieve top by a sieving process together with an outer iron can, a zinc can, a current collecting rod, and a mixture, but there is no description about recovering manganese dioxide alone.

Patent Document 2 below describes a method for separating and recovering manganese dioxide (MnO ₂ ) and zinc chloride (ZnCl ₂ ) from waste dry batteries. In this method, first, a manganese dry battery is crushed and then subjected to a sieving treatment. An undersized product (undersieving material) is dissolved in hydrochloric acid, and after removing impurities from the solution, the solution is concentrated by heating. Next, by adding perchloric acid to this concentrate and heating, a solid mixture of manganese dioxide and zinc chloride is obtained, and water is added to the obtained solid mixture to dissolve zinc chloride, followed by filtration to obtain a solid mixture. Of manganese dioxide and water-soluble zinc chloride.

JP 2004-871 A Japanese Patent Laid-Open No. 11-191439

As described above, Patent Document 1 does not have a description of recovering manganese dioxide alone from a dry battery, and the method of Patent Document 2 separates and recovers manganese dioxide and zinc chloride by a method involving a chemical reaction. There is a problem that solvent cost and waste water cost are large.
An object of the present invention is to recover a manganese oxide such as manganese dioxide (MnO ₂ ) from a dry battery by a low cost method.

In order to solve the above-mentioned problems, the present invention provides a crushing / sieving treatment step for obtaining a crushed material containing manganese oxide particles and zinc oxide particles as a sieving material by performing a sieving treatment after crushing the dry battery. And the sieving material after the crushing / sieving treatment step is put in a liquid, and an aggregate of particles containing manganese oxide particles and zinc oxide particles present in the liquid is separated into each particle, A dispersion treatment step of dispersing the particles in the liquid, and the liquid in a state in which aggregation of the manganese oxide particles and the zinc oxide particles after the dispersion treatment step is prevented ; There is provided a method for recovering manganese oxide from a dry battery, comprising a weight difference separation treatment step for separating zinc oxide particles.

In the method of the present invention, it is preferable to perform the weight difference separation treatment step after performing the low magnetic force separation treatment step of separating iron particles with a low magnetic force from the liquid after the dispersion treatment step. Low magnetic force means a magnetic force of 3000 gauss or less.
The dispersion treatment step is preferably performed by applying ultrasonic vibration to the liquid. The dispersion treatment step can be performed by adding a dispersant to the liquid. However, it is not time-consuming to apply the ultrasonic vibration because it is not necessary to handle the medicine.

  Manganese oxide (MnO) obtained by modifying the manganese oxide particles recovered by the method of the present invention can be used as a steelmaking auxiliary material in the blast furnace ironmaking method.

  Since the method for recovering manganese oxide from the dry battery of the present invention is a technique that does not involve a chemical reaction, the cost can be kept low.

It is process drawing which shows the manganese oxide collection | recovery method from a dry cell corresponding to one Embodiment of this invention. It is a figure which shows the result of having surface-analyzed the sieving thing by EPMA. It is the schematic which shows the apparatus structure which can implement the method of embodiment.

Embodiments of the present invention will be described below.
FIG. 1 is a process diagram showing a method for recovering manganese oxide from a dry battery, corresponding to one embodiment of the present invention.
[Crushing / sieving process]
First, it is confirmed whether or not a secondary battery is contained in the collected used dry battery. If it is contained, a crushing process is performed on the remaining used dry battery from which the secondary battery has been taken out. In this crushing process, a dry cell is primarily crushed using a uniaxial shear type crusher. Next, the crushed material of the dry battery generated by the primary crushing is sieved. This sieving process is performed using, for example, a sieve having a sieve mesh of 5 mm or less. The sieve top is separated into iron pieces and residues by magnetic separation. Most of the sieving materials are particles of 1 mm or less.

  FIG. 2 is a diagram showing the results of surface analysis of this under-sieving material by EPMA (which elements are distributed in which locations). From FIG. 2, it is estimated that the manganese (Mn) element and the zinc (Zn) element exist separately and are not chemically bonded. In addition, it can be seen that the manganese oxide particles are larger in size than the zinc oxide particles because the manganese (Mn) element distribution and the zinc (Zn) element distribution are different in size.

The specific gravity of MnO ₂ is 5.0 g / cm ³ , the specific gravity of MnO is 5.2 g / cm ³ , the specific gravity of Mn ₂ O ₃ is 4.8 g / cm ³ , and the specific gravity of ZnO is 5.6 g / cm ³ , The specific gravity of manganese oxide (MnO ₂ , MnO, Mn ₂ O ₃ etc.) and zinc oxide (ZnO) is almost the same. And since a manganese oxide particle is larger than a zinc oxide particle, it turns out that a manganese oxide particle is heavier than a zinc oxide particle. Moreover, it turns out that the zinc oxide particle has aggregated around the manganese oxide particle.
The sieving material is further crushed (secondary crushing). By this pulverization treatment, for example, most of the particles are 100 μm or less.

[Distributed processing step]
The pulverized particles are put in water (liquid), and ultrasonic vibration is applied to the water. When the pulverized particles are put into water, aggregates of particles containing manganese oxide particles and zinc oxide particles are present in the water, and the aggregates are separated into individual particles by ultrasonic vibration. Becomes dispersed in water.

[Low magnetic force sorting process]
Next, a magnet of about 1000 gauss (low magnetic force) is put in the water in which each particle is dispersed, and iron (Fe) as a ferromagnetic material is taken out. Thus, manganese oxide (MnO ₂ or the like) particles that are weak magnetic substances and zinc oxide (ZnO) particles that are nonmagnetic substances exist in the water.

