JP4224530B2 - Disposal method of waste television - Google Patents

Description

[0001]
[Technical field to which the invention belongs]
The present invention relates to a recycling method of waste home electric appliances whose amount of disposal is increasing, and in particular, is a processing method related to television cathode ray tube processing.
[0002]
[Prior art]
Along with the popularization of household appliances, the amount of household appliances discarded is also increasing. Home appliances are often composed of various materials such as plastics, metals such as iron, and glass, and the recovery and reuse of those materials from waste home appliances has become a social issue in recent years. .
[0003]
However, home appliances are becoming difficult in the industry to recover metal materials and the like from waste home appliances because the metal recovery costs are not commensurate with the recovery amount due to a decrease in metal materials and an increase in plastics. In particular, discarded televisions have seen a decrease in the amount of metal materials used and plastics increased, but due to the miniaturization of circuits, cathode ray tubes have become a major part of waste television. Yes. Accordingly, attention has been focused on the recovery or reuse of glass from cathode ray tubes of waste television.
The material of the cathode ray tube is mostly glass, but the material constituted by the panel portion of the screen and the funnel portion of the rear conical portion is different. Waste color television often contains barium in the panel portion and lead oxide in the funnel portion.
Since the composition of glass varies depending on its application, it is necessary to remove the above metals in order to reuse the glass.
For this reason, in order to recover the glass from the cathode ray tube, the cathode ray tube must be sorted into a panel part and a funnel part, and after being decomposed, it is not necessary to go through many steps such as magnetic separation and dissolving metals with an acid. It was difficult to reuse as glass. In addition, the metal contained in the cathode ray tube is also melted into the glass for the recovery of the metal, and it is difficult to perform physical sorting such as simple shaking, and the above-mentioned numerous steps must be taken. There was nothing for the industry.
Even if the waste CRT is added to the incineration or smelting process as it is, to use it as a solvent due to the metal contained in the CRT, the slag viscosity increases due to the contained rare earth metal, etc., and lead is transferred to smoke ash. There was a bad effect such as mixing into the slag.
For this reason, there has been a demand for a simple processing method for a method for using CRT glass from waste television and a method for recovering metal contained in the CRT.
[0004]
[Problems to be solved by the invention]
The purpose of the present invention is to find a simple and environmentally friendly method of using glass components or recovering metals from waste household electrical appliances that are particularly glass-rich, for example, glass tubes from waste televisions.
[0005]
[Means for Solving the Problems]
For household appliances that contain a lot of glass, especially for waste household appliances, if the parts containing glass that has been dismantled and separated from waste household appliances are crushed to finer particle size and the mixing ratio with other components is applied appropriately, the parts that contain glass Was found to be usable as a solvent for smelting.
In particular, it has been found that a CRT for waste television can be used as a smelting solvent even if the CRT is crushed as it is without disassembling the funnel part and the panel part. Furthermore, the particle size after crushing of the cathode ray tube was adjusted, and it was found that the average particle size is preferably 2 to 3 mm.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
The present invention is a method for dismantling from waste television and treating the separated waste cathode ray tube. The waste cathode ray tube is crushed and put into a smelting smelting process as crushed glass, so that the silicon oxide contained in the waste cathode ray tube is removed. As a solvent for the smelting process, the metal content is recovered more efficiently by adjusting the particle size of the crushing of other metal content, particularly lead. Furthermore, by exposing or including a lot of metal in the vicinity of the surface of the pulverized glass, heat is easily transmitted to the metal, making it easy to sublimate, and it is included in the pulverized glass by suppressing contamination with other recovered metals. In other words, the metal content was recovered and the metal content was desorbed so that the silicon oxide in the crushed glass could be used more effectively as a solvent. Moreover, when using for a smelting process, the addition amount shall be less than 1% with respect to an input ore, and the influence on another ore is restrict | limited and preferable.
[0007]
Waste home appliances are collected from the market by collection companies. Collected waste home appliances are transported to a recycling factory that disassembles waste home appliances, collects parts, and selects materials. Waste television is also included in the waste home appliances brought in.
Waste television carried into the recycling factory begins with disassembly of the housing on a workbench or the like, and is manually disassembled into cathode ray tubes, circuit boards, other parts, materials, and the like.
[0008]
The cathode ray tube is put into a crusher, and the glass of the cathode ray tube is mainly crushed into glass pieces and granules (hereinafter referred to as crushed glass). The crusher may be an impact crusher or a jaw crusher. The term “crushing” as used herein means that the cathode ray tube is divided mainly by shearing force to lower the particle size.
The particle size of the crushed glass is preferably about 2 to 3 mm on average.
