JP2001283871A - Disposal method and system of waste cell - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a disposal method and its system which makes it possible to separate various metals contained in the waste cell roughly into a concentrated high volatile metal which is zinc, lead, cadmium, mercury or the like, a concentrated low volatile metal which is iron, manganese, copper, or the like, and a material containing alkali and halogen, which is potassium, sodium, chlorine, or the like. SOLUTION: A waste cell is put in a container set inside of a furnace and is heated, and vapor and powder which is generated by decomposition of the waste cell, is discharged with gas separately introduced to the container from the high-temperature container, and after cooing the discharged gas, the above powder and coaggulated powder are separately recovered from the discharged gas, and the waste cell remaining in the container is discharged as a solid material in this disposal method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for treating a waste battery, and more particularly, to a method for treating a waste battery containing a substance which may affect human health. This is a technique for recovering in a form that facilitates subsequent processing.

[0002]

2. Description of the Related Art In modern society, batteries are used in various forms. Common batteries include manganese batteries,
So-called "primary batteries" such as alkaline batteries and mercury batteries, and Ni-
There are "secondary batteries" such as Cd batteries and lead storage batteries. Common to these batteries is zinc, lead, cadmium,
That is, a metal having a relatively high vapor pressure such as mercury and a metal having a low vapor pressure such as iron, copper, nickel and manganese are mixed. The former metals, such as zinc, lead, cadmium, and mercury, are called heavy metals and may affect human health. In general, batteries include sodium,
Although a large amount of alkali metals such as potassium and chlorine and halogens are contained, it is considered that these substances can be used as secondary resources if they can be individually concentrated.

[0003] Substances containing such high concentrations of zinc, lead, cadmium, mercury and the like have been conventionally regenerated and recycled using various methods. For example, dry zinc refining, which is now commonly performed, is a technique of simultaneously melting and processing ores, scraps, dusts, etc. containing various types of non-ferrous metals, and separately and simultaneously collecting the non-ferrous metals contained therein. In (2), zinc having a zinc concentration of 99% by mass or more is recovered from dust having a zinc concentration of 20 to 70% by mass. JP-A-7-173548 discloses a furnace in a highly reducing atmosphere in which the zinc concentration is from several mass% to 30 mass%.
And a technique for recovering crude zinc oxide having a zinc concentration of about 50 to 70% by mass. Therefore,
If these technologies are used, there is a possibility that a waste battery can be used as a recycled material having higher utility value. It is also considered that manganese can be used as a raw material that can be easily recovered and recovered by further concentrating.

However, the dry zinc refining method described above
I hate mixing of low volatility metals such as iron and manganese and impurities such as alkali metals and halogens into the raw materials. This is because, since the operation is performed under the condition that the iron and the like are not reduced while reducing the zinc by controlling the reducing power, a large amount of unreduced slag called “iron slag” is generated, and it is difficult to treat the slag.

In the technique described in Japanese Patent Application Laid-Open No. 7-173548, low-volatile metals can be discharged from the lower part of the furnace, and highly volatile metals can be discharged as dust from the furnace top. Although it is compatible with smelting of raw materials containing, even in this case, for example, in order to suppress the incorporation of alkali into zinc, which is a highly volatile metal, it is necessary to reduce the amount of alkali metal in the raw material Is valid.

The present invention has been made in view of the above circumstances, and has been developed to concentrate various metals contained in a waste battery with a highly volatile metal such as zinc, lead, cadmium, and mercury, and iron, so as to facilitate subsequent processing. It is an object of the present invention to propose a processing method and a processing apparatus for a waste battery that can be roughly separated into a low-volatility metal containing concentrated manganese and copper and a substance containing alkali and halogen such as potassium, sodium and chlorine. .

[0007]

Means for Solving the Problems The inventor has conducted intensive studies in order to achieve the above object, and has embodied the results in the present invention.

