JP2002282816A - Observation system for organic halide disposal equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an observation system for a PCB disposal equipment which observes an environment of a harmful substance disposal equipment which can perfectly dispose a PCB pollution equipment of a transformer or the like. SOLUTION: The observation system of this invention has a pretreatment means 1006 to pretreat a PCB preservation vessel 1003, a core separation means 1007 to separate a core 1001a treated by the pretreatment means 1006 into a coil 1001b and an iron core 1001c, a coil separation means 1008 to separate the coil 1001b into a copper wire and paper and wood, a wash means 1011 to wash the iron core, a vessel 1003 and a copper wire 1001d, a harmful substance decomposition disposal means 1013 to decompose a wash liquid waste 1012 and a harmful substance 1002, a drainage monitoring means 1100 to measure a PCB concentration in a drainage 133 drained from the harmful substance decomposition disposal means 1013, an exhaust gas monitoring means 1200 to measure the PCB concentration in the pretreatment means 1006 to take apart the PCB disposed substance and the PCB concentration of an exhaust gas 131 exhausted from the harmful substance decomposition disposal means 1013, an adherend concentration monitoring means 1300 to measure a PCB adherend concentration of parts of a vessel or the like washed at the wash means 1011.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic halide processing equipment monitoring system for monitoring the environment of a toxic substance processing equipment capable of completely processing organic halide contaminated equipment such as a PCB such as a transformer.

[0002]

BACKGROUND ART In recent years, PCB (Polychlorinated biph
enyl, polychlorinated biphenyl: a general term for chlorinated isomers of biphenyl), whose production and import are prohibited because of its high toxicity. Although the production of this PCB began in Japan around 1954, the Kanemi Yusho incident triggered a negative impact on living organisms and the environment.
There was a history of production discontinuation and collection instructions (duty of storage) issued by administrative guidance in 2013.

[0003] PCBs contain 1 to 1 chlorine in the biphenyl skeleton.
0 is substituted, and there are theoretically 209 kinds of isomers depending on the number and position of substituted chlorine.
About 100 or more isomers have been identified in CB products. In addition, the physical and chemical properties between the isomers, the in vivo stability, and the environmental dynamics are diverse, and at present, the chemical analysis of PCBs and the manner of environmental pollution are complicated. Furthermore, PCB is one of the persistent organic pollutants, and is hardly decomposed in the environment, is fat-soluble, has a high bioconcentration rate, is semi-volatile, and has the property of being able to move through the atmosphere. In addition, it is reported that it widely remains in the environment such as water and living things. As a result, PCBs are extremely stable in the body, so they accumulate in the body and cause chronic poisoning (skin damage, liver damage, etc.), and are carcinogenic, reproductive,
Developmental toxicity has been observed.

Since PCBs have been widely used as insulating oils for transformers and capacitors, it is necessary to treat the PCBs.
A hydrothermal oxidative decomposition apparatus for detoxifying CB has been proposed (JP-A-11-253796, JP-A-2000-126).
588, etc.). FIG. 11 shows an example of the outline of this hydrothermal oxidative decomposition apparatus.

[0005] As shown in FIG.
Reference numeral 20 denotes a cylindrical primary reactor 122 provided with a cyclone separator 121, PCB, H ₂ O, and NaOH.
Comprising a pressurizing pump 124 for pressurizing the processing liquid 123, a preheater 125 for preheating the mixed liquid, a secondary reactor 126 having a pipe wound configuration, a cooler 127 and a pressure reducing valve 128. It is. Downstream of the pressure reducing valve 127, a gas-liquid separator 129 and an activated carbon tank 130 are arranged. Exhaust gas (CO ₂ ) 131 is discharged from a chimney 132 to the outside, and waste water (H ₂ O, NaCl) 133 is discharged. Separately, wastewater treatment is performed as needed. Exhaust gas (CONi) 131
May be absorbed and removed by, for example, a potassium hydroxide scrubber.

[0006] Further, the piping 1 of the PCB to be the processing liquid 123
In 34, H ₂ O and NaOH are respectively introduced. The oxygen pipe 135 is directly connected to the primary reactor 125.

In the above apparatus, the pressure inside the primary reactor 122 is increased to 26 MPa by pressurization by the pressurizing pump 124. Further, the preheater 125 preheats the mixed solution 123 of PCB, H ₂ O and NaOH to about 300 ° C. Further, oxygen is jetted into the primary reactor 122, and the temperature rises to 380 ° C to 400 ° C due to internal reaction heat. The cyclone separator 121 is connected to the primary reactor 122
The large Na ₂ CO ₃ crystal particles precipitated inside are separated, and the Na ₂ CO ₃ fine particles are sent to the secondary reactor 126. The action of the cyclone separator 121 prevents the secondary reactor 126 from being blocked. By this stage, the PCB
Causes a dechlorination reaction and an oxidative decomposition reaction,
1, CO ₂ and H ₂ O. Next, in the cooler 127, the fluid from the secondary reactor 126 is cooled to 100 ° C.
At the same time, the pressure is reduced to atmospheric pressure by the pressure reducing valve 128 at the subsequent stage. Then, CO ₂ and water vapor are separated from the treated water by the gas-liquid separator 129, and the CO ₂ is discharged into the environment through the activated carbon tank 130 or absorbed and removed by a potassium hydroxide scrubber. The cyclone separator 121 may be provided as needed.

By treating PCB-containing containers (for example, transformers and condensers) and the like using such a processing apparatus, the detoxification is achieved. Further, monitoring of wastewater discharged from the facility and monitoring of the facility. Environmental monitoring is both important.

