JP3382082B2 - Waste treatment method and treatment device - 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 and an apparatus for treating waste, and more particularly to a foamed resin containing a halogenated hydrocarbon as at least a part of a constituent material.
In addition, the present invention relates to a method and an apparatus for processing and recycling waste in which the foamed resin or other resin and metals are integrated.

[0002]

2. Description of the Related Art Conventionally, when discarding home electric appliances, iron parts are collected by crushing after magnetic crushing, but other parts are shredded by a shredder to reduce the volume, and then landfilled. A method of disposal was adopted.
The dust from this shredder is a mixture of plastic and glass, and there has been no effective recycling method. In addition, in the absence of such crushing equipment, there were cases in which landfill disposal was used.

[0003] Among home electric appliances, for example, a refrigerator uses a foamed resin such as a urethane foam resin as a heat insulating material, and the foaming agent of the foamed resin is mainly a freon 11 or a freon 12. Halogenated hydrocarbons (fluorocarbons) are used. In the case where the waste home electric appliances using such a foamed resin as a constituent material are landfilled, there is a risk that halogenated hydrocarbons (Freon) such as Freon 11 and Freon 12 may be released over time. .

Hitherto, as a method for recovering halogenated hydrocarbons contained in urethane foam resin, a method has been proposed in which urethane foam resin is finely crushed to a size of several tens of μm (Japanese Patent Application No. 5-147038). reference). However, in this method, since the halogenated hydrocarbon easily leaks out of the crusher, the crusher must be tightly sealed.
Therefore, not only the size of the apparatus was increased, but also the crushing process had to be performed in multiple stages. For example, in the case of waste refrigerators, as a method of recycling plastics that account for about 40% by weight of the material composition, a method of crushing and separating each type of resin by specific gravity sorting (Japanese Patent Application No. 3-23909) Reference). However, according to this method, it is very difficult to separate and recover a copper wire and a coating resin such as a vinyl chloride resin with high purity, for example, in electric wire waste. Also, it has been difficult to separate, for example, a copper pipe or a printed wiring board from a foamed urethane resin that is used in a composite manner, and to recover high-purity ones from each. In addition, it is not only applicable to plastics that cannot be regenerated due to deterioration, but it is necessary to separately incinerate the crushed dust generated in the crushing / sorting process. In addition, when metals are separated and collected by specific gravity sorting, foamed resin containing halogenated hydrocarbons and other resins may be mixed into the collected metals, and furthermore, printed wiring boards and electronic components may be mixed. Zn, Pb, Cd used,
Rare metals such as Sb, Se, Te, and Sr could not be recovered.

[0005]

As described above, in the prior art, since a method for treating halogenated hydrocarbons (fluorocarbon) has not been established, foams containing halogenated hydrocarbons such as foamed urethane resins have not been established. Refrigerators made of resin cannot be safely disposed of without polluting the environment. Further, in the method of separating and recycling by specific gravity separation, not only the copper wire and the covering resin, or the copper pipe or the printed wiring board and the urethane foam resin cannot be completely separated, but also deteriorated and the regeneration becomes impossible. There was a problem that it was difficult to apply to possible plastics. Furthermore, not only is it necessary to separately treat crushed dust generated in the crushing / sorting process and resin mixed into the sorted metal, but also it is not possible to collect rare metals used in printed wiring boards and the like. there were.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and wastes having a halogenated hydrocarbon-containing foamed resin, such as urethane foamed resin, as a part of a constituent material are halogenated into the environment. It is an object of the present invention to provide a method and an apparatus for performing a recycling process without releasing hydrocarbons to separate and recover oils, metals and other valuables.

[0007]

Means for Solving the Problems To achieve the above object, the present inventors have developed a waste home appliance having a urethane foam resin as a part of a constituent material and integrating the foam resin and the like with a metal. As a result of intensive research on the treatment of products, as a result of combining the dry distillation / pyrolysis process and the evaporation and recovery process of metal by vacuum heating, and adding the oil recovery process and the halogenated hydrocarbon decomposition process, They have found that they can be efficiently recycled at low cost without polluting the environment, and have completed the present invention.

