JP2003080052A - Hazardous material treating system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hazardous material treating system and a treating method therefor capable of performing the perfect treatment of PCB contaminated apparatuses, such as voltage transformers. SOLUTION: This system is furnished with a pulverizing means 1015 for pulverizing and slurrying organic matter, such as paper, wood and resins, stuck with the hazardous materials or containing these materials and a hazardous material treating means 1013 for decomposing and treating the hazardous materials separated by the treating means 1013 and/or the hazardous materials in the slurry and the maximum grain size of the above slurry 1014 is <=500 μm.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a transformer such as a P
The present invention relates to a hazardous substance treatment system treatment method capable of completely treating CB polluting equipment.

[0002]

BACKGROUND ART In recent years, PCB (Polychlorinated biph)
Since enyl, polychlorinated biphenyl: a generic term for chlorinated isomers of biphenyl) is highly toxic, its production and import are prohibited. Although this PCB was first manufactured in Japan around 1954, its adverse effects on the living body and environment became clear as a result of the Kanemi Yusho incident.
In the past year, there was a history of instructions to discontinue production and collection (duty of storage) due to administrative guidance. PCB is a biphenyl skeleton in which 1 to 10 chlorine atoms are substituted, and 209 kinds of isomers theoretically exist depending on the number and position of the substituted chlorine atoms.
Currently, about 100 or more isomers have been confirmed in commercially available PCB products. In addition, the physical and chemical properties among these isomers, the in vivo stability, and the environmental dynamics are so diverse that the chemical analysis of PCB and the mode of environmental pollution are complicated at present. Further, PCB is one of the persistent organic pollutants, is not easily decomposed in the environment, is fat-soluble, has a high bioconcentration rate, and is semi-volatile, and is capable of being transferred through the atmosphere. In addition, it has been reported that it widely remains in the environment such as water and living things. This PC
B is waste PCB, waste oil containing PCB in 1997,
PCB pollutants were designated as specially controlled waste under the Waste Disposal and Public Cleansing Act.
In the 7th year, wood waste and fiber waste were additionally designated as PCB contaminants. The electrical equipment that becomes a PCB processed product is
There are high-voltage transformers, high-voltage capacitors, low-voltage transformers / capacitors, pole transformers, and as waste PCBs, those used as heat medium include those used as insulating oil, and kerosene used for cleaning these. As the waste pressure-sensitive paper, there is capsule oil used for carbonless paper. Furthermore, it is used when using these PCBs or exchanging heat medium, regenerating insulating oil, cleaning leaks, treating PCB-containing materials, etc. There are PCB pollutants such as activated charcoal, waste white clay, waste wastes, and work clothes. Currently, these are strictly stored, but urgent PCB treatment is desired.

In recent years, various technologies for processing PCBs used in such transformers have been developed.
For example, the technique described in Japanese Patent Laid-Open No. 9-79531 is known.

FIG. 8 shows a flowchart of a PCB processing method according to the above proposal. As shown in FIG. 8, first,
The oil is drained from the transformer in which the PCB is sealed (step S901), and the PCB adhering to the inside is removed by solvent cleaning (step S902), and is collected (step S903). The solvent after cleaning is decomposed together with the oil extracted from the transformer (step S90).
4) It is rendered harmless.

Next, the oil-removed transformer is dried to evaporate the PCB by heating at high temperature and normal pressure in the absence of oxygen (step S905) to prevent the PCB from scattering. Then, the transformer after drying is disassembled (step S906), and the case and the transformer core are separated. The case is provided as a scrap source for an electric furnace or a converter (step S907). On the other hand, the transformer core has its copper coil cut by a mobile shear or the like, and separated into a coil wire and an iron core (step S908).

The separated iron core is melted in the melting furnace and recovered (step S909). Further, the separated copper coil and the organic matter such as paper attached to the copper coil are melted in the induction heating furnace (step S910). Then, the molten copper is recovered, and the PCB gas generated in each melting furnace is detoxified by high-temperature thermal decomposition at 1200 ° C. (step S911).

[0007]

However, in the above-mentioned conventional PCB processing method, since the organic substances such as paper used in the copper coil are burnt in the melting furnace without being separated, the PCB is burned. Exhaust gas containing
Although it is attempted to detoxify it by pyrolyzing it at a high temperature, there is a problem that simply decomposing at a high temperature cannot sufficiently remove PCBs and dioxins that may be by-produced.

Further, since the copper coil is burned without cleaning, there is a risk that copper will be recovered with the PCB still attached.

On the other hand, when cleaning the copper coil,
The PCB or wood used for the copper coil is impregnated with PCB, which takes tens of hours, which is not practical.

Further, in the PCB burning treatment, it is possible to treat the containers storing the PCB, the activated carbon used in the treatment, etc., and the PCB contaminants such as waste white clay, waste waste, work clothes, etc. However, there is a problem that complete processing cannot be performed.

In view of the above-mentioned problems, the present invention is directed to, for example, a PC.
It is possible to completely treat the container of PCB contaminated equipment such as transformers contaminated with B, the contents of the container and the activated carbon used in the treatment, and the PCB contaminants such as waste white clay, waste wastes, and work clothes. An object of the present invention is to provide a hazardous substance treatment system and a method thereof.