In view of the above-mentioned problems, the present invention provides an organic halide processing equipment monitoring system for monitoring the environment of a toxic substance processing equipment capable of completely processing organic halide contaminated equipment such as a PCB such as a transformer. The task is to provide.

[0010]

Means for Solving the Problems A first invention for solving the above-mentioned problems is an organic halide processing equipment monitoring system for monitoring the environment of an organic halide processing equipment,
Exhaust gas monitoring means for measuring the concentration of organic halide inside and outside the dismantling facility for dismantling the organic halide treatment product, and wastewater monitoring means for measuring the concentration of organic halide in wastewater discharged from the organic halide treatment facility The monitoring system for organic halide processing equipment is characterized in that:

A second invention is an organic halide processing equipment monitoring system for monitoring the environment of an organic halide processing equipment for detoxifying an object to be processed on which an organic halide is adhered, contained or stored. Extraction means for extracting harmful substances from the processed material, pretreatment means having one or both of dismantling means for dismantling the object, and components constituting the object processed in the preprocessing means Separation means for separating organic matter such as paper, wood, resin, etc. and inorganic matter such as metal, harmful substance decomposition treatment means for decomposing harmful substances separated by pretreatment means, extraction means, disassembly means, separation Exhaust gas monitoring means for measuring the concentration of organic halides in the exhaust gas discharged from the means or harmful substance decomposition treatment means or in the outdoor atmosphere of the treatment equipment; A water discharge monitoring means for measuring the river or organic halide concentration in seawater effluent during or processing near facilities is discharged from the solution treatment unit, in an organic halide processing facility monitoring system characterized by being provided.

In a third aspect, in the second aspect, a cleaning means for cleaning an inorganic substance such as a metal container separated by the extraction means of the pretreatment means or a metal separated by the separation means with a cleaning liquid, Exhaust gas monitoring means for measuring the concentration of organic halide in the exhaust gas discharged from the cleaning means.

According to a fourth aspect of the present invention, in the first aspect, a cleaning means for cleaning a metal container separated by the extraction means of the pretreatment means or an inorganic substance such as the metal separated by the separation means with a cleaning liquid, An organic halide processing equipment monitoring system characterized by comprising an adhesion concentration monitoring means for measuring an organic halide adhesion concentration of the member cleaned by the cleaning means.

According to a fifth aspect of the present invention, there is provided the organic halide processing equipment monitoring system according to the first aspect, wherein the separating means is a crushing means for dividing and crushing the constituent material.

According to a sixth aspect, in the first or third aspect,
An organic halide processing equipment monitoring system is characterized in that the pretreatment means is isolated and in a negative pressure state.

According to a seventh aspect, in the second or fourth aspect,
The organic halide processing equipment monitoring system is characterized in that the harmful substance decomposition treatment means is a hydrothermal oxidation treatment means for hydrothermal oxidation decomposition treatment or a supercritical water oxidation treatment means for supercritical water oxidation treatment.

According to an eighth aspect of the present invention, there is provided the organic halide processing equipment monitoring system according to the first aspect, wherein the exhaust gas monitoring means is a laser ionization time-of-flight mass spectrometer.

According to a ninth aspect, in the eighth aspect, the exhaust gas monitoring means continuously introduces the collected sample into the vacuum chamber, and irradiates the introduced sample with a laser to perform laser ionization. Laser irradiation means for causing a laser ionized molecule to converge,
An organic halide processing apparatus comprising: an ion trap for selectively concentrating the converged molecules; and a time-of-flight mass spectrometer having an ion detector for detecting ions emitted at a constant period. In the equipment monitoring system.

According to a tenth aspect, in the first aspect, the waste water monitoring means is a solid phase extraction-gas chromatograph apparatus, wherein the monitoring system is for an organic halide processing equipment.

According to an eleventh aspect, in the first aspect, the wastewater monitoring means introduces a collected sample, and holds the organic halide with a solid-phase adsorbent; And a detection means for performing a qualitative and quantitative analysis of the organic halide eluted from the organic halide by the eluate.

According to a twelfth aspect, in the eleventh aspect,
The above-mentioned solid-phase adsorbent is made of silica gel or alumina, and is packed in a solid-phase adsorption column.

In a thirteenth aspect, in the eleventh aspect, the eluate for eluting the organic halide held by the solid-phase adsorbent is a nonpolar solvent, alcohol, toluene, dichloromethane, or acetonitrile. An organic halide processing equipment monitoring system is characterized in that:

According to a fourteenth aspect, in the eleventh aspect,
The detection means is any one of a gas chromatograph-mass spectrometer and a gas chromatograph-electron capture detector spectrometer.

In a fifteenth aspect based on the first aspect, the exhaust gas monitoring means and the waste water monitoring means use a gas / solution solution based on absorption of ultraviolet light, visible light or infrared light, or luminescence such as fluorescence. An organic halide processing equipment monitoring system for measuring the concentration of an organic halide in the apparatus.

A sixteenth invention is characterized in that, in the first invention, the exhaust gas monitoring means and the waste water monitoring means measure the concentration of an organic halide in a gas or a solution using a laser beam as a light source. In the monitoring system for organic halide processing equipment.

According to a seventeenth aspect, in the sixteenth aspect,
An organic halide processing equipment monitoring system is characterized in that a phase is detected by applying phase modulation to the laser.

In an eighteenth aspect based on the first aspect, the adhesion concentration monitoring means wipes the surface of the container with a wiping member, extracts the organic halide from the wiping member, and measures the organic halide concentration. An organic halide processing equipment monitoring system is provided.

In a nineteenth aspect based on the first aspect, the adhesion concentration monitoring means samples a part of the container or the member, extracts the organic halide from the sampled member, and measures the organic halide concentration. An organic halide processing equipment monitoring system is characterized in that:

A twentieth aspect of the present invention is the organic halide processing equipment monitoring system according to the first aspect, wherein the adhesion concentration monitoring means dilutes a cleaning liquid and measures an organic halide concentration.