That is, according to the present invention, a waste battery is charged into a container placed in a furnace and heated, and steam and powder generated by decomposition of the waste battery are caused to accompany gas separately introduced into the container. A waste battery, wherein the waste gas is discharged from a high-temperature container, and after cooling the discharged gas, the powder and the agglomerated powder are separated and recovered from the exhaust gas, and the waste battery remaining in the container is discharged as a solid substance. Processing method. At that time, it is preferable that the solid is sieved and the lump is collected as a lump above the sieve and the lump is collected below the sieve. At this time, the atmosphere temperature in the container is preferably set to 100 ° C. to 900 ° C. By setting the temperature to 100 ° C. or higher, the water contained in the waste battery evaporates rapidly, so that the explosion of the waste battery is facilitated, and the separation of coarse particles and aggregates is facilitated. However, if the temperature is higher than 900 ° C., a melt may be generated in the solid substance, and it may be difficult to sieve coarse particles and agglomerates. Further, when the atmosphere temperature in the container is set to 500 to 900 ° C., highly volatile substances such as zinc, alkali, and cadmium contained in the waste battery are volatilized and separated and discharged to the outside of the container by the separately introduced gas. Since it is recovered as the above-mentioned powder and agglomerated powder, it can be used as a lump, a coarse particle, and a powder, respectively, which is more preferable. Further, the gas separately introduced into the container is (CO + H ₂ ) / (CO ₂ + H ₂
O) If adjusted so as to have a reducing atmosphere of> 0.1, zinc generated in the above-described decomposition of the battery is easily reduced and easily evaporated, so that zinc in the powder is concentrated, and more preferably Separation of substances becomes possible.

In addition, the present invention provides a container for holding a charged waste battery, heating means for heating the atmosphere in the container, gas supply means for introducing gas into the container, and gas discharged from the container. And a gas cooling device for cooling gas.

According to the present invention, a waste battery is retained in a container in which an airflow gas is circulated, and powder condensed from steam generated by heating is collected, and the residue in the container is sieved to a predetermined particle size. After collecting the lump on the sieve as a lump (hereinafter, referred to as lump) and the under sieve as a coarse particle (hereinafter, lump),
Powders, lumps, and coarse particles can be reused as metal smelting raw materials depending on their components. Moreover, since decomposition can be easily performed by heating and adjusting the atmosphere gas in a closed container, cadmium, mercury, and other substances that may affect human health can be safely processed without exposure to the environment. become able to.

At this time, the temperature of the heating atmosphere is set at 10
By setting the temperature to 0 ° C. or higher, rapid evaporation of water contained in the waste battery itself can be promoted to facilitate the separation of aggregates and coarse particles of the waste battery. Further, by setting the temperature to 500 ° C. or higher,
By evaporating and separating the highly volatile substance contained in the waste battery into the flowing gas and aggregating it to obtain a powder,
It facilitates separation as a powder in addition to coarse particles, and facilitates reuse of various substances separated into each state. in this case,
When the ambient temperature exceeds 900 ° C., a substance that melts in the lump and the coarse substance may be formed, and the separation of the lump and the coarse substance may be deteriorated.
Set to 00 ° C. In addition, (C
By introducing a gas of O + H ₂ ) / (CO ₂ + H ₂ O)> 0.1 to form a reducing atmosphere as a whole, it promotes the reduction of zinc and the like from lumps and coarse particles. It can also promote volatile separation.

[0012]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to the circumstances leading to the invention.

In order to find an appropriate method for treating a waste battery, the inventors studied the structure of a dry battery. FIG.
(A) and (b) show the structures of general alkaline batteries and manganese batteries, respectively (these figures are quoted from the journal of the Battery Association of Japan). As shown in FIG. 2A, the manganese battery has a carbon rod 12 in the center, a mixture 13 containing manganese oxide and water as a positive electrode around the carbon rod 12, and a zinc can 14 surrounding the outside thereof. Here, the mixture 13 is obtained by kneading various components with a binder (joining substance) such as moisture. The alkaline battery is shown in FIG.
From (b), a carbon rod 12 serving as a cathode exists at the center, and a mixture 13 containing zinc as a negative electrode surrounds the periphery thereof,
Another mixture 13 containing manganese exists as a positive electrode on the outer periphery of the mixture, which is separated by a partition (referred to as a separator) 15. Therefore, in a dry battery, valuable elements such as zinc and manganese are present separately from each other, and a simple separation method described below was studied by utilizing this characteristic.

First, the inventor considered a device used for experiments. As shown in FIG. 1, a container 4 for holding a waste battery, a heating furnace 10 surrounding the container 4 and heating an internal waste battery 5, and gas supply means for introducing gas into the container 4 (FIG. (Not shown) and a gas cooling device 9 for cooling the gas discharged from the container 4. Specifically, the container 4 is a cylindrical body made of a refractory material, and is provided with a gas inlet 1 and a gas outlet 8 and a charging port 17 and a discharge port 18 of a waste battery so that gas can flow therein. Any structure and shape may be used. As the heating furnace, an electric furnace capable of heating the outer periphery of the container was used. The means for heating the atmosphere in the container 4 is not limited to this electric furnace, and a method of heating the container from the outside with a gas, a heavy oil burner, or the like can be adopted. May be supplied. As a gas supply means, a gas cylinder is generally used. However, in some cases, the exhaust gas may be used by directly connecting to a combustion exhaust gas pipe in various factories. As the gas cooling means, a sedimentation chamber provided with a means for cooling the wall (cooling water pipe 6), a cyclone, or the like can be used. In addition, the powder can be collected as slag by water cooling.