[0012]

A first invention for solving the above-mentioned problems is a harmful substance processing system for detoxifying a processed object on which a harmful substance is attached, contained or stored, which is a processed object. Paper from the pretreatment means having either one or both of the first separating means for separating harmful substances from the product and the disassembling means for disassembling the object to be processed, and the constituent material constituting the object to be processed processed by the preprocessing means Second separation means for separating organic matter such as wood / resin and inorganic matter such as metal, fine crushing means for finely crushing the separated organic matter such as paper / wood / resin into slurry, and pretreatment Means for decomposing harmful substances in the slurry and / or harmful substances in the slurry, wherein the average particle diameter of the slurry is 500 μm or less. To the system That.

A second aspect of the present invention is a hazardous substance processing system for detoxifying an object to be treated having a harmful substance attached, contained or stored, wherein the harmful substance is separated from the object to be treated.
Separation means or pretreatment means having any one or both of disassembly means for disassembling the object to be treated, embrittlement means to embrittle the constituent material constituting the object to be treated in the pretreatment means, and Second separating means for separating organic material such as paper or wood or resin and inorganic material such as metal from the constituent material constituting the object to be processed processed in the embrittlement means, and pulverizing the separated organic material. A fine pulverizing means for making a slurry and a harmful substance decomposition treatment means for decomposing the harmful substance separated by the pretreatment means and / or the harmful substance in the slurry are provided, and the average particle diameter of the slurry is 500 μm or less. It is a hazardous substance treatment system characterized by

A third invention is the hazardous substance treatment system according to the first or second invention, wherein the slurry has an average particle diameter of 1 to 100 μm.

A fourth invention is the invention according to any one of the first to third inventions, wherein the slurry has an apparent viscosity of 10 PaS.
-It is a hazardous substance treatment system characterized by being below 25 ° C.

A fifth aspect of the present invention is the hazardous substance treatment system according to any one of the first to fourth aspects, wherein the slurry concentration is 0.01 to 50% by weight.

A sixth invention is the method according to any one of the first to fourth inventions, wherein the slurry transport speed is 0.01 to 1
It is a hazardous substance treatment system characterized by 0 m / sec.

A seventh invention is the harmful substance treating system according to any one of the first to sixth inventions, characterized in that an additive is added to the slurry.

An eighth invention is the harmful substance treating system according to the seventh invention, wherein the additive is a dispersant or a stabilizer.

In a ninth aspect based on the eighth aspect, the dispersant is selected from anionic surfactants, nonionic surfactants, cationic surfactants, neutral surfactants and amphoteric surfactants. It is a hazardous substance treatment system characterized by being at least one kind.

A tenth aspect of the invention is the hazardous substance treatment system according to the eighth aspect, wherein the stabilizer is a water-soluble polymer compound.

An eleventh aspect of the present invention is the hazardous substance treatment system according to the seventh aspect, wherein the amount of the additive added is 0.1 to 10% by weight of the slurry.

A twelfth invention is the invention according to any one of the first to eleventh inventions, wherein the object to be detoxified is PC.
A hazardous substance treatment system characterized by being a transformer containing B, a condenser or a ballast of a fluorescent lamp, and a PCB contaminant.

A thirteenth invention is that in the first or second invention, the harmful substance decomposition treatment step is a hydrothermal decomposition treatment step of hydrothermal decomposition treatment or a supercritical water oxidation treatment step of supercritical water oxidation treatment. It is a hazardous substance treatment system characterized by.

A fourteenth aspect of the present invention is a toxic substance treating method for detoxifying a substance to be treated having a toxic substance adhered to, contained in, or preserved, which comprises a first separation step of separating the toxic substance from the substance to be treated. A pretreatment process having one or both of a dismantling process for disassembling the object to be treated, and organic materials such as paper, wood, resin, etc. and metal such as metal from the constituent materials constituting the object to be treated in the pretreatment step. Second separation step of separating into inorganic matter, fine grinding step of finely grinding the separated organic matter such as paper, wood, resin, etc. into slurry, and harmful substance and / or slurry separated by pretreatment means And a toxic substance decomposition treatment step of decomposing the toxic substance, wherein the slurry has an average particle diameter of 500 μm or less.

A fifteenth aspect of the present invention is a toxic substance treatment method for detoxifying a substance to be treated in which a toxic substance is attached, contained or stored, and a first separation step for separating the toxic substance from the substance to be treated, A pretreatment step having one or both of a disassembling step of disassembling the object to be treated, an embrittlement step of embrittlement the constituent material constituting the object to be treated in the pretreatment step, and a preembrittlement step Second separation step of separating the organic material such as paper, wood, or resin and the inorganic material such as metal from the constituent materials constituting the object to be treated in (1), and pulverizing the separated organic material into a slurry It comprises a fine pulverization step and a harmful substance decomposition treatment step of decomposing the harmful substance separated by the pretreatment means and / or the harmful substance in the slurry, and the average particle diameter of the slurry is 500 μm or less. Characterized by In hazardous material treatment method.