According to a twenty-first aspect, in the first aspect, the object to be processed is a transformer, a condenser, a stabilizer for a fluorescent lamp, and an organic halide contaminant containing the organic halide. It is in the compound processing equipment monitoring system.

[0031]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment of an organic halide processing equipment monitoring system according to the present invention will be described below.
The present invention is not limited to these embodiments.

Next, an organic halide processing equipment monitoring system using the apparatus of the present invention will be described. As shown in FIG. 1, the system according to the present embodiment is a harmful substance processing system for detoxifying an object to which a harmful organic halide (eg, PCB) is attached, contained, or stored. The harmful substances that are the object to be treated 1001 (
For example, from the container 1003 that stores
02, a pretreatment means 1006 having one or both of dismantling means 1005 for disassembling components 1001a, b,... Constituting the object 1001, and a pretreatment means 1006. A core separating means 1007 for separating a core 1001a, which is a constituent material of the workpiece, into a coil 1001b and an iron core 1001c;
Coil separating means 1008 for separating 1001d from paper and wood 1001e
And a core 1001c separated by the core separating means 1008, a metal container (container body and lid, etc.) 1003 separated by the disassembling means 1005, and a copper wire 1001d separated by the coil separating means 1008.
Cleaning means 1011 for cleaning the same with a cleaning liquid 1010, harmful substance decomposition processing means 1013 for decomposing one or both of the cleaning waste liquid 1012 after cleaning and the harmful substance 1002 separated by the pretreatment means, and PCB treatment equipment. Some harmful substance decomposition treatment means
Wastewater monitoring means 1100 for measuring PCB concentration in wastewater 133 discharged from 1013, and PCB concentration and harmful substance decomposition treatment means in pretreatment means 1006 for dismantling PCB processing
It comprises exhaust gas monitoring means 1200 for measuring the PCB concentration of the exhaust gas 131 and the like discharged from 1013, and adhesion concentration monitoring means 1300 for measuring the PCB adhesion concentration of a member such as a container cleaned in the cleaning means 1011. is there.

When the harmful substance is a liquid or the like,
Detoxification processing is performed by directly charging the harmful substance decomposition processing means 1013, and the stored container can be processed by detoxification processing of the constituent materials.

Here, the waste water and exhaust gas after the treatment are checked using the waste water monitoring means 1100, the exhaust gas monitoring means 1200 or the adhesion concentration monitoring means 1300 so as to confirm that they are equal to or less than the emission standard of PCB. I have. Furthermore, the PCB concentration in the environment outside the facility and in rivers, seawater, lake water, and the like near the facility may be monitored using the wastewater monitoring means 1100 and the exhaust gas monitoring means 1200. .

As the harmful substance processing means 1013, FIG.
In addition to the hydrothermal oxidative decomposition treatment means for performing the hydrothermal oxidative decomposition treatment shown in FIG. 1, for example, a supercritical oxidative treatment means for performing supercritical oxidative treatment or a batch type hydrothermal oxidative decomposition means may be used.

Examples of the object to be treated in the present invention include, for example, transformers and capacitors using PCB as an insulating oil, and storage containers storing paints that are harmful substances, but are not limited thereto. Not something.

In the ballast for fluorescent lamps, PCBs have been used in the past, so that it is necessary to perform detoxification processing. In this case, the capacity is small, and the pretreatment is not performed. Detoxification treatment can be performed by charging.

<Drainage Monitoring Means> Examples of the wastewater monitoring means 1100 include a solid phase extraction gas chromatograph as shown in FIGS.

As shown in FIG. 2, the drainage monitoring means 1100 according to the present embodiment is a detection device for detecting the concentration of an organic halide in an aqueous solution,
And a solid-phase / adsorption means 12 for holding an organic halide (PCB) with a solid-phase adsorbent;
And a detecting means 14 for introducing 1 to 5 μl of an eluate 16 from the extract and performing qualitative and quantitative analysis of the eluted organic halide. The introduction of the eluate into the detection means 14 may be carried out automatically, for example, via an autosampler 13, as shown in FIG.

The PCB density detected by the detection means 14 is sent to the monitoring command room, and is also disclosed to the outside by a predetermined monitor device (for example, PCB density display means) 15 by optical communication or the like. Good.

As shown in FIG. 3A, the solid-phase / adsorbing means 12 has a solid-phase adsorbent 22 inserted into an extraction column 21. The solid-phase adsorbent is made of silica gel or alumina. It is composed of

The reason why silica gel or alumina is selected as the solid-phase adsorbent 22 is that it is suitable to efficiently adsorb and separate an organic halide.

The eluate 16 for eluting the organic halide held by the solid phase adsorbent is not particularly limited as long as it is a solvent that elutes only the target organic halide. In Case of,
Examples include nonpolar solvents (eg, n-hexane), alcohols (eg, methyl alcohol, ethyl alcohol, etc.), toluene, dichloromethane, and acetonitrile. Particularly, it is preferable to use n-hexane from the relation with the detector.

Further, since it is necessary to monitor the drainage at predetermined time intervals, a sample introducing means for periodically introducing a collected sample is provided, and automatic sampling becomes possible.

In order to improve the analysis accuracy, if several samples are to be simultaneously performed at the same time as required, a plurality of the columns 21 are prepared, and the organic halides are solid-phase and adsorbed simultaneously. You may make it.

