JP2003010671A - Operation control system of hazardous substance treating apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic halide decomposition treatment system for realizing complete treatment of materials containing PCB such as an insulating oil. SOLUTION: In the operation control system of a hazardous substance treating apparatus which controls the operation of the treating apparatus for decomposition treatment of organic halides or hazardous substances containing the organic halides, or the like, there is provided a waste water measuring means 201A as a monitoring means measuring the concentration of the organic halides in the waste water 133 discharged from the treating apparatus 120 for decomposition treatment of the above hazardous substances or an index substance of the concentration of the decomposed substances, or the like, at a measuring point A, and when the above index substance exceeds a specified value, the waste water 133 is temporarily stored in a storage tank 202 or treated again in the apparatus without directly discharging the waste water 131.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic halide decomposition treatment system for complete treatment of PCB-containing substances such as insulating oil for transformers and the like.

[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 has 1 to 1 chlorine in the biphenyl skeleton.
It has 0 substitutions, and theoretically there are 209 kinds of isomers depending on the number and position of the substituted chlorine.
About 100 or more isomers have been confirmed in CB 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. As a result, since PCB is extremely stable in the body, it accumulates in the body and causes chronic poisoning (skin disorders, liver disorders, etc.), carcinogenicity, reproduction and reproduction.
Developmental toxicity is noted.

Since PCB has been widely used as an insulating oil for transformers and capacitors, it is necessary to treat the PCB.
A hydrothermal oxidative decomposition apparatus for detoxifying CB has been proposed (JP-A-11-253795, JP-A-11-2537).
96, JP 2000-126588 A, etc.). FIG. 12 shows an example of the outline of this hydrothermal oxidative decomposition apparatus, but the invention is not limited to this.

As shown in FIG. 12, a hydrothermal oxidative decomposition apparatus 1
Reference numeral 20 denotes a cylindrical primary reaction tower 122 provided with a cyclone separator 121, oil (or organic solvent), PCB,
Pressurizing pump 124 for pressurizing treatment liquids 123a to 123d of water (H ₂ O) and sodium hydroxide (NaOH).
And a heat exchanger 125 for preheating the water, a secondary reaction tower 126 having a spirally wound pipe, a cooler 127, and a pressure reducing valve 128. Further, a gas-liquid separator 129 and an activated carbon tank 13 are provided downstream of the pressure reducing valve 127.
0 is arranged, and the exhaust gas (CO ₂ ) 131 is the chimney 1
32 is discharged to the outside, and waste water (H ₂ O, NaCl) 1
33 is stored in the discharge tank 134, and is separately drained if necessary.

Each of the processing liquids 123 of oil (or organic solvent), PCB, H ₂ O, and NaOH which becomes the processing liquid 123.
a to 123d are introduced from the processing liquid tanks 135a to 135d through the pipes 136a to 136d and the ejector 137, respectively. Further, an oxidant such as oxygen (O ₂ ) is supplied by the high pressure oxygen supply equipment 138, and the supply pipe 139.
Are directly connected to the primary reaction tower 122. In addition,
The reason for adding the oil (or the organic solvent) is to accelerate the decomposition reaction of the high-concentration PCB, and to raise the reaction temperature to the optimum temperature when the decomposition device 120 is started. Alternatively, the above-mentioned PCB, H ₂ O and NaOH may be mixed as a treatment liquid and charged into the primary reaction column 122.

In the above apparatus, the pressure in the primary reaction tower 122 is increased to 26 MPa by pressurization by the pressurizing pump 124. The heat exchanger 125 uses H ₂ O at 300 ° C.
Preheat to a degree. In addition, oxygen is ejected into the primary reaction tower 122, and the reaction heat inside causes 380 to 400 ° C.
Up to. The cyclone separator 121 separates large Na ₂ CO ₃ crystal particles precipitated in the primary reaction tower 122 and separates Na ₂ CO ₃ particles into the secondary reaction tower 126.
Send to. The action of the cyclone separator 121 prevents the secondary reaction tower 126 from being blocked. By this stage, the PCB has undergone a dechlorination reaction and an oxidative decomposition reaction and has been decomposed into NaCl, CO ₂ and H ₂ O. Next, in the cooler 127, the fluid from the secondary reaction tower 126 is cooled to about 100 ° C. and the pressure is reduced to atmospheric pressure by the pressure reducing valve 128 at the subsequent stage. Then, the gas-liquid separator 129 separates CO ₂ and steam from the treatment liquid, and the CO ₂ and steam pass through the activated carbon tank 130 and are discharged into the environment. PCB is dechlorinated by treating PCB-containing oil (for example, insulating oil such as a transformer or a capacitor) by using such a treatment device 120, and the PCB is dechlorinated ((C ₆ H
₅ ) Dechlorinated compounds such as ₂ ) are obtained, and the biphenyl is completely detoxified into CO ₂ , H ₂ O, etc. by the action of an oxidizing agent and the like.