A sixteenth invention is that in the fourteenth or fifteenth invention, the harmful substance decomposition treatment step is a hydrothermal decomposition treatment step of hydrothermal decomposition treatment or a supercritical water oxidation treatment step of supercritical water oxidation treatment. There is a method for treating harmful substances.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the harmful substance treatment system according to the present invention will be described below, but the present invention is not limited to these embodiments. FIG. 1 shows an outline of the system configuration of the hazardous substance processing system of the present invention. As shown in FIG. 1, the harmful substance treatment system according to the present embodiment is a harmful substance treatment system for detoxifying an object to be treated in which harmful substances are attached, contained or stored,
A first separating means 1004 for separating the harmful substance 1002 from a container 1003 storing a harmful substance (eg PCB or the like) 1002 which is an object to be treated (eg transformer, condenser etc.);
A pretreatment means 1006 having one or both of a disassembling means 1005 for disassembling the constituent materials 1001a, b, ... Constituting the treatment object 1001 and a constitution constituting the treatment object processed by the pretreatment means 1006. Material (core, capacitor element, etc.) 10
Second separation means 1009 for separating organic matter 1007 such as paper, wood, resin, etc. and inorganic matter 1008 such as metal from 01a, b, ..., Metal container 1003 separated by the pretreatment means 1006 or the above Cleaning means 1011 for cleaning the inorganic substance 1008 such as metal separated by the separation means 1009 of No. 2 with the cleaning liquid 1010, and cleaning waste liquid after cleaning
1012 and a harmful substance decomposition treatment means for decomposing either or both of the harmful substances 1001 separated by the pretreatment means 1013
And a fine powder contacting means 1015 for finely powdering an organic substance such as paper, wood, resin, etc., to which a harmful substance is attached or contained to form a slurry 1014. In the present embodiment,
The concentration of harmful substances (PCB) in the supplied slurry 1014 is measured using a concentration measuring device 1020.

Here, examples of the harmful substances to be detoxified in the present invention include vinyl chloride sheets, hazardous waste paints, waste fuels, harmful chemicals, waste resins, untreated explosives, etc., in addition to the above-mentioned PCBs. However, it is not limited to these as long as they are harmful substances such as environmental hormones caused by environmental pollution.

Further, in the present invention, the object to be treated is, for example, a storage container for storing waste paint which is a harmful substance, explosives and explosives in addition to a transformer and a capacitor using PCB as insulating oil. Examples of the bombs may include, but are not limited to.

Here, a transformer, which is an example of the object to be processed,
An outline of a condenser or a ballast of a fluorescent lamp will be described with reference to FIGS.

FIG. 5 is a partial sectional view showing the structure of a general transformer. As shown in FIG.
Is a configuration in which a transformer core 203 in which a copper coil 202 is wound around an iron core 201 is housed in an iron container 204, and a PCB is enclosed as insulating oil 205 inside. The copper coil 202 has a structure in which an insulating paper is wrapped around a copper wire, and an insulator 208 is provided on an upper portion of the iron frame 207. Further, the opening of the container 204 is sealed by the lid 209. The capacity range of a general transformer is 5
˜100 kVA, and the present invention can process in all ranges.

FIG. 6 is a partial sectional view showing the structure of a general capacitor. As shown in FIG.
0 is filled in the container 215 in a state in which a plurality of elements 211 are bundled by the fixing band 213 via the press board 212 and covered with the insulating paper 214, and the PCB is sealed from the internal sealing port 216 and sealed. It has been done. Reference numeral 217 is a ground terminal, 218 is a discharge resistor, 219.
Is a high voltage terminal and 220 is an insulator. The element 211 is composed of aluminum foil, insulating paper, resin film, spacers and the like. A typical capacitor has a capacity range of several to 500 kvar, and the present invention can process in all ranges.

FIG. 7 is a schematic view showing a ballast of a general fluorescent lamp. As shown in FIG. 7, the ballast body 230 is
It comprises a ballast 231 and a power factor improving capacitor 232, and PCB is used as insulating oil in the capacitor 232.

Pretreatment for removing harmful substances from these objects to be treated is necessary. For example, in the transformer 200 and the condenser 210, the components are separated and crushed after the PCB is drained. I have to.

The harmful substances such as the extracted PCB and explosives are
Complete decomposition is performed by the harmful substance decomposition processing means 1013. The details will be described later.

In the case of the condenser 232 constituting the ballast 230 for a fluorescent lamp, since the capacity is small, it is directly charged into the second separating means 1009 without pretreatment, or if necessary, after cutting, aluminum is used. By separating the foil,
It can be detoxified.

In the case of a bomb, the container is processed after the explosive or explosive is removed from the bomb. The extracted explosive and the like are processed by the harmful substance decomposition processing means 1013, and the container is washed. Further, the resin container is cut and crushed, and then slurried to be processed by the harmful substance decomposition processing means 1013.

When the harmful substance has fluidity such as liquid, it is detoxified by directly putting it into the harmful substance decomposing treatment means 1013, and the container in which it is stored contains organic matter as a constituent material. In this case, the organic substance can be slurried and treated for detoxification.

Here, the second separating means 1009 and the harmful substance decomposition processing means 1013 may be integrally provided in one facility or the like and may be separately provided, and are not particularly limited. .

This is because when it is difficult to move harmful substances, the pretreatment step of the pretreatment means 1006 and the second separation means 1009 is performed, and then the separated matter is separated. This is because the disposed harmful substance decomposition processing means 1013 may be used for processing.

Further, when the cleaning means 1011 is also provided with a separate cleaning facility to centrally manage the cleaning solvent and treat the exhaust gas, it does not necessarily have to be provided integrally with the present system.

For continuous detoxification of harmful substances, it is preferable in view of management that they are integrally provided in one facility. It is also possible to install this system on a gantry or the like, convey it by the gantry-conveying means, move to a hazardous substance treatment site, and treat it on site.

Further, the second separating means 1009 uses a crushing means for separating the constituent cores, capacitor element parts 1001a, 100b, ... The efficiency of the subsequent processing is improved.

Examples of the crushing means include a crushing device such as a biaxial shear mill, but the present invention is not limited to this.

Further, since the second separating means 1009 includes a selecting means for selecting the crushed pieces crushed by the crushing means into organic substances such as paper, wood and resin, and inorganic substances (copper wire) such as metal, It is possible to recover useful inorganic substances such as copper. For example, the copper coil contains paper and wood that are contaminated with PCB, so the paper and wood that are organic matter and the copper wire that is inorganic matter are separated from the crushed pieces, and PCB is attached to the organic matter. The harmful substance decomposition treatment 1013 is performed while the inorganic substance is washed by the cleaning means 1011.