According to the method for treating waste of the present invention, waste containing a halogenated hydrocarbon-containing foamed resin as a part of a constituent material and a metal integrated with the foamed resin is subjected to dry distillation and thermal decomposition. A pyrolysis step of generating the halogenated hydrocarbon gas and generating the hydrocarbon gas, a step of cooling and condensing the hydrocarbon gas to recover oil, and a step of halogenating the halogenated hydrocarbon gas. A halogenated hydrocarbon decomposition step of decomposing into hydrogen and carbon dioxide,
Heating the residue of the pyrolysis step while adjusting the temperature and pressure in a closed vessel maintained in a vacuum, and evaporating and collecting a metal having a high vapor pressure contained in the residue. And

Further, the waste treatment apparatus of the present invention is characterized in that a waste having a halogenated hydrocarbon-containing foamed resin as a part of the constituent material and a metal integrated with the foamed resin is subjected to dry distillation and heat treatment. A cracking device for cracking and generating the halogenated hydrocarbon gas and hydrocarbon gas; an oil recovery device for cooling and condensing the hydrocarbon gas to recover oil; and a hydrogenation device for converting the halogenated hydrocarbon gas to hydrogen halide. A halogenated hydrocarbon decomposer that decomposes into carbon dioxide and
A closed container for containing the waste residue, a mechanism for heating the inside of the closed container, a mechanism for reducing the pressure in the closed container to a vacuum, a control mechanism for adjusting the temperature and pressure in the closed container, A vacuum evaporation and recovery device having a mechanism for cooling and recovering the metal vapor.

In the waste treatment method of the present invention, the heating in the pyrolysis step is performed in an atmosphere having an oxygen concentration of 0 to 5% by weight.
Heat to a temperature of 400-800 ° C. By adjusting the oxygen concentration and the heating temperature in this way, halogenated hydrocarbons contained as a foaming agent are generated as a gas from the foamed resin contained in the waste, and the foamed resin and other resins are produced. Hydrocarbon gas is generated by the thermal decomposition. Further, at this time, the metal contained in the waste is not oxidized, and is kept in a simple substance or alloy state.

In the oil-recovery step of cooling and condensing the hydrocarbon gas generated in such a pyrolysis step and recovering it as oil (fuel oil), the cooling temperature is desirably between room temperature and 250 ° C. . Further, by controlling the cooling temperature in a plurality of stages, heavy oil (heavy oil) and light oil can be separated and collected. The oil thus recovered can be used to heat the inside of the closed vessel in a metal evaporation and recovery step by vacuum heating described later.

In the step of decomposing the halogenated hydrocarbon gas generated in the thermal decomposition step, a decomposition method using a catalyst (catalyst decomposition method) or a decomposition method using plasma (plasma decomposition method) may be employed as the decomposition method. it can. In the catalytic decomposition method, W / ZrO ₂ —ΤiO ₂ , Pt / SiO ₂ —ΤiO _2
2 , Pt / Zr-ΤiO ₂ , ₃ PO ₄ / ZrO ₂ , A
u / Al ₂ O ₃ , Cr ₂ O ₃ / Al ₂ O ₃ , Cr ₂ O ₃
/ ZrO ₂ , Pt-H ₃ PO ₄ / ZrO _{2 and the} like. Further, such a decomposition catalyst and an adsorbent for adsorbing hydrogen halide, which is a decomposition product of halogenated hydrocarbon, for example, CaCO ₃ , Ca (OΗ) ₂ , Ca
By mixing and using O, activated carbon, and the like, the catalyst life can be further extended.

Further, in the plasma decomposition method, for example, steam is used as the plasma gas. Then, after the halogenated hydrocarbon is adsorbed on an adsorbent such as activated carbon or hydrophobic zeolite and concentrated, the concentrated halogenated hydrocarbon is desorbed using steam and decomposed using steam plasma. Can be taken.

The hydrogen halide generated in such a halogenated hydrocarbon decomposition step can be recovered and reused as a hydrohalic acid solution by performing treatments such as cooling and spraying with an aqueous solution.