[0008] However, by treating harmful substances such as PCB using the above-mentioned treatment equipment, it has been made completely harmless, but its efficient operation is desired.

In view of the above-mentioned problems, the present invention provides an operation control system for a hazardous substance treatment facility for efficiently controlling the operation of a hazardous substance treatment facility for treating harmful substances such as PCB from a transformer or the like. Is an issue.

[0010]

A first invention for solving the above-mentioned problems is a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing an organic halide or a hazardous substance containing the organic halide. The operation control system of the above, comprising a monitoring means for measuring the concentration of the indicator substance such as an organic halide or its decomposition product in the wastewater discharged from the treatment facility for decomposing the harmful substance, the concentration of the indicator substance is When the value exceeds a predetermined value, the operation control system of the organic halide treatment equipment is characterized in that the wastewater is temporarily stored or treated again in the treatment equipment without being discharged.

A second aspect of the present invention is an operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing and treating an organic halide or a harmful substance containing the organic halide. Equipped with wastewater monitoring means to measure the concentration of indicator substances such as organic halides or their decomposition products in the wastewater discharged from the treatment facility for decomposition treatment, and if the concentration of the indicator substance in the wastewater exceeds a prescribed value, decomposition It is an operation control system of an organic halide treatment facility characterized by optimizing the decomposition conditions of the treatment facility.

A third aspect of the present invention is an operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing and treating an organic halide or a harmful substance containing the organic halide. Equipped with wastewater monitoring means to measure the concentration of indicator substances such as organic halides or their decomposition products in the wastewater discharged from the treatment facility for decomposition treatment, and if the concentration of the indicator substance in the wastewater exceeds a prescribed value, decomposition An operation control system for an organic halide treatment facility, characterized in that the supply amount of a harmful substance supplied to the treatment facility is adjusted or stopped.

A fourth aspect of the present invention is an operation control system of a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing and treating an organic halide or a harmful substance containing the organic halide. Equipped with reaction solution monitoring means for measuring the concentration of indicator substances such as organic halides or their decomposition products in the decomposition reaction liquid, and if the concentration of the above-mentioned indicator substances exceeds a specified value, the decomposition conditions of the decomposition treatment equipment should be appropriate. An operation control system for an organic halide treatment facility, which is characterized in that

A fifth aspect of the present invention is an operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing and treating an organic halide or a harmful substance containing the organic halide. Equipped with a reaction solution monitoring means for measuring the concentration of the indicator substance such as the concentration of organic halides in the decomposition reaction solution or the concentration of its decomposition products, and when the indicator substance in the reaction solution exceeds a specified value, it is supplied to the decomposition treatment facility. In the operation control system of the organic halide treatment facility, which is characterized by adjusting or stopping the supply of the harmful substance.

A sixth aspect of the present invention is an operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing and treating an organic halide or a harmful substance containing the organic halide. When the concentration of the indicator substance in the exhaust gas exceeds the specified value, equipped with wastewater monitoring means that measures the concentration of the indicator substance such as organic halides or its decomposition products in the exhaust gas discharged from the treatment facility for decomposition treatment. The operation control system of an organic halide treatment facility is characterized by optimizing the decomposition conditions of the decomposition treatment facility.

A seventh aspect of the present invention is an operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing and treating an organic halide or a harmful substance containing the organic halide. When the concentration of the indicator substance in the exhaust gas exceeds the specified value, equipped with wastewater monitoring means that measures the concentration of the indicator substance such as organic halides or its decomposition products in the exhaust gas discharged from the treatment facility for decomposition treatment. The operation control system for an organic halide treatment facility is characterized by adjusting or stopping the supply of a harmful substance to be supplied to a decomposition treatment facility.