Examples of the above-mentioned sorting means include automatic sorting methods such as a specific gravity sorting method, a magnet sorting method, a sieve sorting method, and the like. The known sorting means can separate organic substances and inorganic substances. It is not limited to these as long as it is possible.

Further, the selection method may be either dry selection or wet selection. In the case of the above dry sorting method, degreasing and drying are performed by the degreasing treatment means and the drying treatment means before the sorting, so that the subsequent treatment efficiency is improved. On the other hand, in the case of wet sorting, the above-mentioned degreasing treatment and drying treatment are not necessary, and since the sorting is performed by water treatment, the sorted products are directly sent to the harmful substance decomposition treatment means 1013, for example, the hydrothermal decomposition treatment means thereafter. Because you can move
preferable. This wet sorting method is advantageous, as compared with the dry sorting method, because it is not necessary to treat contaminated air. In addition, the treated water used in the wet selection can be reused.

As typical selection methods below, a wet specific gravity difference separation method, an air specific gravity difference separation method, a preheat pretreatment air specific gravity difference separation method, a physical pretreatment post-air specific gravity difference separation method, a chemical method The separation method will be described.

In the wet specific gravity difference separation method, crushed pieces of an organic substance and an inorganic substance are put on a slope where running water is flowing and vibrating, and the slope of the slope is reversed by the vibration of the slope causing the inorganic bump to push up due to the difference in specific gravity. Is a method of bidding to the upper side, and one of the organic substances flows downward along the slope along with the water flow to be separated.

The in-air specific gravity difference separation method is a method in which a crushed material of an organic substance and an inorganic substance is dropped in an air stream, and an organic material having a low specific gravity is blown away by the air stream to separate the crushed material.

In the air-specific gravity difference separation method after pre-heating treatment, when the air-specific gravity difference separation method is wet with organic matter, water or oil, the difference in specific gravity from the inorganic matter becomes small and separation becomes difficult. Therefore, a method is to dry (carbonize) the crushed pieces of organic matter and inorganic matter to reduce the weight of the organic matter and then drop it in an air stream to separate the organic matter having a low specific gravity by the air stream.

After the physical pretreatment, the method for separating the specific gravity in the air is such that, for example, when an aluminum foil which is an inorganic material such as a capacitor element is relatively light and a simple method for separating the specific gravity in the air is difficult, it is possible to separate the organic matter from the inorganic material The crushed pieces are heated to embrittle the organic matter. After that, it is placed in a cylindrical rotating basket with pores, an air stream is generated from the cylinder center axis to the outside of the cylinder, and carbide (brittleness) is crushed by the air stream and discharged through the pores to the outside of the cylinder. This is a separation method in which the foil remains in the cylinder. It should be noted that the crushing of the carbide can be promoted by providing a blade or the like inside the cylinder and rotating and stirring.

The chemical separation method is an acid-alkali separation method,
There is an oil-water separation method. The acid-alkali separation method can be applied when the inorganic substance to be separated is a metal (such as Al). First, crushed pieces of an organic substance and an inorganic substance are dissolved with an acid or an alkali to separate the organic substance. The metal after dissolution is recovered as a metal salt by neutralization. When the metal surface is coated with resin, oil, etc., dissolution by acid and alkali may be hindered, but in this case, the resin or oil is removed by pretreatment, for example, by heat treatment, The metal can be rapidly melt processed.

The oil-water separation method can be applied to the case of separating aluminum foil such as a capacitor element from paper or resin film. First, after cutting the element and the like, the element and the like are poured into a two-phase liquid of water and oil such as kerosene. The aluminum foil and film are peeled off by stirring, and they fall apart. Since the paper contains PCB and has a high specific gravity, it sediments in the lower part of the lower aqueous phase. On the other hand, since the aluminum foil and film have a high affinity with oil, the surface is coated with oil, and as a result, the aluminum foil and film do not move to the water phase side due to the interfacial tension with water and collect at the interface between oil and water. It can be separated by collecting each with a wire mesh or the like.

The separated organic substances such as paper, wood and resin are slurried by the fine pulverizing means 1015.

In addition, activated carbon used in various treatments of harmful substances, waste white clay, waste waste, PCB of work clothes, etc.
When treating pollutants, after cutting or crushing through cutting or crushing means as necessary, it is supplied to the fine crushing means 1015 to form a slurry 1014, and thereafter, harmful substance decomposition treatment. It can be continuously supplied to the means 1013 as it is.

As a result, not only the harmful substance, but also the container used for the treatment, various harmful substance pollutants generated during the treatment, and the like can be consistently rendered completely harmless.

Also, when the object to be processed is, for example, a gun shell, torpedo, or bomb, it can be crushed by embrittlement by crushing the shell.

Examples of the embrittlement means include a method in which the constituent material is embrittled by heating, freezing, or irradiation with ultraviolet rays. The constituent material can be embrittled by known embrittlement means. If there is any, it is not limited to these.

Examples of the harmful substance decomposition treatment means 1013 include hydrothermal decomposition treatment means for hydrothermal decomposition treatment, supercritical water oxidation treatment means for supercritical water oxidation treatment, and batch type hydrothermal decomposition treatment means. However, the present invention is not limited to these as long as the harmful substances can be decomposed by the known harmful substance treatment means. As the harmful substance decomposition treatment means 1013, a continuous treatment method and a batch treatment method can be appropriately adopted.