When the waste battery 5 is heated using the above-described experimental apparatus, the waste battery 5 is utilized by utilizing the moisture contained in the waste battery 5.
Can explode and decompose. When a plurality of manganese batteries or alkaline batteries were actually loaded into the container 4 and heating experiments were performed individually while flowing nitrogen gas, when the atmosphere temperature in the container 4 exceeded 100 ° C., In the battery 5 as well, the inner rod rose, the contact points of the positive and negative electrodes, which were structurally weak, exploded, and the carbon rod inside jumped out. When the carbon rod popped out, the above-mentioned various mixtures filled and solidified in the center became powdered as the water evaporated. This means that a manganese battery is divided into a granular material (coarse particle) containing a large amount of manganese oxide and a lump composed of a zinc can and a metal (iron) jacket. (Referred to as coarse particles) and lumps composed of manganese oxide and a metal jacket (iron). In other words, depending on the type of the waste battery, the contents of the lump and the coarse particles are different,
Originally, a waste battery is an aggregate of objects having various functions such as a cathode, an anode, an electrolyte, a jacket, and the like. Therefore, it is possible to sort materials only by separating a lump and a coarse particle.
In the above example, in the case of a manganese battery, manganese, iron, and zinc can be separated, and in the case of an alkaline battery, zinc, manganese, and iron can be easily separated.

Next, when the atmosphere temperature in the container 4 was gradually increased from 500 ° C. to 900 ° C., a large amount of carbon monoxide gas was generated in the atmosphere in the container. Further, powder 7 accumulates in the gas cooling device 9 for the exhaust gas, and the powder 7 is
It contained a high concentration of zinc. This is because when the temperature in the furnace is increased, in the alkaline and manganese batteries, the zinc component is vaporized, or the zinc or the like of the electrode reacts with the reducing gas to be reduced and vaporized by the reaction shown in the following formula, and condensed by cooling. To a fine powder.

Zn (s) → Zn (g) ZnO + C → Zn (g) + CO By the way, the zinc vapor obtained by the above reaction has a very high reactivity to oxygen and must be in a reducing atmosphere or in an inert gas stream. However, there is a possibility that the gas cooling device 9 cannot be stably reached. That is, it is re-oxidized in the container 4 (peripheral oxide, for example, manganese oxide or the like), becomes a solid, accumulates in the container 4, and cannot be separated as zinc. Therefore, the inventor aims to stabilize the zinc vapor by making CO or H ₂ into the gas introduced into the container 4 and making the inside of the container 4 a reducing atmosphere under the same temperature condition. did. The reducing atmosphere will be described in Examples below, but it has been found that the valuable metal in the battery can be separated by the separation according to the particle size after the heat treatment.

Further, the inventor conducted similar experiments to lead storage batteries and nickel-cadmium batteries other than manganese and alkaline batteries, and confirmed that similar results were obtained. In other words, in the same way as manganese and zinc, which have high vapor pressure in powder and coarse particles in alkaline batteries and iron and manganese in lumps are concentrated, lead in lead batteries and In a nickel-cadmium battery, cadmium is concentrated in powder and coarse particles, and nickel and iron are concentrated in a lump. In a subsequent investigation,
It was found that in the coarse particles and the powder, alkali metals such as potassium and chlorine and a halogen element were concentrated at the same time as zinc. Since these elements may hinder the subsequent zinc recovery and recovery process, the recovered powder and coarse particles may be used after being subjected to dehalogenation and dealkalization metal treatment by washing with water or the like. I knew it was desirable.

Then, the inventor arranged these experimental results, and as described above, stated that "a waste battery was put into a container arranged in a furnace and heated, and steam and powder generated by decomposition of the waste battery were charged. Is discharged from the high-temperature container with the gas separately introduced into the container, and after the discharged gas is cooled, the powder and the agglomerated powder are separated and recovered from the exhaust gas, and the waste remaining in the container is removed. The present invention has conceived a processing method of “discharging a battery as a solid substance”, and has provided a processing apparatus based on the above experimental apparatus.