An eighth aspect of the present invention is the fuel cell system according to any one of the first to seventh aspects, wherein the treatment facility for decomposing the harmful substances is sodium carbonate (Na) in the heated and pressurized reaction tower.
₂ CO ₃ ) in the presence of sodium chloride (NaC) by dehalogenation reaction and oxidative decomposition reaction of an organic halide.
1), a hydrothermal oxidative decomposition apparatus for decomposing into carbon dioxide (CO ₂ ), etc., in an organic halide treatment facility monitoring system.

In a ninth aspect based on the eighth aspect, the hydrothermal oxidative decomposition apparatus comprises a cylindrical primary reaction tower provided with a cyclone separator, and an oil or an organic solvent, an organic halide, water (H ₂ O). ) And sodium hydroxide (NaOH)
A pressurizing pump for pressurizing each treatment liquid, a preheater for preheating the water, and a secondary reaction tower having a configuration in which a pipe is spirally wound,
An organic halide treatment facility monitoring system comprising a cooler for cooling the treatment liquid from the secondary reaction tower, a gas-liquid separation means for separating the treatment liquid into gas and liquid, and a pressure reducing valve.

In a tenth aspect based on the ninth aspect, the reaction solution during the reaction process is monitored in the reaction solution between the primary reaction column and the secondary reaction column in the hydrothermal oxidative decomposition apparatus, or gas-liquid separation. The organic halide treatment facility monitoring system is characterized in that it is carried out either in the wastewater after separation by means.

The eleventh invention is the tenth invention, wherein
The above-mentioned operation control includes heating control of the organic halide decomposition treatment facility, pressurization control, control of the amount of the organic halide treatment solution, control of the amount of the oxidizing agent, or sodium hydroxide (N).
The organic halide treatment equipment monitoring system is characterized in that it is at least one of the control of the input amount of aOH).

A twelfth invention is the organic halide treatment equipment monitoring system according to the first invention, wherein the exhaust gas monitoring means is a laser ionization time-of-flight mass spectrometer.

A thirteenth invention is the tenth invention, wherein
The sample introduction means for the exhaust gas monitoring means to continuously introduce the sample to be collected into the vacuum chamber, the laser irradiation means for irradiating the introduced sample with a laser to cause laser ionization, and the converging unit for converging the laser ionized molecules. And an ion trap for selectively concentrating the converged molecules, and a time-of-flight mass spectrometer equipped with an ion detector for detecting ions emitted at a constant cycle. It is in the chemical treatment equipment monitoring system.

The fourteenth invention is any one of the first to seventh inventions.
In the invention, the wastewater monitoring means is a solid-phase extraction gas chromatograph, which is an organic halide treatment equipment monitoring system.

The fifteenth invention is any one of the first to seventh inventions.
In the invention described above, the wastewater monitoring means introduces a sample to be collected, and a solid phase / adsorption means for holding an organic halide with a solid phase adsorbent, and an organic halide eluted from the solid phase / adsorption means by an eluent The organic halide treatment facility monitoring system is provided with a detecting means for performing qualitative and quantitative analysis.

The sixteenth invention is any one of the first to seventh inventions.
In the above invention, the organic halide is PCB or P.
It is a PCB processing equipment monitoring system characterized by being CB contaminants.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of an operation control system in a hazardous substance treatment facility according to the present invention will be described below, but the present invention is not limited to these embodiments.

[First Embodiment] FIG. 1 is a schematic diagram of an operation control system for a hazardous substance treatment facility according to the present embodiment. As shown in FIG. 1, the operation control system for a hazardous substance treatment facility according to the present embodiment operates a treatment facility for decomposing an organic halide (for example, PCB) or a harmful substance containing the organic halide. An operation control system for a hazardous substance treatment facility to be controlled, the wastewater 13 being discharged from a treatment facility 120 for decomposing and treating the harmful substance.
The drainage measuring means 201A is provided as a monitoring means for measuring the index substance such as the organic halide concentration or its decomposition product concentration in 3 at the measuring point A. When the index substance exceeds a predetermined value, the wastewater 131 is temporarily stored in the storage tank 202 without being discharged as it is, or is treated again by the treatment facility.