Hereinafter, the extraction step of the solid-phase / adsorption means 12 will be described with reference to FIGS. Conditioning process To obtain reproducible results,
The conditioning liquid 31 is supplied to the solid-phase adsorbent material 22 to allow it to conform (see FIG. 3A). Holding Step Next, the sample 32 is introduced into the column 21 (FIG. 3).
(B)). Here, in the sample, the target PCB
33, impurity X (unnecessary matrix) and impurity Y
(Other components in the matrix). Cleaning Step Next, the impurities X retained on the solid-phase adsorbent 22 are washed away with a cleaning liquid (for example, methyl alcohol) (FIG. 3C).
reference). Elution Step Next, the target substance PCB held by the solid-phase adsorbent 22
33 is eluted with an eluate (n-hexane) 35. At the time of this elution, the impurity Y remains in the solid
33 is separated (see FIG. 3D). In the present embodiment, the PCB has been described as an example of the organic halide. However, the present invention is not limited to this. For example, dioxins in wastewater from factories or incinerators or in water such as rivers. Etc. can also be applied.

FIG. 4 shows a process chart of solid-phase extraction using the above-mentioned organic halide detector. First, 20 mL of n-hexane is supplied to the solid phase adsorbent 22, and solid phase drying (evacuating) is performed for 5 minutes (S101). Next, 20 mL of methyl alcohol and 20 mL of ultrapure water were added.
After flowing mL, a sample (0.1 to 1 L) was introduced, and PCB
Is collected and subjected to solid-phase extraction (S102). At this time, 1% of methyl alcohol was added to the sample. This addition of methyl alcohol has the function of dispersing the PCB. After that, 5 mL of a cleaning liquid (methyl alcohol) is flowed (flow rate: 0.3 cc / s) to perform cleaning (S103). Thereafter, the solid-phase adsorbent 22 is dried (evacuated) for 5 minutes (S104). Then, using n-hexane, the flow rate was 0.3 cc /
As s, PCB is eluted (S105), and the volume is adjusted to 5 mL (S106). Then, a gas chromatograph-mass spectrometer (GC-M
Analyze 1-5 μl with either S) or a gas chromatograph-electron capture detector analyzer (GC-ECD) (S
107), and measure the PCB concentration (S108). The column from which the PCB has been eluted can be backwashed with a mixed solution of n-hexanetoacetone (1: 1), regenerated, and then subjected to PCB measurement again.

The analysis time at this time was less than about 2 hours.
For comparison, a comparison with the conventional official method (measurement time: 2 days) was as follows. The detector was a gas chromatograph-electron capture detector analyzer (GC-EC
D) was used.

The environmental emission standard value is 3 ppb (0.003 mg).
/ L) is required, but according to the apparatus of the present invention, the lower limit of quantification is 0.5 ppb to 0.1 ppb, and it can be adequately dealt with by a rapid analysis and a simple apparatus. Was completed.

Therefore, the present measuring device can be used to analyze at predetermined time intervals to constantly monitor whether or not the wastewater discharge standards are satisfied.
If the concentration exceeds the discharge standard, the tank is switched and sent to the PCB processing device 1013 to treat the PCB in the wastewater again, thereby preventing external environmental pollution.

<Exhaust Gas Monitoring Means> Next, when monitoring the exhaust gas according to the present invention, for example, a laser ionization time-of-flight mass spectrometer can be used.

FIG. 5 shows a specific device of the exhaust gas monitoring means. As shown in FIG. 5, a laser ionization time-of-flight mass spectrometer 50 includes a capillary column 54 which is a sample introduction means for continuously introducing a collected sample into a vacuum chamber, and a leaked molecular beam which is an introduced sample. A laser irradiating means 56 for irradiating the laser 53 with a laser beam 55 to be laser-ionized, a converging section for converging the laser-ionized molecules, an ion trap 57 for selectively concentrating the converged molecules; And a time-of-flight mass spectrometer 60 provided with an ion detector 59 for detecting ions reflected by the Ron 58.

Then, from the comparison of the signal intensities detected by the detector 59, the concentration of the PCB to be measured can be obtained.

FIG. 6 shows a measurement system using the above laser ionization time-of-flight mass spectrometer. As shown in FIG. 6, in the PCB concentration measurement system 62, a gas sampling line 63 branched from a PCB discharge line is connected to a vacuum chamber 52, and leaks into the vacuum chamber 52 from the line 61, and a sample is formed as a molecular beam. Is introduced, ionized by a laser beam 55 from a laser irradiation device 56, and ions are detected by a time-of-flight mass spectrometer 60. In the drawing, reference numeral 63 denotes a vacuum exhaust device for evacuating the vacuum chamber 52, and 64 denotes a controller for controlling these devices. By using this measurement system, detection sensitivity of PCB concentration is 0.01 mg / Nm ^3, the detection time enables highly sensitive rapid analysis within one minute, taking possible real-time analysis.

FIGS. 7A and 7B show an example of a signal from the ion detector that has detected PCB. here,
The horizontal axis is the flight time (second), and the vertical axis is the ion signal intensity (V). Fig. 7 shows the PCB for 4-chlorine.
FIG. 7B is an enlarged view of FIG.

Here, the working environment reference value is determined by the pre-processing means 10.
It is required that the working environment allowable concentration within 06 is 0.1 mg / m ³ or less, but according to the system of the present invention,
The detection lower limit is 0.01 mg / m ³ (10 ppb),
The quick analysis and simple equipment were sufficient to respond.

Also, by monitoring the exhaust gas 131 discharged from the hydrothermal oxidative decomposition device as the harmful substance treatment means 1013, it is possible to monitor whether the hydrothermal oxidative decomposition is performed well.

Exhaust gas from various treatment facilities is concentrated and discharged to the outside after passing through the activated carbon tank. At this time, the PCB concentration can be monitored.