[0015] Residues in the above-mentioned pyrolysis step still contain metals contained in the original waste, but resins such as foamed resins are dry-dried and pyrolyzed. Exist in a state where they can be easily separated physically or mechanically. Therefore, a predetermined metal can be physically removed by subjecting the residue of the pyrolysis process to an appropriate sorting process. As a physical sorting process,
There are magnetic force sorting, eddy current sorting, specific gravity sorting, and the like. By combining these, metals such as iron, copper, and aluminum can be separated and collected.

In the present invention, a step of evaporating and recovering metal by vacuum heating is performed on the residue from which iron and non-ferrous metals (copper and aluminum) have been removed by subjecting them to physical sorting if necessary. It is. In this vacuum evaporation recovery, a metal having a high vapor pressure is selectively vaporized by heating in a closed vessel close to a vacuum, and then cooled again to recover the precipitated metal. Therefore, high-purity metals can be separated and recovered at a temperature much lower than the boiling point at normal pressure. Thus,
From the residue after physically removing metals, Zn, P
Metals such as b, Cd, Sb, Se, Τe, and Sr are respectively recovered. Separation and recovery of the plurality of metals is performed by changing the metal to be evaporated by changing the pressure and temperature in the closed vessel, and changing each of the metals. By preparing a cooling recovery container for each metal, it is easy to carry out.

In the present invention, such a metal evaporation and recovery step by vacuum heating produces a residue mainly composed of carbides. If a fuel component remains in the obtained residue, the residue is removed. Further, the solidified fuel can be reused by subjecting it to a pressurized solidification treatment or the like.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

FIG. 1 is a diagram showing a schematic configuration of an apparatus used in the waste disposal method of the present invention, and FIG. 2 is a flowchart of an embodiment in which waste disposal is performed using the apparatus shown in FIG. .

In FIG. 1, reference numeral 1 denotes a waste product, such as a waste refrigerator, having a halogenated hydrocarbon-containing foamed resin such as a urethane foamed resin as a constituent material (heat insulating material) and integrating the resin and metal. Reference numeral 2 denotes a two-shaft shearing type coarse crusher for coarsely crushing the waste 1 (to a size of 300 mm or less). A double damper 3 and a pusher 4 are provided below the coarse crusher 2, and the waste crushed by the coarse crusher 2 is sent to a pyrolysis furnace 5 such as a rotary kiln without touching the waste. It has become. Further, the double damper 3 and the double damper 6 provided at the outlet of the residue of the pyrolysis furnace 5 effectively prevent air from entering the pyrolysis furnace 5. Pyrolysis furnace 5
In, by the oxygen concentration control device not shown,
The oxygen concentration in the furnace is controlled so that it is always maintained at 0 to 5% by weight, and the temperature inside the furnace and the rotation speed and inclination of the rotary kiln are kept constant by the dry distillation furnace control device, also not shown. It is controlled to be held in. As described above, in the pyrolysis furnace 5, the oxygen concentration and the temperature in the furnace are respectively controlled to predetermined values, and the halogenated hydrocarbon gas contained in the urethane foam resin or the like is first converted from the waste X that has been charged. It is configured to generate a gas (hydrocarbon gas) of the fuel oil due to thermal decomposition of the resin.

A discharge pipe 7 for these gases generated in the furnace is connected to the pyrolysis furnace 5. The gas discharge pipe 7 is connected to a cooling water introduction pipe 8, a discharge pipe 9, and a cooling pipe. Tube 1
0 and an oil recovery device 12 having an oil recovery container 11. In the oil recovery device 12, three cooling chambers A, B, and C are separately provided in order to cool the gas at three temperatures. And the gas cooling temperature of each cooling chamber,
For example, the cooling temperature of the cooling room A is 250 to 150 ° C., the cooling temperature of the cooling room B is 50 to 150 ° C., and the cooling temperature of the cooling room C is room temperature to 50 ° C.
The temperature is controlled by a cooling temperature control device so that the oil is condensed in each of the cooling chambers, and is collected in separately provided collecting containers.