As the harmful substance treatment facility 120, as shown in FIG. 12, a cylindrical primary reaction tower 122 provided with a cyclone separator 121, oil (or organic solvent), PCB, water (H ₂ O). And a pressurizing pump 124 for pressurizing each treatment solution 123a to 123d of sodium hydroxide (NaOH), and a heat exchanger 125 for preheating the water.
And a secondary reaction tower 126 having a configuration in which pipes are spirally wound,
It is provided with a cooler 127 and a pressure reducing valve 128. In the primary reaction tower 122, in the height direction,
Thermometers are provided at predetermined intervals to measure the temperature.

The harmful substance treatment facility 120 may be, for example, a supercritical water oxidation treatment means for performing supercritical water oxidation or a batch type hydrothermal oxidation decomposition means in addition to the hydrothermal oxidation decomposition treatment means described above. Good.

The harmful substances in the present invention include, for example, insulating oils used in transformers and capacitors, such as PCB and PC.
Examples thereof include paints containing B and PCB contaminants, but are not limited thereto.

<Drainage Monitoring Means> As the wastewater measuring means 201A, for example, a solid phase extraction gas chromatograph apparatus as shown in FIGS.

As shown in FIG. 2, the wastewater measuring means 210 according to the present embodiment is a detection device for detecting the concentration of organic halides in an aqueous solution. Qualitative and quantitative analysis of the eluted organic halide by introducing the solid phase / adsorption means 12 that holds the organic halide (PCB) with the solution and the eluate from the solid phase / adsorption means 12 through the autosampler 13. And a detection means 14 for performing the above.

Although PCB itself was detected as the indicator substance in the above measurement, a decomposed product of PCB such as biphenyl may be used as the indicator substance instead of PCB.

As shown in FIG. 3 (A), the solid phase / adsorption means 12 has a solid phase adsorbent 22 inserted in an extraction column 21, and the solid phase adsorbent is silica gel or alumina. It consists of

The eluent for eluting the organic halide retained on the solid phase adsorbent is not particularly limited as long as it is a solvent for eluting only the target organic halide.
For example, in the case of PCB, a nonpolar solvent (for example, n-hexane) can be used.

Further, since it is necessary to monitor the drainage every predetermined time, it is possible to automatically sample the sample by providing a sample introducing means for periodically introducing the sample to be collected.

In addition, in order to improve the analysis accuracy, when several objects are simultaneously processed at one time as needed, a plurality of the columns 21 are prepared and at the same time, the organic halide is solid-phased. You may make it adsorb | suck.

The extraction process of the solid phase / adsorption means 12 will be described below with reference to FIGS. Conditioning process To obtain reproducible results, before feeding the sample,
The conditioning liquid 31 is supplied to the solid-phase adsorbent 22 so as to be conditioned (see FIG. 3 (A)). Holding Step Next, the collected sample 32 is introduced into the column 21 (see FIG. 3).
(See (B)). Here, in the sample, the target PCB
33, impurities X (unnecessary matrix) and impurities Y
(Other components in the matrix) are included. Washing Step Next, the impurities X retained on the solid phase adsorbent 22 are washed away with a washing liquid (eg, methyl alcohol) (FIG. 3C).
reference). Elution Step Next, the target PCB retained by the solid phase adsorbent 22
33 is eluted with an eluent (n-hexane) 35. During this elution, the impurity X remains in the solid phase adsorbent 22 and PCB.
It is separated from 33 (see FIG. 3D). In the present embodiment, PCB has been described as an example of the organic halide, but the present invention is not limited to this. For example, dioxins in wastewater from factories or incinerators or in water of rivers, etc. It can also be applied to measurement such as.

FIG. 4 is a process diagram of solid phase extraction using the above-mentioned organic halide detecting device. First, 20 mL of n-hexane is supplied to the solid phase adsorbent 22 and solid phase drying (vacuum drawing) is performed for 5 minutes (S101). Then, 20 mL of methyl alcohol and 20 mL of ultrapure water
After flowing in mL, a sample (0.1 to 1 L) is introduced, the PCB is captured, and solid phase extraction is performed (S102). At this time, 1% of methyl alcohol was added to the sample. The addition of this methyl alcohol has the function of dispersing the PCB. After that, 5 mL of the cleaning liquid (methyl alcohol) is flowed (liquid passing rate: 0.3 cc / s) for cleaning (S103). Then, the solid phase adsorbent 22 is dried (vacuum drawing) for 5 minutes (S104). Then, using n-hexane, the flow rate was 0.3 cc /
PCB is eluted as s (S105), and the volume is adjusted to 5 mL (S106). Then, a gas chromatograph-mass spectrometer (GC-M
S) or gas chromatograph-electron capture type detector analyzer (GC-ECD) (S107), P
The CB concentration is measured (S108). The column from which the above-mentioned PCB has been eluted can be subjected to a regeneration treatment and then subjected to PCB measurement again.