By using the above-mentioned measuring device, for example, the gas in the PCB decomposition treatment equipment can be measured quickly and accurately.
Based on the measurement results, the processing steps can be monitored.

The measured PCB concentration may be sent to a monitoring command room, and may be disclosed to the outside by, for example, a monitor device (not shown).

Although the wastewater monitoring means and the exhaust gas monitoring means are monitored using separate devices, they are not specified in the present invention, but may be, for example, absorption of ultraviolet light, visible light or infrared light or fluorescence. The PCB concentration in the gas / solution may be determined by using a light emission phenomenon such as the above.

In the measurement, it is preferable that the ultraviolet region is 300 nm or less, particularly 200 to 300 nm, the visible region is around 400 to 760 nm, and the infrared region is 900 cm ^-1 or less.
When used for quantification of PCBs, 1 in the infrared region.
This is preferable because there is absorption at 457 cm ^-1 .

At this time, a plurality of wavelengths may be measured at the same time to make a comprehensive judgment in order to ensure that they are PCBs. For example, two wavelengths in the infrared region, two wavelengths in the ultraviolet region, or a combination of the infrared region and the ultraviolet region.

Alternatively, a laser may be used as a light source, and a predetermined optical path length may be set to measure the PCB concentration in exhaust gas or wastewater.

Further, as shown in FIG. 8, a PCB may be detected with high sensitivity by a phase modulation measuring device using a laser. As shown in FIG.
1, a laser light source 73 that irradiates the laser light 72, a laser driving device 74 that controls the light source to emit the laser light 72 of a desired wavelength, and an oscillation that generates a modulation signal that modulates the oscillation wavelength of the laser light. A detector 75 for receiving the transmitted laser light; a frequency multiplier 77 for generating a signal having a cycle of n (n ≧ 2, n is an integer) times the frequency component of the output signal of the oscillator 75; A phase sensitive detector (lock-in amplifier: PSD) 78 that generates a detection signal based on the output signal of the multiplier and the output signal of the detector 76 is provided. According to the phase modulation measurement method using this laser, a modulation is applied to an oscillation laser, and synchronous detection is performed by a frequency-multiplied modulation signal when receiving the laser light.
By obtaining a high-order differential absorption signal as the output, the PCB concentration in the measured object (gas or drainage) can be measured with high accuracy and continuously.

Further, the exhaust gas may be concentrated by, for example, solid phase adsorption, and the PCB concentration may be measured by a gas chromatograph-electron capture detector analyzer (GC-ECD).

Further, the PCB in the exhaust gas is absorbed by a solvent (such as n-hexane), then concentrated and separated by liquid-liquid extraction, and the PCB is analyzed by a gas chromatograph-electron capture detector analyzer (GC-ECD). The concentration may be measured.

Further, a solid phase absorbing material is interposed in a passage of exhaust gas or waste water, PCB is adsorbed on the solid phase absorbing material, and then the concentration of PCB is measured by the absorbance (UV method) by ultraviolet irradiation. Is also good.

<Adhesion Concentration Monitoring Means> Next, a case of monitoring the PCB adhesion concentration after washing according to the present invention will be described.

As the adhesion concentration monitoring means,
The surface of the container after the treatment by the washing means 1011 is formed in a predetermined area (500
cm ² (approximately 25 cm square)) with a wiping member (for example, absorbent cotton), and PCB was extracted from the wiping member with n-hexane.
The CB concentration is measured.

Further, instead of the above-described gas chromatograph method, the above-mentioned gas chromatograph-electron capture detector analyzer (GC-ECD) can be used.

In the case where the wiping area is not large like a container, a rectangular parallelepiped 50 g of about 1 cm ³ or less can be used.
-Extraction of PCB using hexane, and then measurement of PCB concentration by gas chromatography. Further, instead of the gas chromatograph method, the above-described gas chromatograph-electron capture detector analyzer (G
C-ECD) can also be used.

Further, the cleaning solution is diluted to a predetermined concentration, and the diluted solution is subjected to gas chromatography / electron capture detector analyzer (GC-EC).
The PCB concentration can also be measured by D) or the like.

Therefore, by using the present measuring device, it is possible to analyze at predetermined time intervals and to constantly monitor whether or not the wastewater discharge standard is satisfied. In the event of an emergency, the PCB concentration is adjusted to the discharge standard. If it exceeds, the tank is switched and sent to the PCB processing apparatus 1013 to treat the PCB in the drainage again, thereby preventing external environmental pollution.

[0075]

DESCRIPTION OF THE PREFERRED EMBODIMENTS A preferred embodiment of the present invention will be described below, but the present invention is not limited to this embodiment.

FIG. 9 is a plan view of a system according to an embodiment of the processing of the PCB-containing transformer. As shown in FIG. 9, the harmful substance processing system according to the present embodiment is a harmful substance processing system for detoxifying a transformer containing a PCB, and includes a pretreatment for separating a core and a container by pretreatment. A first processing means 301; a second processing means 302 for cutting the core to separate it into a coil and an iron core; and a fourth processing means 304 for crushing the coil and separating it into paper / wood organic matter and copper wire inorganic matter.
And a fifth processing means 305 for cleaning the container, the lid and the separated copper wire, and a sixth processing means 306 for finely pulverizing organic matter of paper and wood to obtain a slurry 95. Is high concentration), a seventh processing means 307 for vacuum drying is interposed between the first processing means 301 and the second processing means 302.

In the present embodiment, when the PCB content of the transformer is low, the first processing means 301 is isolated and the environmental standard is set to a high (class 3) management, and safety is considered. Further, the second processing means 302 to the seventh processing means 307 set the standard of the management area to Class 2 which is the highest after Class 3, and set the safety management level so that the inside of the building becomes Class 1 environmental atmosphere. The classification may be set more finely as needed.