When the slurry is to be completely decomposed continuously, it is preferable to use a hydrothermal oxidative decomposition treatment means.

Here, in the embodiments described below, with respect to the container containing PCB as the object to be treated,
A processing system for detoxifying the PCB and detoxifying the container constituent material will be specifically described.

As the container containing the PCB, there are, for example, a transformer, a condenser, a ballast for a fluorescent lamp and the like, and the detoxification treatment of these can be performed by the present system. The transformer is the one shown in FIG. 5 described above, which is a low-concentration (several ppm to 100 ppm) PCB container, and the capacitor shown in FIG. 6 is a high-concentration PCB container containing 100 to 60% PCB, In either case, the system of the present invention enables complete detoxification of the PCB and its container.

In the treatment facility of the present invention, harmful substances such as PCB are decomposed by hydrothermal decomposition, and the container is washed in the washing process. However, the organic material such as paper, wood, or resin, which is the constituent material, is impregnated with harmful substances such as PCB, and thus cannot be completely treated by the cleaning treatment.
Therefore, in the present invention, an organic substance containing a harmful substance is finely pulverized to form a slurry 1014, which is decomposed.

The outline of this slurry treatment is shown below.

As shown in FIG. 2, the organic substance 1007 such as paper or wood generated in the second separating means 1009 is slurried in the ultrafine crushing mill 94 to obtain a slurry 1014. In this slurry formation, a piece of cloth wiped off the PCB adhering to the container or the like can be used as the slurry 1014 at the same time.

The above-mentioned slurry formation can be carried out using the fine pulverizing mill shown in FIG. As shown in FIG. 3, the fine crushing mill 94 is provided with a hopper 10 for introducing the separated organic matter.
1 and an outer cylinder drum 102 to which a hopper 101 is attached,
Inner cylinder 10 installed in the outer cylinder drum 102 and rotating inside
3, an agitating blade row 104 provided inside the outer cylinder drum 102 and on the surface of the inner cylinder 103, and a filler 10 for promoting atomization.
4a, a bearing 105 of the inner cylinder 103, a motor and a speed reducer (not shown). Further, a classifying plate 106 is provided downstream in the outer cylinder drum 102, and a nozzle 1 for introducing oil or water used for slurrying is provided in a mounting portion of the hopper 101 and the outer cylinder drum 102.
07 is provided. Further, a slurry discharge port 108 is provided downstream of the outer cylinder drum 102, and the discharge port 108 is connected to a slurry tank 109 for receiving the slurry 1014.

Here, the slurry 1014 slurried in the above-mentioned slurry forming step is processed in the primary reactor 122 of the harmful substance processing means 1013.
It is necessary to efficiently carry 1014. The same applies to the case of treating activated carbon used in various treatments of harmful substances and PCB pollutants such as waste white clay, waste waste, work clothes, etc., as well.

First, when decomposing the slurry,
When transporting a slurry, the properties of viscosity, particle size and static stability are important. The slurry viscosity is determined by the concentration of the slurry and the average particle size of the slurry. When the slurry concentration is high, the viscosity is high, and when the average particle size is small, the viscosity is high. Considering these conditions, the properties of the slurry are preferably set as follows.

The maximum particle size of the above slurry is 500 μm or less, preferably 200 μm or less, more preferably 10 μm or less.
The thickness is preferably 0 μm or less. This has a maximum particle size of 500μ
If it exceeds m, malfunctions such as blockage may occur in the valve or the like of the transfer means for transferring the slurry.

The average particle size of the above slurry is 1 to 100 μm.
The range is m, preferably 10 to 100 μm. This is because when the average particle size is smaller, the decomposition reaction proceeds faster and the stability of the slurry increases, but when it is less than 1 μm, the viscosity of the slurry increases, so that it takes time to generate the slurry, which is not preferable.

The apparent viscosity of the above slurry is 10
PaS (10000cP / 100- ^S ) ・ 25 ° C or less, preferably 3PaS (3000cP / 100- ^S ) ・ 25 ° C
The following is recommended. This is because if it exceeds 10 PaS · 25 ° C., the pump pressure will be burdened and the slurry transfer efficiency will decrease, which is not preferable.

The slurry concentration is 0.01-5.
It is preferably 0% by weight, preferably 1 to 10% by weight.
This is because when it exceeds 50% by weight, the viscosity of the slurry increases, a burden is imposed on the transportation, and the efficiency of the transportation of the slurry decreases, which is not preferable. Also, 0.01% by weight
If it is less than the above value, the amount of water increases, so that the amount of treated organic matter per unit becomes small and the treatment efficiency deteriorates.

Further, the flow velocity in the pipe when the slurry is conveyed is preferably 0.01 to 10 m / sec. This is because when the flow velocity is less than 0.01 m / sec, the shear rate in the pipe becomes small, the viscosity of the slurry increases, and a burden is imposed on the transport by the pump, and the slurry transport efficiency decreases, which is not preferable. . On the other hand, if it exceeds 10 m / sec, the abrasion of the inside of the pipe due to the ash contained in the slurry becomes a problem, which is not preferable.

Additives may be added to the slurry. The addition of the additive may increase the dispersibility to exhibit a dispersion effect for preventing the agglomeration of the slurry, and may increase the stability to exhibit a stabilizing effect for preventing the sedimentation of the slurry. Therefore, the dispersant and the stabilizer may be appropriately used depending on the purpose of adjusting the slurry.