Using the above-mentioned measuring device 201A, the indicator substance (PCB or its decomposition product) in the wastewater is analyzed every predetermined time, and when PCB or the decomposition product above the predetermined value is present in the wastewater, Efficient processing can be performed by issuing a command to the control means 211 and reviewing the processing conditions in the PCB processing equipment 120.

As the command from the control means 211, for example, oil (or organic solvent) to be the processing liquid 123, PCB,
By appropriately changing the supply amount of each of the processing liquids 123a to 123d of H ₂ O and NaOH, for example, heating control, pressurization control of the PCB decomposition processing facility 120, control of the input amount of the PCB processing liquid, or sodium hydroxide ( At least one of the controls of the input amount of (NaOH) is controlled to improve the decomposition efficiency. In addition, the PCB disassembly processing device 12
By adjusting the supply amount of various oils, such as kerosene and insulating oil, which are supplied to 0 to the processing liquid tank 135a,
You may make it adjust the viscosity etc. of a reaction liquid.

By adjusting the amount of oxygen supplied from the high-pressure oxygen supply equipment 138 and the pressure reducing valve 128, the decomposition reaction of harmful substances is optimized.

In addition, by adjusting the pressure reducing valve 128,
The reaction time in the apparent reaction tower may be increased.

At this time, if the PCB has a predetermined value or more, the drainage cannot be discharged as it is, so the drainage line is switched by the switching valve 220 and stored in the storage tank 221 which is separately stored. The waste water stored in the storage tank 221 is subjected to the hydrothermal oxidative decomposition treatment again so as to be completely treated.

If it is within the standard value, drainage 133
Is sent to the discharge tank 134 and discharged.

[Second Embodiment] FIG. 5 is a schematic diagram of an operation control system for a hazardous substance treatment facility according to the present embodiment. As shown in FIG. 5, the operation control system of the harmful substance treatment equipment according to the present embodiment operates the treatment equipment for decomposing the organic halide (for example, PCB) or the harmful substance containing the organic halide. An operation control system of a hazardous substance treatment facility to be controlled, wherein an index substance such as the concentration of an organic halide in the decomposition reaction liquid 231 of the harmful substance or the concentration of its decomposed substance is measured at a measurement point B (the primary reaction tower 12
2 in the middle of a pipe 141 connecting the secondary reaction tower 126) with a reaction solution measuring means 201B,
When the index substance exceeds a predetermined value, the decomposition conditions of the decomposition treatment equipment are optimized.

As the measuring means 201B, the measuring device described in the first embodiment can be used. Therefore, when the indicator substance (PCB or its decomposition product) in the reaction liquid is analyzed at predetermined time intervals by using the above-mentioned measuring means 201B, and when the reaction liquid contains a PCB or decomposition product having a predetermined value or more, , Issues a command to the control means 211, and the PCB processing equipment 12
Efficient processing can be performed by reviewing the processing condition of 0.

As the command from the control means 211, for example, oil (or organic solvent) to be the processing liquid 123, PCB,
By appropriately changing the supply amount of each of the processing liquids 123a to 123d of H ₂ O and NaOH, for example, heating control, pressurization control of the PCB decomposition processing facility 120, control of the input amount of the PCB processing liquid, or sodium hydroxide ( At least one of the controls of the input amount of (NaOH) is controlled to improve the decomposition efficiency. In addition, the PCB disassembly processing device 12
By adjusting the supply amount of various oils, such as kerosene and insulating oil, which are supplied to 0 to the processing liquid tank 135a,
You may make it adjust the viscosity etc. of a reaction liquid.

By adjusting the amount of oxygen supplied from the high-pressure oxygen supply equipment 138 and the pressure reducing valve 128, the decomposition reaction of harmful substances is optimized.

In addition, by adjusting the pressure reducing valve 128,
The reaction time in the apparent reaction tower may be increased.

In addition, the secondary reaction tower 126 was directly charged with NaOH.
Of the secondary reaction tower 12 by supplying oxygen or oxygen.
You may make it promote the reaction inside.