The oil recovery device 12 is provided with the gas discharge pipe 1.
The catalyst 3 is connected to a halogenated hydrocarbon (fluorocarbon) decomposition device (catalytic decomposition device) 14 through a catalyst 3. W / ZrO, which is a catalyst for decomposing chlorofluorocarbon, is provided in the catalytic decomposition device 14.
_2- ΤiO ₂ and CaC which is an adsorbent for hydrogen halide
O ₃ is used as a mixture, and the temperature of the catalyst tank is controlled to be 500 ° C. by heating.

Further, the catalytic decomposition device 14 is connected to a hydrogen halide recovery device 16 via a gas discharge pipe 15. The hydrogen halide recovery device 16 includes a cooling unit including a cooling water introduction pipe 17, a discharge pipe 18 and a cooling main pipe 19, an aqueous solution spraying apparatus 20 for spraying an aqueous solution onto the cooled hydrogen halide gas, and an aqueous solution circulation pump 21. , And a recovery container 22 for a hydrogen halide (acid) solution. Further, a gas discharge pipe 23 is connected to the hydrogen halide recovery device 16 so as to discharge a gas having a halogen concentration below an environmental standard into the atmosphere. In the recovery of hydrogen halide, each component can be separated and recovered depending on the difference between the condensation temperatures of hydrogen chloride and hydrogen fluoride.

On the other hand, the residue discharge port of the pyrolysis furnace 5 is connected to a biaxial shearing crusher 24 via a double damper 6, and the crusher 24 is connected to a magnetic separation device 25 while being sealed. ing. The magnetic force sorting device 25 includes the magnet belt 2
6, a residue transport conveyor 27, a magnetically separated iron transfer conveyor 28, and an iron recovery container 29. In addition, the residue discharge port of such a magnetic force sorting device 25 is sealed with an eddy current sorting device 31 through a residue transfer pipe 30.
It is connected to the. The eddy current selection device 31 includes an eddy current generation device 32, a residue transport conveyor 33, and a non-ferrous metal transfer conveyor 34. The eddy current generated by the eddy current generation device 32 sorts copper and aluminum contained in the residue. And transferred to the non-ferrous metal transfer conveyor 34. At the end of the non-ferrous metal transfer conveyor 34, there is provided a wind generator 35, a copper recovery container 36 and an aluminum recovery container 37, and a wind separator 38 for separating copper and aluminum using a specific gravity difference. It is connected.

Further, a residue discharge port of the eddy current sorting device 31 is connected to a vacuum evaporation and recovery device 40 via a residue transport pipe 39. The vacuum evaporation recovery device 40 has three chambers, a vacuum preheating chamber 42, a vacuum heating chamber 43, and a pressurized cooling chamber 44, each of which is hermetically sealed by a closed door 41, and transports the residue through these chambers in order. Residue conveyor 45
And a vacuum evacuation device 46, and a metal vapor recovery device 4 that cools, deposits and recovers the metal evaporated in the vacuum heating chamber 43.
7 is provided. The temperature and pressure in each chamber and the residence time of the residue are each optimally controlled by a controller (not shown).

Here, the reduced pressure preheating chamber 42 is a chamber for preliminarily heating under vacuum or under reduced pressure into which a small amount of nitrogen gas (inert gas) is introduced. However, it is introduced in order to add heating by convection and efficiently raise the temperature. Further, the pressurized cooling chamber 44
Is a chamber for returning to atmospheric pressure while introducing nitrogen gas (inert gas) and for gradually cooling to room temperature. In order to protect the vacuum seal in the closed door 41, the vacuum heating chamber 43 is pressurized. An intermediate pressure chamber can be further provided between the cooling chamber 44 and the cooling chamber 44. Further, in order to efficiently collect the metal vaporized and vaporized in the vacuum heating chamber 43 by the metal vapor recovery device 47, an inlet for a carrier gas is provided in the vacuum heating chamber 43, and the metal vapor is supplied to the vapor discharge section 48 together with the carrier gas. And may be sent to the metal vapor recovery device 47 through the. When the metal is continuously evaporated and recovered by vacuum heating, an apparatus having a structure in which three processing chambers (a reduced pressure preliminary heating chamber 42, a vacuum heating chamber 43, and a pressurized cooling chamber 44) are arranged in this manner. Although it is necessary, when performing the processing in a batch, only the vacuum heating chamber 43 is provided, and the pressure and the heating temperature are changed over time, so that the reduced pressure preliminary heating, the vacuum heating, and the pressurized cooling are sequentially performed. May be.

