JPH08937B2 - Method for recovering silver oxide and metal from used silver oxide button batteries - 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 recovering silver oxide and metal from a used silver oxide button battery, and more particularly, by physically separating the battery casing and its contents, silver oxide, silver, It relates to a method for recovering zinc, iron and nickel.

[0002]

2. Description of the Related Art Button batteries are generally classified into silver oxide batteries, mercury batteries, lithium batteries and alkaline manganese batteries. Among them, the silver oxide battery contains silver oxide and silver metal, and the battery outer covering part is made of zinc, iron and nickel. It is desired that such a silver oxide battery recovers and reuses silver oxide, silver and other metals after use.

However, at present, as shown in FIG. 3, only silver oxide and silver are recovered. That is,
The cell envelope is chemically dissolved (1) and separated (2) to recover the solid phase silver oxide and silver (5), which is dry smelted (for example, by adding NaCO ₃ and C to 1000
Refining by a soda method of heating to ° C) to obtain 95% of crude silver (6). After that, the crude silver is further refined by the conventional method to be re-sold as a silver ingot having a purity of 99.99% (7, 8), and metal components other than silver contained in the liquid phase are recovered. It is thrown away without being (3,
The current situation is 4). Further, in the above-mentioned silver recovery process, there is a problem that exhaust gas and waste water are contaminated and cause serious environmental problems. That is, in the method conventionally used for silver recovery, aqua regia consisting of concentrated nitric acid and hydrochloric acid is used to dissolve the outer coat of the battery (1), and silver oxide and silver are recovered. The wastewater after being treated is strongly acidic and contains environmental pollutants (3, 4), and produces exhaust gas such as NOx. Thus, conventional methods of silver recovery are very environmentally-friendly, and removing these contaminants and treating them to meet effluent standards requires complex techniques and high costs. Has become.

[0004]

SUMMARY OF THE INVENTION The present invention was made in view of the above-mentioned problems, and its purpose is to prevent the generation of harmful substances that may lead to environmental pollution, and to improve the quality of spent oxidation. A method for recovering silver oxide and metal from used silver oxide button batteries, which enables recovery of silver oxide, silver and other metals from silver button batteries, and recovery of valuable metals that were previously discarded. To provide.

[0005]

In order to achieve the above-mentioned object, the present invention destroys a used silver oxide button battery into pieces, and heats the pieces to a temperature of 100 ° C or more to dry them.
Is allowed, heating, dry and transferred to the debris to a vigorously stirred 30 ° C below the cold water are stripped jacket from the contents of the cell, the cold water and a stripped jacket and the contents further solid Phase and liquid phase, and from the separated solid phase, magnetic materials such as iron and nickel and non-magnetic materials such as silver oxide, silver and zinc are separated and recovered.

[0006]

[Operation] First, a used battery is crushed into pieces by mechanical means. The debris is then heated to a high temperature and immediately the heated debris is transferred to vigorously stirred cold water. In this way, by continuing the heating action and the cooling action, the contents can be physically peeled off from the battery casing. Then, solids such as silver oxide, silver, iron, zinc and nickel are separated from other liquids, and further, iron and nickel as magnetic materials and silver oxide as non-magnetic material are separated from the separated solids by magnetic means. Separate from silver and zinc.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT An embodiment of the present invention will be described with reference to FIG. First, a used silver oxide button battery is crushed into pieces by mechanical means such as a ball mill (9).
This shard is heated in a heating furnace to a temperature of 100 ° C. or higher (10) to be dried, and immediately transferred to chilled water which is kept at a temperature of 30 ° or lower and is vigorously stirred (11). . In this way, when the destroyed battery fragments are immediately transferred from the heated state to the cooled state, the physical action based on exaggeration and contraction causes the battery jacket (iron, zinc, nickel) and its contents (silver oxide, silver) to be removed. It can be easily separated. Then, after separating into a solid phase and a liquid phase by means such as sieving (12, 13, 15), the liquid phase is discarded (1
4), the solid phase is magnetically separated by magnetic separation means into iron and nickel which are magnetic substances and silver oxide, silver and zinc which are non-magnetic substances (16, 17, 19). Iron and nickel are sold and reused as they are without refining (18), but zinc metal among non-magnetic substances is separated by distillation by the dry refining method, concentrated and recovered (20, 23, 24), The remaining silver oxide and silver are purified by conventional methods and resold as silver ingots (19-24) (22).