When the value is within the reference value, the decomposition may be continued while maintaining the reaction conditions.

[Third Embodiment] FIG. 6 is a schematic diagram of an operation control system for a hazardous substance treatment facility according to the present embodiment. As shown in FIG. 6, the operation control system for hazardous substance treatment equipment according to the present embodiment operates the treatment equipment for decomposing and treating an organic halide (for example, PCB) or a harmful substance containing the organic halide. An operation control system of a hazardous substance treatment facility to be controlled, wherein an index substance such as an organic halide concentration or its decomposed substance concentration in exhaust gas 131 discharged from a treatment facility 120 for decomposing the harmful substance is measured point C ( Between gas-liquid separator 129 and activated carbon tank 130) and measurement point D (activated carbon tank 130 and chimney 1)
32C) is provided with a reaction liquid / wastewater measuring means 201C as a monitoring means for measuring.

Further, in the present embodiment, an index such as the concentration of the organic halide in the waste water 133 discharged from the treatment facility 120 which is the measurement system according to the above-mentioned first and second embodiments or the concentration of its decomposed products. Monitoring means 201A for measuring a substance at a measurement point A ((between the gas-liquid separation device 129 and the release tank 134), and an organic halide concentration in the reaction liquid 231 or a decomposition product thereof in the reaction process of the processing facility 120. A reaction liquid monitoring means 201B for measuring an index substance such as a concentration at a measurement point B (between the primary reaction tower 122 and the secondary reaction tower 126).

Further, in this embodiment, as shown in FIG. 7, two activated carbon tanks 130A, 1A are used as the activated carbon tanks 130.
30B is provided, and while the activated carbon is being regenerated and exchanged in one of the activated carbon tanks, the other activated carbon tank is used to perform the exhaust gas treatment, thereby continuously and efficiently performing the treatment.

In addition, the two measurement points for measuring the index substance such as the organic halide concentration in the exhaust gas 131 or the decomposition product concentration thereof are to regenerate and exchange the activated carbon before the activated carbon breaks through. This is to do it promptly.

Further, the activated carbon having a reduced adsorption capacity may be subjected to a regenerating process, or may be pulverized into a slurry form and treated by the hydrothermal oxidative decomposition treatment device 120. This is because PCB is contained in the incineration process, and therefore, the incineration gas needs to pass through the activated carbon tank, and the treatment of the activated carbon tank is also required, which is not efficient. Because there is no. As a result, the activated carbon that has adsorbed the harmful substances is not discarded, and the complete treatment can be achieved.

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

FIG. 8 shows a concrete device of the exhaust gas monitoring means. As shown in FIG. 8, the laser ionization time-of-flight mass spectrometer 50 includes a capillary column 54 which is a sample introducing means for continuously introducing a sample to be collected into a vacuum chamber, and a leaking molecular beam which is the sample introduced. Laser irradiation means 56 for irradiating laser light 55 to 53 for laser ionization, a converging part for converging the laser ionized molecules, an ion trap 57 for selectively concentrating the converged molecules, and a laser beam emitted at a constant cycle and reflected. The time-of-flight mass spectrometer 60 is provided with an ion detector 59 for detecting the ions reflected by the ron 58.

Then, the PCB concentration of the measurement object can be obtained by comparing the signal intensities detected by the detector 59.

FIG. 9 shows a measurement system using the laser ionization time-of-flight mass spectrometer. As shown in FIG. 6, in the PCB concentration measuring system 62, a gas sampling line 63 branched from the PCB discharge line is connected to the vacuum chamber 52, and the sample gas is leaked from the line 61 into the vacuum chamber 52 as a molecular beam. Are introduced, and are ionized by the laser beam 55 from the laser irradiation device 56, and the ions are detected by the time-of-flight mass spectrometer 60. In the figure, reference numeral 63 is a vacuum evacuation device that evacuates the vacuum chamber 52, and 64 is a controller that controls these devices. By using this measurement system, high-sensitivity rapid analysis with a detection sensitivity of 0.01 mg / Nm ³ for PCB concentration and a detection time of less than 1 minute becomes possible, and real-time analysis becomes possible.

FIGS. 10 (a) and 10 (b) show an example of the signal from the ion detector detecting the PCB. here,
The horizontal axis represents the flight time (seconds), and the vertical axis represents the ion signal intensity (V). In addition, about PCB of 4 chlorine
FIG. 10B is an enlarged view of FIG.