In the first processing means 301, processing is performed in the glove box in order to prevent leakage of the PCB to the outside, and the inside of the glove box is set to a negative pressure. In the first processing means 301, a step of opening a lid that has transported a transformer, a step of opening a transformer lid, a step of setting a lid for cleaning, a step of draining PCB, and a step of rough cleaning And a process of disassembling and extracting the core.

The separated containers 30a, lids 30b, copper wires 90, and irons and other metals are used to finish the fifth cleaning means 30.
Washed in 5 and the valuable material is recycled.
Here, as the PCB adhesion concentration monitoring means,
A post-wash container inspection means 308 for inspecting the washed container is provided.

Further, the washing wastewater after washing and the PCB and the slurry 95 separated by the pretreatment means are decomposed by a hydrothermal oxidative decomposer 120 which is a harmful substance decomposition treatment means 1013. In addition, PCB contaminants (for example, chips, cutting oil, wiping cloth, work clothes, and the like) generated in the processing are similarly decomposed by the hydrothermal decomposition apparatus 120. In addition, the ventilation in the equipment is passed through a purification treatment device such as an activated carbon tank and exhausted to the outside.

After passing through the two-stage activated carbon tanks 130A and 130B, the exhaust gas 131 from the hydrothermal oxidative decomposition device 120 is monitored by exhaust gas monitoring means 309A to 309C and discharged to the outside.

Since the first processing means 301 drains the PCB, the exhaust line 351 is connected to the activated carbon adsorbing device 3.
51 are interposed, and also in this exhaust gas line, first to third exhaust gas monitoring means 309A to 309C are provided.
Monitor the PCB concentration.

Then, the first monitoring means 309A
If the value exceeds the specified value in, the ventilation is sufficient and it is checked whether there is any abnormality in the activated carbon adsorption device.

Also, in the vacuum drying step as the seventh processing means 307, since the PCB concentration is high, the exhaust line 3
50 is provided with an activated carbon adsorption device, and the exhaust gas is monitored in the same manner. Further, the second and third exhaust gas monitoring means 309B and 309C monitor that the exhaust gas is surely processed.

Further, a fourth exhaust gas monitoring means 309D is provided as a working environment inspection means in the control area so as to monitor the inside of the control area 314.

Further, a fifth exhaust gas monitoring means 309D for monitoring the working environment of the container processing chamber in the room of the first means 301 is provided. Thereby, even when there is an abnormal leakage of the PCB during the opening operation of the PCB container, it is possible to quickly monitor the leakage.

The sixth exhaust gas monitoring means 309F for monitoring the environment in the receiving warehouse 320 for storing a plurality of PCB-containing containers before transporting to the first means 301.
Is provided. Thus, when the received PCB container is slightly damaged or the like, and when there is a leakage of the PCB, it is possible to quickly monitor the leakage.

Further, a seventh exhaust gas monitoring means 309G for monitoring the external environment outside the management area is provided. Thus, it is possible to monitor not only the inside of the management area, but also the surrounding environment outside the management area.

Further, in order to improve the reliability of the exhaust gas monitoring, the exhaust gas is concentrated and subjected to solid-phase extraction, which is then subjected to gas chromatography-electron capture detector analysis (GC-EC).
According to D), the concentration can be measured according to the official method.

On the other hand, the wastewater 113 is temporarily stored in the treated water tank 140, and when the wastewater monitoring means 310A as the wastewater inspection means meets the wastewater drainage standard,
It is moved to the buffer tank 141 and then drained.

Further, a river / seawater monitoring means 310 for monitoring a river / seawater in an external environment outside the above-mentioned management area.
B is provided. Thus, it is possible to monitor not only the inside of the management area, but also the surrounding environment outside the management area.

FIG. 10 shows an example of the flow of the processing system described above. As shown in FIG.
Is received, the transformer 30 is opened (S10).
01). Since the internal pressure is applied to the capacitor,
It is necessary to prevent the PCB liquid from blowing out.
Next, the PCB is drained (S1002). The transformer 30 from which the PCB has been extracted is roughly cleaned to reduce the level of the attached PCB (S1003). Next, the lid 30
The transformer container 30a from which b has been removed is placed in a vacuum heating furnace 81, and heated under vacuum (S1004). Subsequently, the transformer 30 having completed the vacuum heating is disassembled (S1005). In addition, the core is cut into an iron core and a coil (S1006). The coil is separated into copper wire and paper / wood (S1007). Slurry paper and wood (S100
8). Subsequently, the metal and insulator generated in the disassembly step of S1005, the iron core separated in the core cutting step of step S1006, and the copper piece separated in step S1007 are washed in an ultrasonic cleaning tank (S1009). Since the iron core is laminated, it is disassembled (S101).
In 1), it is desirable to perform finish cleaning. Next, PCB
In the processing facility 120, the insulating oil drained in step S1002, the cleaning waste liquid, and the slurry generated in step S1008 are hydrothermally oxidatively decomposed (S1010).

The valuable metals such as iron, copper and the like after the above-mentioned finish cleaning are provided for recycling, and the insulators are provided for disposal.

In the container inspection means 309, the surface of the container is subjected to a chemical analysis inspection by wiping or collecting a member, and the surface is set to a predetermined value or less. If the specified value is exceeded,
The finish cleaning process 305 is performed again.

In the present embodiment, the PCB
The concentration control value is monitored by setting a standard of 0.003 mg / L or less.

[0096] By the above monitoring device, P
The amount of CB is monitored. Here, in the present embodiment, the building 31
In order to make the inside of 3 an environmental air standard, the PCB concentration in the environment is set to an area of 0.5 μg / m ³ N or less. This management level is class 1.