That is, when the additive is not added, the flocculation state is established, the cut surface becomes active, and the slurry particles are apt to aggregate. Therefore,
For the purpose of eliminating this flocculation, a dispersant suitable for the slurry is added to prevent the particles from aggregating.

Further, after the slurry is formed, it is preferable to prevent the agglomeration of the slurry by stirring the stored slurry with a stirring means. Examples of the stirring means include those using a double helical blade.

Here, the dispersant is not particularly limited, but one or more of those having a surface-active action are selected from anionic surfactants, nonionic surfactants, and cationic surfactants. Seeds can be used.

Examples of the anionic surfactants include sodium lignin sulfonate, sodium naphthalene sulfonate, sodium polystyrene sulfonate, and the like. In particular, the above-mentioned sodium ligninsulfonate is recovered from pulp waste liquid, and is effective in adsorbing to paper and wood.

Examples of the above nonionic surfactants include polyoxyethylene and nonyl phenyl ether.

Examples of the above-mentioned cationic surfactants include alkylamines.

The above-mentioned stabilizer is not particularly limited, but a water-soluble polymer compound which exhibits a property of increasing viscosity in an aqueous solution can be used.

Examples of the water-soluble polymer compound include carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA) and the like.

The amount of the above surfactant added is based on the organic matter.
The amount is preferably 0.1 to 10% by weight, more preferably 0.3 to 5% by weight. This is because no further addition efficiency is exhibited even if it is added in excess of 10% by weight, while the addition effect is not exhibited if it is less than 0.1% by weight.

Further, the cleaning water containing the surfactant or the cleaning agent used in the container cleaning step 55 may be used.

Next, in the hydrothermal decomposition system, PCB which is the insulating oil deoiled by the pretreatment means 1006 of the object to be treated, the cleaning waste liquid generated by the cleaning in stage 2, and the slurry 1014 generated in the slurry forming step Etc. are hydrothermally decomposed.

In this hydrothermal decomposition, sodium carbonate (Na ₂ CO ₃ ) crystals are precipitated in hot water, and due to the high surface activity of these crystals, the crystals react with chlorine (Cl) in PCB to form Na.
Process of generating Cl (dechlorination reaction) and PC after dechlorination
It is composed of a step of oxidizing B and oil to decompose into carbon dioxide and water (oxidative decomposition reaction). In this hydrothermal decomposition, the Cl separated from PCB by using sodium carbonate is not corrosive HCl but harmless NaCl.
Therefore, it becomes possible to discharge into the environment.

FIG. 4 shows P used in the harmful substance treating means 1013.
It is a block diagram of the hydrothermal decomposition treatment system 120 of CB.

As shown in FIG. 4, a cylindrical primary reactor 1
22 and oil 123a for combustion, drained PCB123
b, pressurizing pumps 124a to 124d that pressurize each of sodium hydroxide 123c and water 123d, a preheater 125 that preheats a mixed liquid of water and sodium hydroxide, and a secondary reactor 126 having a configuration in which, for example, a pipe is wound. And a cooler 127 and a pressure reducing valve 128. Further, a steam separator 129 and an activated carbon tank 130 are arranged downstream of the pressure reducing valve 127, the exhaust gas (CO ₂ ) 131 is discharged from the chimney 132 to the outside, and the waste water (H ₂ O, NaCl) 133 is discharged. Separately, wastewater is treated as necessary. Also, the oxygen pipe 135
Are directly connected to the primary reactor 122. As for the reactor, if necessary, for example, a primary reactor may be installed in parallel,
Alternatively, the secondary reactor 126 may be omitted if necessary.

In the above apparatus, the pressure pumps 124a ...
Due to the pressurization by d, the inside of the primary reactor 122 is about 26MP.
It is boosted to a. Also, the preheater 125 is a PCB, H
The mixed treatment liquid 123 of ₂ O and NaOH is preheated to about 300 ° C. Also, oxygen is jetting out into the primary reactor 122, and the temperature rises from 370 ° C to 400 ° C due to the heat of reaction inside. The crystals of sodium carbonate (Na ₂ CO ₃ ) precipitated in the subcritical state hydrothermally react with PCB to cause a dechlorination reaction and an oxidative decomposition reaction.
It has been decomposed into ₂ and H ₂ O. Next, the cooler 127
Then, the fluid from the secondary reactor 126 is cooled to about 100 ° C., and is depressurized to atmospheric pressure by the depressurization valve 128 at the subsequent stage. Then, CO ₂ and steam are separated from the treated water by the steam separator 129, and the CO ₂ and steam pass through the activated carbon tank 130 and are discharged into the environment.

Here, the hydrothermal decomposition reaction of PCB in the primary reactor 122 and the secondary reactor 122, which are reactors, will be described.

First, at the start of the reaction, oil, an organic solvent or the like is oxidized by an oxidizing agent (oxygen is used in this embodiment) supplied into the tower from an oxidizing agent supply source to generate carbon dioxide. For example, as an organic solvent, toluene (C ₆ H ₅ C
H ₃ ) is used as an example, C ₆ H ₅ CH ₃ +
CO ₂ is produced by the reaction of 9O ₂ → 4H ₂ O + 7CO ₂ . This oxidation reaction is an exothermic reaction, whereby the temperature in the system rises and the pressure rises accordingly. In the present embodiment, when the temperature and pressure in the primary reactor 122 are maintained at about 370 ° C. and about 26 MPa, respectively, the PCB is the most
It has been found that the decomposition rate of is improved.