In the present invention, the waste batteries remaining in the furnace after the completion of the heat treatment are discharged as solids, which are classified by a sieve having a sieve of about 3 to 5 mm, and a lump is placed on the sieve. ,
The under sieve will be recovered as coarse particles. In the present invention, it is preferable that the atmosphere temperature in the container is set to 500 to 900 ° C. The reason is that, when the temperature exceeds 500 ° C., as described above, the amount of zinc evaporated in the alkaline battery further increases. On the other hand, if the temperature exceeds 900 ° C., what is melted in the furnace residue is generated, which hinders the classification of coarse particles and lumps. Therefore, the upper limit is preferably 900 ° C. Further, in the present invention, it is preferable that only the same type of batteries are separated from the above-mentioned various batteries and then charged into the furnace. This is because it is easy to make the components of the obtained recovered products constant. However, in the present invention, various types of batteries may be mixed and charged. This is because the composition of the recovered material may be determined according to the smelting capacity of the post-processing step of the recovered material.

As described above, the atmosphere temperature and composition in the container are appropriately selected so that the waste battery is decomposed so as to be concentrated into any of a lump, a coarse particle, and a powder according to the type of metal to be recovered. Since the treatment can be performed, it is possible to confirm the respective compositions of the lump, the coarse particles, and the powder that have been decomposed and separated, and to perform an appropriate post-treatment.

[0022]

EXAMPLE An alkaline battery and a manganese battery (AA) shown in Table 1 were mixed in an amount of 100 g each and charged into a container 4 having a capacity of 10 liters shown in FIG. Using a gas supply means (gas cylinder and piping), nitrogen gas was introduced into and circulated through the vessel 4 at a flow rate of 1 liter / min, and the heating furnace 10 surrounding the vessel 4 was turned on to start heating. The temperature of the atmosphere in the container 4 is raised to a predetermined temperature in one hour, and is kept constant at that temperature for one hour.
The temperature was lowered to room temperature in minutes. The predetermined temperature is 25, 1
Six levels of 00, 300, 500, 700 and 900 ° C were set.

[0023]

[Table 1]

Thereafter, the powder 7 adhering to the inner wall of the gas cooling device 9 was separated and collected, and the residue in the furnace was separated using a 3 mm sieve to separate the coarse particles and the lump. The composition of the recovered powder 7 is shown in Table 2, the composition of the coarse particles is shown in Table 3, the composition of the lump is shown in Table 4, and the amount of each collected is shown in Table 5 by weight.

[0025]

[Table 2]

[0026]

[Table 3]

[0027]

[Table 4]

[0028]

[Table 5]

From these tables, it can be seen that manganese and iron are concentrated in the lump and zinc is concentrated in the coarse particles and the powder. If each component is concentrated to the degree shown in the table, for example,
The recovered powder in the cooling device can be used as a raw material for zinc smelting,
The lump can be used as a raw material for producing ferromanganese. Table 6 summarizes the yield of manganese and iron in the lump and the yield of zinc in the cooling device recovered powder and coarse particles.

[0030]

[Table 6]

Table 7 shows the concentration of carbon monoxide in the exhaust gas at each of the above temperatures, and shows the composition of the atmosphere gas in the container at each temperature, and the weight of the recovered powder, coarse particles and lump in the cooling device. 3
Shown in FIG. 3 shows that when the atmosphere temperature in the container becomes 500 ° C. or higher, the concentration of carbon monoxide in the gas increases, and the amount of the recovered powder sharply increases. This is because zinc vapor was generated by the reduction reaction of zinc by carbon and the zinc concentration of the powder was increased, indicating that the value of the powder as a raw material for regenerating zinc was increased.

[0032]

[Table 7]

Next, the gas introduced into the container 4 is changed and C
The mixed gas of O and CO ₂ is mixed at a CO / CO ₂ ratio of 0.0
While changing the flow rate to 1, 0.1, and 10, the flow was introduced at a flow rate of 10 liters / minute, and circulated. As a result, the weight of the recovered material is shown in Table 8, and the yields of manganese and iron in the lump and the yields of zinc in the powder collected by the cooling device and the coarse particles are shown in Table 9 and FIG.

[0034]

[Table 8]

[0035]

[Table 9]

As shown in Table 8 and FIG. 4, CO / CO ₂
With a gas of = 0.01, the zinc yield was reduced. This is probably because the zinc vapor generated by the direct reduction was oxidized and attached to the lump. On the contrary,
As CO / CO ₂ is increased above 0.01, the zinc yield is progressively increasing. This is considered to be because zinc atmosphere was stabilized because the inside of the furnace became a reducing atmosphere, and oxidized or solidified after being transported to the cooling device. Further, as a reducing gas, natural gas was partially burned with air, the value of (CO + H ₂ ) / (CO ₂ + H ₂ O) was adjusted and introduced into the vessel, and the same test was performed. Table 10 shows the yield of manganese and iron in the lump in the collected material and the yield of zinc in the powder collected by the cooling device and the coarse particles. In this test, almost the same results were obtained as in the experiment using a mixed gas of CO and CO ₂ . Accordingly, in the present invention, the gas separately introduced into the container is (CO + H ₂ ) / (CO ₂ + H
_It was determined that it was better if the relationship of ₂ O)> 0.1 was satisfied.