Further, such a vacuum evaporation and recovery device 40
Is connected to a solid fuel production device 49. The solid fuel production device 49 has a compression device and a molding device (not shown), and after compressing a residue containing carbide as a main component at a predetermined pressure, forms a shape suitable for use as a solid fuel. It is configured to be molded.

Using such a device, the waste treatment of the present invention is carried out as follows. That is, as shown in the flowchart of FIG.
A waste 1 having a foamed urethane resin or the like and in which the resin and metal are integrated is first coarsely crushed to a size of 300 mm or less by a biaxial shear type coarse crusher 2 in a coarse crushing step.
It is sent to a pyrolysis furnace (rotary kiln) 5 by a double damper 3 and a pusher 4. Next, in the dry distillation / pyrolysis step, the crushed waste is subjected to dry distillation / pyrolysis in the pyrolysis furnace 5, and the halogenated hydrocarbon gas contained in the urethane foam resin or the like is discharged and generated. Further, a fuel oil gas (hydrocarbon gas) is generated by thermal decomposition of the urethane foam resin and other resins.

The halogenated hydrocarbon gas and the fuel oil gas generated in the pyrolysis furnace 5 are both guided to the oil recovery device 12 through the gas discharge pipe 7. And
In the oil-recovery process, the fuel oil gas passes through three cooling chambers A, B, and C and is cooled and condensed in three stages at each temperature and separated as heavy oil, a mixture of heavy oil and light oil, and light oil. Is collected in the oil collecting container 11. The oil thus recovered can be reused as a fuel and a chemical raw material, and can also be used as a fuel in the vacuum evaporation recovery device 40.

The gas discharged from the oil recovery device 12 is
This is a gas containing a halogenated hydrocarbon (Freon) as a main component. The gas is led to a catalytic decomposition device 14 through a gas discharge pipe 13 and is heated and held at 500 ° C. in a catalyst tank.
/ ZrO ₂ -ΤiO ₂ ) to be decomposed into hydrogen halide and carbon dioxide (fluorocarbon decomposition step).

Next, hydrogen halide (hydrogen chloride or hydrogen fluoride) discharged from such a catalytic decomposition device 14 is used.
A mixed gas of carbon dioxide and carbon dioxide is introduced into a hydrogen halide recovery device 16 through a gas discharge pipe 15 to recover the hydrogen halide. That is, the hydrogen halide gas is turned into an aqueous solution of hydrohalic acid (hydrochloric acid or hydrofluoric acid) by being cooled by the cooling main pipe 19 and further sprayed with the aqueous solution by the aqueous solution spraying device 20. The aqueous solution of hydrohalic acid thus generated is circulated between the aqueous solution spraying device 20 by the aqueous solution circulating pump 21 and sprayed repeatedly to obtain a highly concentrated hydrohalic acid solution (about 35% by weight for hydrochloric acid and about 35% by weight for hydrofluoric acid). 55% by weight saturated aqueous solution). The concentration of the obtained solution is constantly monitored by a concentration measuring device or the like, and is transferred to the collection container 22 when the concentration reaches the specified concentration. The recovered hydrogen halide (acid) solution can be reused as an industrial raw material. The gas from which the halogen has been removed below the environmental standard by the hydrogen halide recovery device 16 is discharged into the atmosphere through the gas discharge tube 23.