The CO ₂ produced as described above reacts with sodium hydroxide supplied with the PCB in the primary reactor 122 to produce sodium carbonate (Na ₂ CO ₃ ). 2NaOH + CO ₂ → Na ₂ CO ₃ + H ₂ O (A) Next, Na ₂ CO produced by the reaction of the above (A)
₃ reacts with PCB, desalting and oxidatively decomposing PCB. C ₁₂ H ₆ Cl ₄ + 12.5O ₂ + 2Na ₂ CO ₃ → 4NaCl + 3H ₂ O + 14CO ₂ (B) In the case of the above-mentioned PCB having a chlorine number of 4, the same reaction is obtained for other chlorine numbers. Occurs, PCB is H ₂
It is decomposed into O, CO ₂ , and NaCl. The CO ₂ generated by the above reaction (B) is further converted into N ₂ by the above reaction (A).
Na ₂ CO that reacts with aOH and is required for the reaction of (B)
_Will generate ₃ . By the way, the above (B) PC
In the B decomposition reaction, sodium carbonate (Na ₂ C
O ₃ ) acts not only as a reaction agent but also as a catalyst for promoting the decomposition reaction of (B). Further, it has been found that the decomposition reaction of the above (B) is promoted in an alkaline atmosphere (for example, pH 10 or higher).

According to the hydrothermal decomposition apparatus 120, it can be decomposed to 0.5 ppb or less, which is less than the current PCB emission standard value (3 ppb), and can be completely decomposed. This allows PCB
It becomes possible to completely treat the contained article and completely eliminate the PCB.

Further, by setting the properties of the slurry 1014 supplied to the primary reactor 122 to the above-mentioned peculiar parameters, the transport efficiency and the decomposition efficiency of the slurry are improved, and the PCB is improved.
It is possible to quickly and efficiently treat harmful substances such as.

Thus, the hydrothermal decomposition system 120
By using, it becomes possible to surely decompose the PCB in hot water. In addition, organic compounds other than PCB can also be decomposed, and dioxins contained in PCB, organic substances such as paper, wood, cloth contaminated with PCB, and cleaning agents used for cleaning the case can also be decomposed. It will be possible. The above hydrothermal decomposition method has already been disclosed by the applicant of the present application, and for details, refer to JP-A Nos. 11-639 and 11-253795. According to the PCB processing method described above, it is possible to safely and reliably process a transformer or the like including a PCB.

In the above system, the slurry 1014
Even if the concentrations of the cleaning waste liquid 1012, the cleaning waste liquid 1012, and the PCB contaminants supplied from the outside vary, before the treatment with the hydrothermal decomposition treatment apparatus 120, the PCB concentration measuring means 1020.
I am trying to measure using. The PCB concentration measuring means 1020 is, for example, a carbonizing means for carbonizing a sample (slurry) taken in a fixed amount, an extracting means for extracting an organic halide from the carbonized sample with an organic solvent, and an organic halide in the organic solvent. And a fluorescent X-ray measuring means for measuring the total amount of the organic halide impregnated in the slurry 1014 is exposed by carbonization, the PCB is extracted with an organic solvent, and the PCB concentration is determined from the X-ray intensity of chlorine. It is a simple and quick measurement. This enables high concentration PCB
It can be confirmed each time whether it is a low concentration PCB (several ppm). Therefore, if necessary, it is possible to perform a decomposition process according to the PCB concentration.

As described above, in the above-mentioned embodiment and its modification, the hydrothermal decomposition apparatus by the applicant of the present application is mentioned, but the present invention is not limited to this configuration, and any apparatus capable of implementing the same principle can be used. It may have any configuration. Furthermore, in the above-described first embodiment and its modification, the hydrothermal decomposition method is mentioned as the PCB treatment method, but a supercritical water oxidation method may be used instead of this. The supercritical water oxidation method is a method in which water is pressurized to a pressure higher than the critical pressure by a high-pressure pump, an organic substance containing PCB and a cleaning waste liquid are charged therein, and oxidatively decomposed by an oxidizing agent. According to the supercritical water oxidation method, high reaction efficiency can be obtained in an extremely short time. Further, similar to the hydrothermal decomposition method, there is an advantage that harmful substances such as dioxins are not generated.

[0100]

As described above, according to the present invention, the characteristics of the slurry supplied to the processing equipment for decomposing harmful substances such as PCB are set to the above-mentioned specific parameters, whereby the slurry Transport efficiency and decomposition efficiency are improved, and harmful substances such as PCB can be processed quickly and efficiently.

[Brief description of drawings]

FIG. 1 is a schematic diagram of a system configuration of a hazardous substance processing system.

FIG. 2 is a schematic view of a finely divided means.

FIG. 3 is a process drawing of a fine grinding mill.

FIG. 4 is a schematic diagram of a hydrothermal decomposition treatment system.

FIG. 5 is a cross-sectional view showing the structure of a general transformer.

FIG. 6 is a cross-sectional view showing the structure of a general capacitor.

FIG. 7 is a cross-sectional view showing a structure of a general ballast.

FIG. 8 is a flowchart showing a conventional PCB processing method.