Further, the inside of the first control area 314 is an area where the PCB concentration in the environment is 0.1 mg / m ³ N or less. This management level is set to class 2. When working in this area, wear protective gear and work. Furthermore, the PC in the environment is located in the second management area 315.
It is an area where the B concentration can be 0.1 mg / m ³ N or less. This management level is set to class 3 and workers are prohibited from entering this area, and work is performed using, for example, a glove box so as to perform isolated processing. The first management area 314 and the second management area 3
A negative pressure state of 15 is set to prevent contamination from spreading to the outside.

According to the present embodiment, when the transformer having a low PCB content is completely detoxified, the transformer is monitored while monitoring the PCB concentration, so that the working environment can always be maintained in a good state. .

[0099]

As described above, according to the first aspect of the present invention, a PCB for monitoring the environment of a PCB processing facility is provided.
An exhaust gas monitoring means for measuring a PCB concentration inside and outside a dismantling facility for disassembling a PCB processed material, and a P in wastewater discharged from the PCB processing facility.
Since the apparatus is provided with the wastewater monitoring means for measuring the CB concentration, it is possible to perform the PCB treatment while monitoring the PCB concentration.

The second invention is a PCB processing equipment monitoring system for monitoring the environment of a PCB processing equipment for detoxifying an object to be processed on which PCB is attached, contained or stored,
Extraction means for extracting harmful substances from the processing object, pretreatment means having one or both of dismantling means for dismantling the processing object, and components constituting the processing object processed in the preprocessing means Separation means for separating organic matter such as paper, wood, resin and the like and inorganic matter such as metal, and harmful substance decomposition treatment means for decomposing harmful substances separated by pretreatment means,
Exhaust gas monitoring means for measuring the concentration of PCB in exhaust gas discharged from the extraction means, disassembly means, separation means or harmful substance decomposition treatment means, and PCB in wastewater discharged from the harmful substance decomposition treatment means Wastewater monitoring means for measuring the concentration,
The processing of a transformer or the like containing PCB can be integrally and continuously performed, and the processing can be performed while monitoring the PCB concentration, so that the processing can be performed while ensuring the safety of the working environment.

In a third aspect, in the second aspect, there is provided a washing means for washing an inorganic material such as a metal container separated by the extraction means of the pretreatment means or a metal separated by the separation means with a washing liquid. Since exhaust gas monitoring means for measuring the PCB concentration in the exhaust gas discharged from the cleaning means is provided, it is possible to carry out the treatment while cleaning the PCB contaminated material while ensuring the working environment.

A fourth aspect of the present invention is the cleaning apparatus according to the first aspect, wherein the cleaning means is for cleaning an inorganic substance such as a metal container separated by the extraction means of the pretreatment means or the metal separated by the separation means with a cleaning liquid. PC of the member cleaned by the above-mentioned cleaning means
Since it is provided with an adhesion concentration monitoring means for measuring the B adhesion concentration, it is possible to recycle after confirming that PCB is not attached to the recycled member.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a container processing system according to a first embodiment.

FIG. 2 is a schematic diagram of a drainage monitoring system.

FIG. 3 is a process diagram of a drainage monitoring system.

FIG. 4 is a flowchart of a drainage monitoring system.

FIG. 5 is a schematic diagram of an exhaust gas monitoring system.

FIG. 6 is a schematic diagram of a PCB concentration measurement system.

FIG. 7 is an example of a measurement chart from an ion detector that has detected PCB.

FIG. 8 is a schematic diagram of a laser phase modulation measurement device.

FIG. 9 is a schematic diagram of a container processing system according to an example.

FIG. 10 is a flowchart of a drainage monitoring system.

FIG. 11 is a schematic diagram of a hydrothermal oxidative decomposition device.

[Explanation of symbols]

 1001 Object to be treated 1002 Hazardous substances (for example, PCB) 1003 Container 1004 Separation means 1005 Disassembly means 1006 Pretreatment means 1007 Organic matter 1008 Inorganic matter 1009 Separation means 1010 Cleaning liquid 1011 Cleaning means 1012 Cleaning waste liquid 1013 Hazardous substance decomposition treatment means 1014 Slurry 1015 Slurry means 1100 Wastewater monitoring means 1200 Exhaust gas monitoring means 1300 Adhesion concentration monitoring means 11 Sampling sample 12 Solid phase / adsorption means 13 Autosampler 14 Detection means 15 Monitoring device 16 Eluent 50 Laser ionization time-of-flight mass spectrometer 55 Laser light 56 Laser irradiation Means 57 Ion trap 58 Reflectron 59 Ion detector 60 Time-of-flight mass spectrometer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C02F 1/00 G01N 21/27 Z G01N 1/10 21/33 1/22 21/35 Z 21/27 21 / 39 21/33 27/62 K 21/35 V 21/39 27/64 B 27/62 30/00 A 30/72 A 27/64 30/74 E 30/00 F 30/72 30/88 C 30 / 74 33/00 D B09B 3/00 304Z 30/88 ZABZ 33/00 5 / 00Z (72) Inventor Chiyuki Tsukahara 5-717-1 Fukahori-cho, Nagasaki-shi, Nagasaki Sanishi Heavy Industries, Ltd. (72) Inventor Yoshihiro Deguchi 5-717-1, Fukabori-cho, Nagasaki-shi, Nagasaki F-term in Nagasaki Research Laboratory, Mitsubishi Heavy Industries, Ltd. ED03 ED11 GA11 GA24 GA27 JA13 2G059 AA01 BB01 BB04 DD12 EE01 GG01 GG09 HH01 HH02 HH03 HH06 KK01 4D00 4 AA22 AB06 AC05 BA05 CA02 CA04 CA12 CA22 CA39 CA40 DA01 DA10 4D017 AA01 BA04 CA05 CB01 DA03 EB03