The particle size may be adjusted by shaking or the like.
The reason is not clear, but it seems to be as follows. When the average particle size was about 2 to 3 mm, it was suitable for metal recovery when used in the smelting process. This is because the cathode ray tube is mainly made of glass. Normally, when crushing glass, it is amorphous, so crushing does not have a starting point at which crushing (shearing) occurs due to solid solution in the internal crystal. The starting point is determined. Since the cathode ray tube contains various kinds of metal, the portion containing the metal becomes the starting point of crushing, and the metal components are exposed on the crushing surface, so heat is generated when reacting at high temperatures such as in the smelting process. It is transmitted quickly and becomes easy to sublimate. At the same time, the metal content is reduced and the glass surface is exposed, so the reactivity is improved as a glass component. However, even if it is crushed finer than this, the glass is crushed from the part containing the metal, making it difficult for the metal content to come out on the surface. It seems that the reaction such as sublimation of the metal itself is difficult because of the small amount. This is because if the particle size is too fine, it will cause scattering in the subsequent process, and if it is too large, the bulk density will increase and affect the transportation cost.
[0009]
The control of the particle size distribution may be appropriately adjusted according to the method used and the specifications of the equipment for introducing glass. If necessary, the crushed glass may be put into a pulverizer to further reduce the particle size. The crushed glass is separated from iron and nickel through a magnetic separator. In addition, when crushed glass is mixed with foreign matter or the like, it may be washed with water as necessary.
[0010]
The components of the pulverized glass include SiO ₂ 50 to 65%, aluminum oxide 2 to 4%, sodium oxide 0 to 6%, lead oxide 10 to 25%, other calcium oxide, magnesium oxide, barium oxide and the like. The form is the situation where most are melted in glass.
The crushed glass is stored in a hopper, a container, a bag or the like and conveyed.
[0011]
The crushed glass thus obtained can be used as a solvent in the smelting process of copper smelting because it is mainly composed of SiO ₂ which is a glass component.
In dry-type copper smelting of copper from sulfide ore, silicate ore (main component, SiO ₂ ) is used as a solvent, iron and sulfur contained in sulfide ore are separated, and copper is recovered as metal.
For example, as a smelting process of copper smelting, there is a method using a flash smelting furnace or a converter. As a smelting process, in the case of copper smelting using a flash furnace,
The reaction is represented by the following formula.
1) 2CuFeS ₂ + O ₂ → 2Cu ₂ S + FeS + SO ₂
2) FeS + 2O ₂ + SiO ₂ → FeO · SiO ₂ + SO ₂
As shown in the formula (2), silicate ore is used as a solvent, and pulverized glass can be used in place of the silicate ore.
Copper sulfide, iron sulfide, and the like generated in the flash furnace are transferred to the converter, where oxidation reaction and the like are performed, and crude copper is obtained in the converter. In the case of a converter, the following reaction formula is fundamental.
3) Cu ₂ S + O ₂ → 2Cu + SO ₂
4) FeS + O ₂ + SiO ₂ → xFeO · ySiO + SO ₂
4) x and y in the equation are coefficients.
As shown in the formula (4), silicate ore is used as a solvent, and pulverized glass can be used in place of the silicate ore.
Moreover, if the lead contained in the crushed glass is volatilized together with sulfurous acid gas and recovered as lead sulfate, it can be used as a raw material for lead smelting. Other components contained in the crushed glass also become oxides and can be recovered within the smelting process.
As described above, since a plurality of components are mixed in the crushed glass, it was found that the crushed glass was used for smelting in the smelting process even though it was difficult to develop a utilization method. The metal inside can also be recovered.
[0012]
【Example】
The waste television was dismantled manually to obtain 100 kg of CRT.
The cathode ray tube was crushed to obtain crushed glass having an average particle diameter of 2 mm.
The components of the crushed glass at this time are SiO ₂ It contained 55%, aluminum oxide 4%, sodium oxide 6%, lead oxide 25%, other calcium oxide, magnesium oxide and barium oxide.
[0013]
It was confirmed whether the crushed glass can be used as a solvent for copper smelting. To the crucible, chalcopyrite powder and 1 wt% of crushed glass were added together so as to have the same composition ratio as in the flash furnace. The crucible was covered and heated to 1300 ° C. in an oven in an oxidizing atmosphere and allowed to cool. What was produced | generated from the inside of a crucible was taken out, and metallic copper was obtained. In addition, it was confirmed by qualitative analysis that lead oxide was produced from the material adhering to the crucible lid.
From this, it was found that crushed glass can be used as a solvent for copper smelting, and that metal can also be recovered.
[0014]
【The invention's effect】
According to the present invention, it has been found that by separating the glass component from the dismantled and separated glass parts from the waste home appliances, it can be used as a raw material for smelting or metal recovery. We found a method for processing glass in waste television CRTs, and also made it possible to recover metals, thereby contributing to a recycling-oriented society and making effective use of resources.

Claims (1)

A method for treating waste television, comprising pulverizing a discarded television cathode ray tube , adjusting the particle size of the pulverized glass by the pulverization to an average of 2 to 3 mm, and adding it to a smelting step of copper smelting.