[Weight difference separation process]
Next, this water is applied to, for example, a cyclone sorter to separate manganese oxide (MnO ₂ or the like) particles that are heavy and zinc oxide (ZnO) particles that are lightweight, due to the difference in weight.

[Modification process]
The manganese oxide particles separated and taken out are subjected to a modification treatment to make manganese oxide (MnO), which is used as a steelmaking auxiliary material. Zinc oxide (ZnO) particles are also collected and provided to zinc refining manufacturers.

The crushing (secondary crushing) processing step and the low magnetic force sorting processing step may be omitted. If the low magnetic separation process is omitted, heavy iron (Fe) is separated from the manganese oxide together with the manganese oxide in the weight difference separation process and separated from the manganese oxide before the reforming process. To do.
In the method of this embodiment, manganese oxide (MnO ₂ or the like) can be recovered from the dry battery by a technique that does not involve a chemical reaction, so that the cost can be kept low.

For example, as shown in FIG. 3, the method of this embodiment is performed by an apparatus configured using a rotating magnet 11, water tanks 21 and 22, an ultrasonic transducer 3, a scraper 4, and a cyclone sorter 7. be able to.
The ultrasonic vibrator 3 is installed in the front part 21A of the upstream water tank 21, and the rotating magnet 11 and the scraper 4 are installed in the rear part 21B. The portion of the water tank 22 that is the water surface position is connected to the bottom portion of the rear portion 21 </ b> B of the water tank 21 by the pipe 5. Ultrasonic vibration by the ultrasonic vibrator 3 is applied to the water in the front portion 21A of the water tank 21 and the water in the water tank 22. The rotating magnet 11 is a magnet of about 1000 gauss (low magnetic force).

  An ultrasonic transducer 3 and a pump 8 are installed in the downstream water tank 22. A pipe 81 from the pump 8 is connected to the cyclone sorter 7. A container 71 for receiving heavy objects is installed below the cyclone sorter 7. A pipe 72 is connected to the upper part of the cyclone sorter 7, and a container 73 for collecting the overflow through the pipe 72 is installed. In addition, you may provide the piping 78 which returns the contents of the container 71 which receives a heavy article to the water tank 22. FIG.

  By putting the sieving material 6 after the pulverization treatment into the front part 21A of the water tank 21, an aggregate of particles including manganese oxide particles and zinc oxide particles is present in water. This aggregate is separated into each particle by ultrasonic vibration, and each particle is dispersed in water. The contents of the front part 21A move to the rear part 21B, and the ferromagnetic material (iron) in water adheres to the rotating magnet 11 in the rear part 21B. The adhered ferromagnetic material (iron) is recovered by the scraper 4.

  The contents of the rear stage portion 21 </ b> B move to the water tank 22 through the pipe 5. Thereby, dispersed water of manganese oxide particles and zinc oxide particles is introduced into the water tank 22. In the water tank 22, the state where the manganese oxide particles and the zinc oxide particles present in the water are prevented from aggregating by ultrasonic vibration, and the dispersed water of the manganese oxide particles and the zinc oxide particles is supplied by the pump 8. Pumped up and introduced into the cyclone sorter 7 from the pipe 81.

The cyclone sorter 7 separates the manganese oxide particles and the zinc oxide particles due to the difference in weight. The heavy manganese oxide particles enter the container 71, and the lightweight zinc oxide particles enter the container 73. enter. In the case where the pipe 78 is provided, the contents of the container 71 are returned to the water tank 22 and circulated, so that the collection purity of heavy objects is improved.
In the method of this embodiment, the dispersion treatment step is performed by applying ultrasonic vibration to the liquid in the water tank. Alternatively, it may be performed by introducing a dispersant into the liquid in the water tank. . Moreover, you may carry out combining injection | pouring of a dispersing agent with provision of an ultrasonic vibration. In addition, a liquid containing an aggregate of particles containing manganese oxide particles and zinc oxide particles is dispersed in a shear peeling device (the slurry is extruded by a pump and dispersed by an shearing force generated when passing through an orthogonal narrow tube. And an impact crushing device (a device that crushes and disperses the aggregates by pressurizing the slurry with a pump and causing the slurry to collide with the chamber).

DESCRIPTION OF SYMBOLS 11 Low-magnetism rotating magnet 12 High-magnetism rotating magnet 21 Upstream water tank 21A First stage part 21B Rear stage part 22 Downstream water tank 3 Ultrasonic vibrator 4 Scraper 5 Piping 6 Under sieve after grinding 7 Cyclone sorter 71 Container 72 Piping 73 Container 78 Piping 8 Pump

Claims (3)

Crushing treatment after crushing the dry battery to obtain a crushed material containing manganese oxide particles and zinc oxide particles as an under-sieving material;
The sieving material after the crushing and sieving treatment step is put into a liquid, and an aggregate of particles containing manganese oxide particles and zinc oxide particles present in the liquid is separated into each particle. A dispersion treatment step of dispersing in the liquid;
A weight difference separation treatment step of separating the manganese oxide particles and the zinc oxide particles by the difference in weight from the liquid in a state where aggregation of the manganese oxide particles and the zinc oxide particles is prevented after the dispersion treatment step; ,
Method for recovering manganese oxide from a dry battery having   The method for recovering manganese oxide from a dry battery according to claim 1, wherein the weight difference separation treatment step is performed after performing the low magnetic force separation treatment step of separating iron particles with a low magnetic force from the liquid after the dispersion treatment step.   The method for recovering manganese oxide from a dry battery according to claim 1 or 2, wherein the dispersion treatment step is performed by applying ultrasonic vibration to the liquid.

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