On the other hand, the pyrolysis residue discharged from the pyrolysis furnace 5 is crushed to a size of 100 mm or less by a two-shaft shearing crusher 24 (crushing step), and then charged into a magnetic separation device 25. Iron in the crushed residue is separated (magnetic separation step). The sorted iron is collected in an iron collection container 29 by an iron transfer conveyor 28, and can be reused as a metal resource. Next, the residue from which iron has been removed by the magnetic force sorting device 25 is transferred to the eddy current sorting device 31 through the residue transfer pipe 30, where copper and aluminum contained in the residue are sorted, and the non-ferrous metal transfer conveyor 34 is separated. (Eddy current selection step). The sorted copper and aluminum are further separated by a non-ferrous metal transfer conveyor 34 into a wind separation device 38.
And the difference in specific gravity between the two (copper specific gravity: 8.96 g / cm ³ ,
Wind separation can be performed based on the specific gravity of aluminum: 2.70 g / cm ³ ).
And are collected separately (wind sorting process). The recovered copper and aluminum can be reused as metal resources like iron. The residue from which iron, copper and aluminum have been removed in this way is introduced into a vacuum evaporator / recovery device 40 through a residue discharge pipe 39, and a vacuum evaporator / recovery process is performed. In other words, the residue transport conveyor 45 uses the reduced pressure preliminary heating chamber 42, the vacuum heating chamber 43,
Are sequentially transported through the chambers and evaporated and evaporated by vacuum heating.
Metals such as n, Pb, Cd, Sb, Se, Δe, and Sr are cooled and deposited and recovered by the metal vapor recovery device 47. In the vacuum heating chamber 43, the pressure is reduced, for example, from 10 ^-1 to 10 ^-5 Torr by the vacuum exhaust device 46, and the temperature is maintained at a temperature of 400 to 900 ° C. by an electric heater or the like.
In such a vacuum heating chamber 43, for example, lead in the residue
Released as vapor lead. The released lead vapor passes through a vapor discharge section 48 and is sent to a metal vapor recovery device 47 cooled and maintained at a temperature of, for example, about room temperature. Here, the lead vapor precipitates as metallic lead due to a decrease in vapor pressure, and crystallized lead is recovered. Recovered Zn, Pb, Cd, S
Rare metals such as b, Se, Te, and Sr can be reused as valuable resources.

The residue from which the valuable metal is recovered is mainly composed of carbides, which are cooled to normal temperature in the pressurized cooling chamber 44 and pressurized to atmospheric pressure. It is conveyed and compression molded (solid fuel production process). The compression molded residue can be reused as a solid fuel.

Next, another embodiment of the apparatus used in the waste disposal method of the present invention is shown in FIG. In FIG. 3, the same portions as those in FIG. 1 are denoted by the same reference numerals, and description thereof will be omitted.

In the processing apparatus of this embodiment, a chlorofluorocarbon decomposition apparatus (plasma decomposition apparatus) 50 is provided between the oil recovery apparatus 12 and the hydrogen halide recovery apparatus 16.
Are connected to the respective devices via gas exhaust pipes 13 and 15. The plasma decomposition apparatus 50 is provided with a cylindrical honeycomb-type concentrator 54 for concentrating halogenated hydrocarbons (Freon) in front of a plasma generator 53 having a high-frequency induction plasma coil 51 and a plasma frame 52. The concentrator 54 has a rotation mechanism 55 for rotating at a constant speed.

According to the processing apparatus of the embodiment in which such a plasma decomposition apparatus 50 is provided in place of the catalyst decomposition apparatus 14, the gas containing halogenated hydrocarbons as a main component discharged from the oil recovery apparatus 12 is used. Is concentrated by being adsorbed by an adsorbent such as activated carbon or hydrophobic zeolite in a concentrator 54, and then desorbed by steam introduced from a steam introduction pipe 56. The desorbed halogenated hydrocarbon is converted into steam. Along with the plasma flame 52, where it is decomposed into hydrogen halide and carbon dioxide by steam plasma.