[Explanation of symbols]

1001 object 1002 Hazardous substances (eg PCB) 1003 containers 1004 Separation means 1005 Dismantling method 1006 Pretreatment means 1007 organic matter 1008 inorganic 1009 Separation means 1010 cleaning solution 1011 Cleaning means 1012 Wash waste liquid 1013 Hazardous substance decomposition processing means 1014 slurry 1015 Slurrying means

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification symbol FI theme code (reference) C07B 37/06 B09B 5/00 C C07C 25/18 3/00 Z (72) Inventor Takashi Yamamoto Nagasaki Nagasaki Prefecture 5-717-1, Fukahori-cho, Nagasaki, Sanryo Heavy Industries Co., Ltd. Nagasaki Research Institute (72) Inventor Kenji Nishizawa 5-717-1, Fukahori-cho, Nagasaki City, Nagasaki Sanryo Heavy Industries Co., Ltd. (72) Inventor Oura Koji No. 1-1, Atsunoura Town, Nagasaki City, Nagasaki Prefecture Mitsubishi Heavy Industries, Ltd. Nagasaki Shipyard F Term (reference) 2E191 BA13 BC01 BD11 4D004 AA07 AA12 AA22 AB06 CA02 CA04 CA12 CA39 CB04 CB13 CB31 CB42 CC02 CC05 CC12 DA02 DA03 DA06 DA07 DA10 DA12 DA12 DA20 4H006 AA05 AC13 AC26 BA73 EA22

Claims (16)

[Claims] 1. A hazardous substance treatment system for detoxifying an object to be treated having a harmful substance attached, contained or stored, comprising: a first separating means for separating the harmful substance from the object to be treated; Pretreatment means having one or both of the disassembling means for disassembling, and separating from the constituent materials constituting the object to be treated by the pretreatment means into organic substances such as paper, wood and resin, and inorganic substances such as metals A second separating means, a fine pulverizing means for finely pulverizing the separated organic matter such as paper, wood, resin, etc. into a slurry, and decomposing the harmful substance separated by the pretreatment means and / or the harmful substance in the slurry. A toxic substance treatment system comprising: a toxic substance decomposing treatment means for treating the toxic substance, wherein the slurry has a maximum particle size of 500 μm or less. 2. A hazardous substance treatment system for detoxifying an object to be treated having a harmful substance attached, contained or stored, comprising: a first separating means for separating the harmful substance from the object to be treated or the object to be treated. Pretreatment means having one or both of the disassembling means for disassembling, the embrittlement means for embrittlement the constituent material constituting the object processed by the pretreatment means, and the object processed by the preembrittlement means Second separating means for separating organic matter such as paper or wood or resin and inorganic matter such as metal from the constituent materials constituting the treated product, and finely pulverizing means for finely pulverizing the separated organic matter to form a slurry, And a harmful substance decomposition treatment means for decomposing the harmful substance separated by the pretreatment means and / or the harmful substance in the slurry, wherein the maximum particle diameter of the slurry is 500 μm or less. object Processing system. 3. The hazardous substance processing system according to claim 1, wherein the slurry has an average particle size of 1 to 100 μm. 4. The hazardous substance processing system according to claim 1, wherein the apparent viscosity of the slurry is 10 PaS · 25 ° C. or less. 5. The hazardous substance processing system according to claim 1, wherein the slurry concentration is 0.01 to 50% by weight. 6. The hazardous substance processing system according to claim 1, wherein a transportation speed of the slurry is 0.01 to 10 m / sec. 7. The hazardous substance processing system according to claim 1, wherein an additive is added to the slurry. 8. The hazardous substance treatment system according to claim 7, wherein the additive is a dispersant or a stabilizer. 9. The dispersant according to claim 8, wherein the dispersant is at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants, neutral surfactants and amphoteric surfactants. Hazardous substance treatment system characterized by being present. 10. The hazardous substance treatment system according to claim 8, wherein the stabilizer is a water-soluble polymer compound. 11. The hazardous substance processing system according to claim 7, wherein the additive is added in an amount of 0.1 to 10% by weight with respect to the slurry. 12. The harmful substance according to any one of claims 1 to 11, wherein the object to be detoxified is a transformer containing a PCB, a condenser or a ballast of a fluorescent lamp, and a PCB contaminant. Material processing system. 13. The harmful substance according to claim 1 or 2, wherein the harmful substance decomposition treatment step is a hydrothermal decomposition treatment step of hydrothermal decomposition treatment or a supercritical water oxidation treatment step of supercritical water oxidation treatment. Material processing system. 14. A method for treating a harmful substance, which detoxifies a substance to which the harmful substance is attached, contained or stored, comprising: a first separation step of separating the harmful substance from the substance; A pretreatment process that has one or both of a dismantling process to dismantle, and separates the constituent materials that make up the object processed in the pretreatment process into organic substances such as paper, wood, resin, etc., and inorganic substances such as metals. A second separation step, a fine pulverization step of finely pulverizing the separated organic matter such as paper, wood, resin, etc. into a slurry; and a harmful substance separated by the pretreatment means and / or a harmful substance in the slurry. And a step of decomposing a harmful substance, which is characterized in that the average particle diameter of the slurry is 500 μm or less. 15. A method of treating a harmful substance, which detoxifies a substance to which the harmful substance is attached, contained or stored, comprising: a first separation step of separating the harmful substance from the substance to be treated; A pretreatment process that has one or both of a disassembly process for dismantling, an embrittlement process that embrittles the constituent materials that make up the object processed in the pretreatment process, and a preembrittlement process A second separation step of separating organic substances such as paper or wood or resin and inorganic substances such as metal from the constituent materials constituting the object to be treated, and a fine pulverization step of finely pulverizing the separated organic substances to form a slurry A toxic substance decomposition treatment step of decomposing the toxic substance separated by the pretreatment means and / or the toxic substance in the slurry, wherein the average particle diameter of the slurry is 500 μm or less. Hazardous substance Management method. 16. The harmful substance according to claim 14 or 15, wherein the harmful substance decomposition treatment step is a hydrothermal decomposition treatment step of hydrothermal decomposition treatment or a supercritical water oxidation treatment step of supercritical water oxidation treatment. Material processing method.