[0037]

[Table 10]

From the above-mentioned results, it is clear that the valuable metal component in the waste battery can be separated without adversely affecting the environment and can be used as a secondary resource which can be more easily regenerated. The powder recovered by the method of the present invention is not limited to a zinc smelting furnace, but may be a coke packed bed type two-stage tuyere smelting reduction furnace, a cupola vacuum heating furnace rotary kiln equipped with a zinc recovery device, an electric furnace, or a rotary hearth gas. Use in a heating type melting furnace is also possible. It can also be effectively used in hydrometallurgy such as electrolysis.

[0039]

As described above, according to the present invention, various metals contained in a waste battery are mixed with a highly volatile metal such as zinc, lead, cadmium, and mercury so as to facilitate the subsequent treatment. , Iron, manganese, copper and the like, and low-concentration and low-volatile metals, and potassium, sodium, chlorine and other alkali and halogen-containing substances.

[Brief description of the drawings]

FIG. 1 is a vertical sectional view showing a waste dry battery processing apparatus according to the present invention.

FIG. 2 is a longitudinal sectional view showing a general structure of a dry battery;
(A) is a manganese battery, (b) is an alkaline battery.

FIG. 3 is a diagram showing a change in the weight of a collected product obtained in the practice of the present invention depending on a heating temperature.

FIG. 4 is a diagram showing a change in the weight of the recovered material obtained in the practice of the present invention depending on the composition of the introduced gas.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Gas inlet 2 Heating element 3 Insulation material 4 Container 5 Waste battery 6 Cooling water pipe 7 Powder 8 Exhaust gas exhaust port 9 Gas cooling device 10 Heating furnace 11 Waste battery inlet or outlet 12 Carbon rod 13 Mixture 14 Zinc can 15 Partition (separator) 16 Arrow indicating gas flow direction

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C22B 7/00 C22B 9/02 5H031 H01M 10/54 9/02 C22B 19/04 H01M 10/54 19/34 // C22B 19/04 B01D 53/34 136Z 19/34 B09B 5/00 ZABA F term (reference) 4D002 AA28 AA29 AA31 AC10 BA06 BA13 DA35 DA54 DA55 EA13 GA01 GA03 GB03 GB08 HA01 4D004 AA23 AB03 BA05 CA08 CA24 CA03 CB32 CC01 CC DA02 DA03 DA06 DA10 4D021 FA09 GA18 GA23 GB10 HA10 4K001 AA06 AA09 AA10 AA14 AA16 AA20 AA30 AA34 AA35 BA22 CA02 DA06 DA07 DA10 EA03 GA15 GB02 GB09 GB11 HA09 5H025 BB01 MM10 5H031 AA01 AA03RR

Claims (6)

[Claims] 1. A waste battery is charged into a container placed in a furnace and heated, and steam and powder generated by decomposition of the waste battery are discharged from the container along with gas separately introduced into the container. ,
A method for treating a waste battery, comprising: cooling the discharged gas, separating and collecting the powder and the agglomerated powder from the exhaust gas, and discharging a waste battery remaining in the container as a solid. 2. The solid matter is sieved, and the mass on the sieve is
2. The method according to claim 1, wherein the undersize is collected as coarse particles.
A method for treating a waste battery as described in the above. 3. The atmosphere temperature in the container is 100 to 90.
The method for treating a waste battery according to claim 1 or 2, wherein the temperature is set to 0 ° C. 4. An atmosphere temperature in said container is 500 to 90.
The method for treating a waste battery according to claim 1 or 2, wherein the temperature is set to 0 ° C. 5. A includes a gas separately introduced into the vessel CO and / or H ₂ and CO ₂ and / or H ₂ O, their relationship is _{(CO + H 2) / (} CO 2 + H 2 O)> 0 .1
The method for treating a waste battery according to claim 1 or 2, wherein the following condition is satisfied. 6. A container for holding the inserted waste battery, heating means for heating the atmosphere in the container, gas supply means for introducing gas into the container, and cooling gas discharged from the container. A waste battery processing device comprising a gas cooling device.