Next, such a plasma decomposition apparatus 50 is used.
Mixed gas of hydrogen halide (hydrogen chloride or hydrogen fluoride) and carbon dioxide, which is discharged from the apparatus, is introduced into a hydrogen halide recovery device 16 through a gas discharge pipe 15 to recover hydrogen halide. . That is, the hydrogen halide gas is turned into an aqueous solution of hydrohalic acid (hydrochloric acid or hydrofluoric acid) by being cooled by the cooling main pipe 19 and further sprayed with the aqueous solution by the aqueous solution spraying device 20. The concentration of the obtained solution is constantly monitored by a concentration measuring device or the like, and is transferred to the collection container 22 when the concentration reaches the specified concentration. The gas from which the halogen has been removed below the environmental standard by the hydrogen halide recovery device 16 is discharged into the atmosphere through the gas discharge tube 23.

Next, specific examples of the present invention will be described.

Example 1 Using a continuous waste disposal apparatus shown in FIG. 1, a 450 L-class waste refrigerator was treated. In the dry distillation / pyrolysis process, the controller controls the rotation speed and tilt of the rotary kiln, maintains the furnace temperature at 300 ° C,
The dwell time was 30 minutes. Then, the mixed gas (halogenated hydrocarbon gas and gas of fuel oil) generated in the pyrolysis furnace 5 is introduced into the liquefaction and recovery device 12, where the cooling temperature of the cooling chamber A is reduced to 250. ~ 1
The cooling temperature is controlled such that the cooling temperature of the cooling chamber B is 50 to 150 ° C., and the cooling temperature of the cooling chamber C is room temperature to 50 ° C., and heavy oil, heavy oil and light oil The mixture and light oil were collected separately. Thus, a total of 30 kg of fuel oil was recovered per refrigerator.

In the catalytic decomposition device 14, W, which is a decomposition catalyst, is used.
/ ZrO ₂ -ΤiO ₂ and CaCO ₃ , which is an adsorbent for hydrogen halide generated by decomposition, were used as a mixture. Further, the flow rate of the halogenated hydrocarbon (Freon) gas supplied to the catalyst decomposition device 14 is determined by the SV (space velocity) with the catalyst.
Adjust to 3000 hr ^-1 and raise the temperature of the catalyst tank to 5
Decomposition was performed while maintaining the temperature at 00 ° C. The concentration of chlorofluorocarbon was measured before and after the chlorofluorocarbon decomposition step thus constituted, and the decomposition rate was determined. The decomposition rate was 99.99%, indicating that the decomposition was almost complete.

Next, in the hydrogen halide recovery step, about 1.5 kg of a hydrogen halide (acid) solution was recovered per refrigerator. Also, in the magnetic separation process, per refrigerator
53 kg of iron was recovered, and in the eddy current sorting and wind sorting processes, 3 kg of copper and 0.7 kg of aluminum were used per refrigerator.
Each was recovered.

Further, in the vacuum evaporation and recovery step, the pressure in the vacuum heating chamber 43 is reduced to 10 ^-3 Torr, the temperature is maintained at 630 ° C., and vacuum heating is performed.
When the temperature in 7 was kept at room temperature and the metal was evaporated and recovered by vacuum, 15 g of lead was recovered. Further, after recovering the lead in this manner, 2 kg of a residue mainly composed of carbide was obtained per refrigerator, and the residue was sufficiently usable as a solid fuel after compression molding.

Example 2 Using a continuous waste disposal apparatus shown in FIG. 3, a 450 L-class waste refrigerator was recycled as in Example 1.

The CFC concentration was measured before and after the CFC decomposition step using plasma, and the decomposition rate was determined.
It was found to be 9.99%, almost completely decomposed. In each of the other steps, Example 1 was used.
Good recovery results were obtained as in.

[0045]

As is apparent from the above description, according to the present invention, waste containing foamed resin containing halogenated hydrocarbon such as foamed urethane resin as a constituent material can be substantially converted into halogenated hydrocarbon. It can be completely decomposed, made harmless and collected, and the exhaust gas treatment device can be downsized. In addition, such foamed resin and other resins can be efficiently dried and thermally decomposed to be liquefied and recovered, and the recovered oil can be reused as a chemical raw material or fuel. Further, according to the present invention, metals in waste can be separated and recovered with high purity, and rare metals used in printed wiring boards, electronic components, and the like can be recovered and reused.