Claims (21)

[Claims] 1. An organic halide processing equipment monitoring system for monitoring the environment of an organic halide processing equipment, comprising: an exhaust gas monitoring means for measuring an organic halide concentration inside and outside the dismantling facility for disassembling the organic halide processing product. A wastewater monitoring means for measuring the concentration of organic halide in wastewater discharged from the organic halide treatment equipment, the system for monitoring organic halide treatment equipment. 2. An organic halide treatment equipment monitoring system for monitoring the environment of an organic halide treatment equipment for detoxifying an object to be treated on which an organic halide is attached, contained or stored, wherein the object is harmful. A pre-processing means having one or both of an extracting means for extracting a substance, and a disassembling means for disassembling an object to be processed; and paper / tree / wood from constituent materials constituting the object processed in the pre-processing means. Separation means for separating organic matter such as resin and inorganic matter such as metal; harmful substance decomposition treatment means for decomposing harmful substances separated by pretreatment means; extraction means, disassembly means, separation means or harmful substances An exhaust gas monitoring means for measuring an exhaust gas discharged from the decomposition processing means or an organic halide concentration in an outdoor atmosphere of the processing equipment; Organic halides processing facility monitoring system and drainage monitoring means, characterized by being provided for measuring the river or organic halide concentration in seawater near or during treatment facility effluent discharged from. 3. The cleaning means according to claim 2, wherein the metal container separated by the extraction means of the pretreatment means or the inorganic substance such as the metal separated by the separation means is washed with a cleaning liquid; Exhaust gas monitoring means for measuring the concentration of organic halide in the exhaust gas to be processed. 4. The cleaning means according to claim 1, wherein said cleaning means is for cleaning an inorganic material such as a metal container separated by said extraction means of said pretreatment means or metal separated by said separation means with a cleaning liquid; And an adhesion concentration monitoring means for measuring an adhesion concentration of the organic halide on the selected member. 5. The organic halide processing equipment monitoring system according to claim 1, wherein the separation means is a crushing means for dividing and crushing a constituent material. 6. An organic halide processing equipment monitoring system according to claim 1, wherein said pretreatment means is isolated and in a negative pressure state. 7. The harmful substance decomposition treatment means according to claim 2, wherein the harmful substance decomposition treatment means is a hydrothermal oxidative decomposition treatment means for performing a hydrothermal oxidative decomposition treatment or a supercritical water oxidation treatment means for performing a supercritical water oxidation treatment. Organic halide processing equipment monitoring system. 8. The system according to claim 1, wherein said exhaust gas monitoring means is a laser ionization time-of-flight mass spectrometer. 9. The sample introducing means according to claim 8, wherein said exhaust gas monitoring means continuously introduces the collected sample into the vacuum chamber, and a laser irradiating means for irradiating the introduced sample with a laser and ionizing the laser. A converging section for converging laser-ionized molecules, an ion trap for selectively concentrating the converged molecules, and a time-of-flight mass spectrometer provided with an ion detector for detecting ions emitted at a constant period. An organic halide processing equipment monitoring system, characterized in that: 10. An organic halide processing equipment monitoring system according to claim 1, wherein said wastewater monitoring means is a solid phase extraction-gas chromatograph. 11. The solid-phase / adsorption means according to claim 1, wherein said wastewater monitoring means introduces a collected sample, and holds an organic halide with a solid-phase adsorbent.
An organic halide processing equipment monitoring system, comprising: a detection means for performing qualitative and quantitative analysis of the organic halide eluted by the eluate from the solid phase / adsorption means. 12. The organic halide processing equipment monitoring system according to claim 11, wherein the solid phase adsorbent is made of silica gel or alumina and is packed in a solid phase adsorption column. 13. The method according to claim 11, wherein the eluate for eluting the organic halide held by the solid-phase adsorbent is any one of a nonpolar solvent, alcohols, toluene, dichloromethane, and acetonitrile. Characteristic organic halide processing equipment monitoring system. 14. An organic halide processing equipment monitoring system according to claim 11, wherein said detecting means is one of a gas chromatograph-mass spectrometer and a gas chromatograph-electron capture detector spectrometer. 15. The organic halide in a gas or a solution according to claim 1, wherein the exhaust gas monitoring means and the waste water monitoring means use an emission phenomenon such as absorption of ultraviolet light, visible light or infrared light, or fluorescence. An organic halide processing equipment monitoring system characterized by performing a concentration measurement. 16. The organic halide processing apparatus according to claim 1, wherein the exhaust gas monitoring means and the waste water monitoring means measure the concentration of the organic halide in the gas / solution using a laser beam as a light source. Equipment monitoring system. 17. The system according to claim 16, wherein the laser is subjected to phase modulation to detect a phase. 18. The method according to claim 1, wherein the adhesion concentration monitoring means wipes the surface of the container with a wiping member, extracts the organic halide from the wiping member, and measures the concentration of the organic halide. Organic halide processing equipment monitoring system. 19. The method according to claim 1, wherein the adhesion concentration monitoring means collects a part of the container or the member, extracts the organic halide from the collected member, and measures the organic halide concentration. Organic halide processing equipment monitoring system. 20. An organic halide processing equipment monitoring system according to claim 1, wherein said adhesion concentration monitoring means dilutes a cleaning solution and measures an organic halide concentration. 21. The transformer according to claim 1, wherein the object to be treated contains an organic halide.
An organic halide processing equipment monitoring system, characterized in that it is a condenser, a fluorescent light ballast, and an organic halide contaminant.