Next, an example in which a 100-gram used silver oxide button battery is actually processed will be described with reference to FIG. That is, 100 grams of a used silver oxide button battery was broken by a ball mill (25), and the broken battery fragments were heated in a heating furnace at 400 ° C for 30 minutes (26).
The heated cell fragments were then immediately transferred to 10 ° C. cold water and the cold water was vigorously stirred and cooled for 10 minutes (27). This separated the battery envelope and its contents. Then, the cold water in which the battery casing and its contents are separated is sieved by a sieve of mesh 20,
82 g of solid phase could be obtained (28,3
0). Filter the remaining cold water through a filter and
8 grams of solid phase was removed and the cold water as filtrate was 0.
With a silver content of less than 1 ppm, it was discarded as it was (29,3
1, 33, 34, 35). 1 collected in this way
00 grams of solids (82 grams from the sieve and 18 grams from the filter) were magnetically separated into magnetic and non-magnetic materials using magnetic means, and magnetic materials iron and nickel 5
9.2 grams, non-magnetic silver oxide and silver and zinc 4
I got 0.8 grams. The silver oxide, silver, and other metals thus recovered were refined by a conventional method, or sold as they were for reuse. As mentioned above, heating the cell debris, especially at 400 ° C.
By keeping the zinc at a high temperature for 0 minutes without melting it, the cooling of the heating debris is also increased, especially at 10 °
By performing the stirring condition with cold water of C or lower for 10 minutes,
The contents can be efficiently peeled from the outer cover by utilizing the physical effect based on the exaggerated shrinkage caused by the rapid cooling. Finally, a table is provided which compares the advantages of the present invention with conventional chemical methods of melting jackets.

[0009]

[Table 1]

[0010]

As described above, according to the present invention, a used silver oxide button battery is mechanically broken into pieces,
The solid phase was recovered by stripping its contents from the outside and transferred to cold water being vigorously stirred After heating the pieces, it was to separate into a non-magnetic metal and a magnetic metal by further magnetic means Therefore, it does not emit polluted wastewater and harmful substances such as exhaust gas as in the case of performing conventional scientific treatment, and therefore does not cause a problem of environmental pollution, and
A method of recovering silver oxide and a metal from a used silver oxide button battery, which makes it possible to recover and reuse a valuable metal that has been conventionally discarded. Well
In addition, mechanically destroyed and heated debris is stirred vigorously.
Is transferred to cold water, but is thus heated
In addition to simply putting the debris into cold water to quench it,
If cold water is stirred vigorously in advance, the
The temperature of cold water is temporarily or locally increased by adding one piece.
You can avoid rising. Therefore, of debris
Cooling can be done quickly and the peeling caused by rapid cooling
It can be performed reliably and efficiently. In addition, cold water
What is the peeling due to the temperature difference by stirring vigorously
Separately, or in combination with the peeling due to the temperature difference,
Whether debris will come into contact or collide in water
Therefore, the peeling can be performed more reliably and efficiently.
Will be able to

[Brief description of drawings]

FIG. 1 is a flowchart showing steps of an embodiment of the present invention.

FIG. 2 is a flow chart showing steps for an example of actual processing of 100 grams of used silver oxide button battery.

FIG. 3 is a flowchart showing a chemical treatment process in a conventional example.

[Explanation of symbols]

 9 ・ ・ Pulverization 10 ・ Heating (100 ° C or higher) 11 ・ Cooling (vigorous stirring; 30 ° C or lower) 12 ・ Separation 16 ・ Magnetic separation

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Lee Haoxing, Republic of China (Taiwan) Zhongxing Road, Zhongxing Town, Hsinchu County, No. 195, 64th Building, No. 64 (56) References JP-A-63-24560 (JP, A) Kai 51-69261 (JP, A) JP 57-152433 (JP, A) JP 2-209433 (JP, A) JP 2-290928 (JP, A)

Claims (1)

[Claims] 1. A used silver oxide button battery is broken into pieces, and the pieces are heated to a temperature of 100 ° C. or higher and dried, and the heated and dried pieces are vigorously stirred at 30 °.
The contents are peeled from the battery casing by transferring to cold water of C or lower, and the cold water containing the peeled casing and contents is further separated into a solid phase and a liquid phase, A method for recovering silver oxide and metal from a used silver oxide button battery, characterized in that magnetic materials such as iron and nickel are separated from non-magnetic materials such as silver oxide, silver and zinc.