Therefore, particularly in the case of a waste refrigerator having a structure in which a large amount of a heat insulating material and a urethane foam resin are used and a structure in which such a foam resin and a metal are integrated, such as a waste refrigerator, conventionally, there is a problem. Although there was only a treatment method such as landfill, by employing the method of the present invention, it is possible to efficiently treat without polluting the environment at a low treatment cost and to reuse various constituent materials respectively. It can be separated and recovered in a form, and is extremely useful from the viewpoint of effective use of limited resources.

[Brief description of the drawings]

FIG. 1 is a diagram showing a schematic configuration of an apparatus used for a waste treatment method of the present invention.

FIG. 2 is a flowchart showing an outline of an embodiment of the waste disposal method of the present invention.

FIG. 3 is a diagram showing a schematic configuration of another embodiment of the waste treatment apparatus of the present invention.

[Explanation of symbols]

2 ... Coarse crusher 5: Pyrolysis furnace 12 .... Oil recovery device 14 Catalyst decomposer 16 ... Halogen halide recovery equipment 24 ……… Crusher 25 .... magnetic separation device 31 ... Eddy current sorting device 38 ... Wind filter 40 Vacuum evaporation recovery device 43 ... Vacuum heating chamber 47 Metal vapor recovery device 49 ...... Solid fuel production equipment 50 Plasma decomposition equipment 54 ... Concentrator

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08J 11/12 B09B 5/00 C // C10B 53/00 ZABQ (72) Inventor Yoshiaki Yokoyama 1807- Takabayashi Hisashi-cho, Ota, Gunma Prefecture 1 Ogihara Ecology Co., Ltd. (72) Inventor Eihisa Ogihara 1807-1 Takabayashi Kotobukicho, Ota City, Gunma Prefecture Ogihara Ecology Co., Ltd. (56) References JP-A-8-229539 (JP, A) JP-A-7-144185 (JP, A) JP-A-3-68486 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B09B 3/00-5/00 B29B 17/00-17 / 02 C08J 11/00-11/28 A62D 3/00

Claims (4)

(57) [Claims] A waste containing a halogenated hydrocarbon-containing foamed resin as a part of a constituent material, and a metal integrated with the foamed resin, is subjected to dry distillation and thermal decomposition to produce the halogen. A pyrolysis step of generating a hydrocarbon gas and generating a hydrocarbon gas; a step of cooling and condensing the hydrocarbon gas to recover oil; and a step of converting the halogenated hydrocarbon gas to a hydrogen halide and a dioxide. A halogenated hydrocarbon decomposition step of decomposing into carbon, and heating the residue of the pyrolysis step while adjusting the temperature and pressure in a closed vessel maintained in a vacuum to remove a metal having a high vapor pressure contained in the residue. And evaporating and recovering the waste. 2. The method according to claim 1, wherein the halogenated hydrocarbon is thermally decomposed by a catalyst in the halogenated hydrocarbon cracking step. 3. The process according to claim 1, wherein in the halogenated hydrocarbon decomposition step, the halogenated hydrocarbon is adsorbed on an adsorbent, concentrated, and then decomposed using steam plasma. Processing method. 4. A halogenated hydrocarbon-containing foamed resin as a part of a constituent material, and a waste having a metal integrated with the foamed resin is subjected to dry distillation and thermal decomposition to produce the halogen. A pyrolysis device that generates a hydrocarbon gas and a hydrocarbon gas; an oil recovery device that cools and condenses the hydrocarbon gas to recover as oil; and converts the halogenated hydrocarbon gas into hydrogen halide and carbon dioxide. A decomposed halogenated hydrocarbon decomposer, a closed container for containing the residue of the waste, a mechanism for heating the inside of the closed container, a mechanism for reducing the pressure in the closed container to a vacuum, and a temperature in the closed container. A waste treatment apparatus, comprising: a control mechanism for adjusting pressure and pressure; and a vacuum evaporation and recovery apparatus having a mechanism for cooling and recovering the evaporated metal vapor.