By monitoring the exhaust gas 131 discharged from the hydrothermal oxidative decomposition apparatus 120, which is a means for treating harmful substances, 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, and the PCB concentration at that time is monitored.

Using the above measuring device, for example, the exhaust gas from the PCB decomposition treatment facility can be measured quickly and accurately, and the treatment process can be monitored based on the measurement result.

When the indicator substance (PCB or its decomposition product) in the exhaust gas 131 is analyzed at predetermined time intervals using the above-mentioned measuring means 201C, and when PCB or the decomposition product above a predetermined value is present in the waste water, , Issues a command to the control means 211,
Efficient processing can be performed by reviewing the processing conditions in the PCB processing facility 120.

As the command from the control means 211, for example, oil (or organic solvent) to be the processing liquid 123, PCB,
By appropriately changing the supply amount of each of the processing liquids 123a to 123d of H ₂ O and NaOH, for example, heating control, pressurization control of the PCB decomposition processing facility 120, control of the input amount of the PCB processing liquid, or sodium hydroxide ( At least one of the controls of the input amount of (NaOH) is controlled to improve the decomposition efficiency. In addition, the PCB disassembly processing device 12
By adjusting the supply amount of various oils, such as kerosene and insulating oil, which are supplied to 0 to the processing liquid tank 135a,
You may make it adjust the viscosity etc. of a reaction liquid.

Further, since the analysis of the harmful substances in the exhaust gas can be carried out quickly, the analysis accuracy can be improved by using it together with the measurement of the PCB in the waste water and the reaction solution.

The wastewater monitoring means and the exhaust gas monitoring means are monitored by using separate devices, but they are not limited to this in the present invention. For example, absorption or fluorescence of ultraviolet light, visible light or infrared light is used. The light emission phenomenon such as the above may be used to determine the PCB concentration in the gas / solution.

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

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

Further, 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 waste water.

The PCB may be detected with high sensitivity by a phase modulation measuring device using a laser. According to the phase modulation measurement method using this laser, the oscillating laser is modulated, synchronous detection is performed by the frequency-multiplied modulation signal when the laser beam is received, and a higher-order differential absorption signal is obtained as the output. By this, DUT (gas or drainage)
It is possible to measure the PCB concentration in the sample with high accuracy and continuously.

Alternatively, 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 type detector analyzer (GC-ECD).

Further, PCB in the exhaust gas is absorbed with a solvent (n-hexane or the like), and then liquid-liquid extraction is performed to concentrate and separate the PCB, and the gas chromatograph-electron capture type detector analyzer (GC-ECD) is used for PCB. The concentration may be measured.

Further, a solid phase absorbent is inserted in the passage of exhaust gas or drainage, PCB is adsorbed on the solid phase absorbent, and then the PCB concentration is measured by the absorptiometry by UV irradiation (UV method). Good.

[0077]

As described above, according to the first aspect of the present invention, the harmful substance for controlling the operation of the treatment facility for decomposing the organic halide or the harmful substance containing the organic halide is controlled. An operation control system for a treatment facility, comprising monitoring means for measuring the concentration of an indicator substance such as an organic halide or its decomposed product in wastewater discharged from the treatment facility for decomposing the harmful substance, If the concentration exceeds the specified value, it will be temporarily stored or treated again in the treatment facility without discharging the wastewater.
When the indicator substance in the wastewater is analyzed every predetermined time and the concentration in the wastewater exceeds the predetermined value, a command is issued to the control means,
Efficient treatment can be performed by reviewing the treatment conditions in the organic halide treatment equipment.

According to a second aspect of the present invention, there is provided an operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing and treating an organic halide or a harmful substance containing the organic halide. Equipped with wastewater monitoring means for measuring the concentration of indicator substances such as organic halides or their decomposition products in the wastewater discharged from the treatment facility for decomposing substances, and when the concentration of the indicator substances in the wastewater exceeds a prescribed value Since the decomposition conditions of the decomposition treatment equipment are optimized, efficient treatment can be performed.

According to a third aspect of the present invention, there is provided an operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing an organic halide or a harmful substance containing the organic halide, which is the above harmful substance. Equipped with wastewater monitoring means for measuring the concentration of indicator substances such as organic halides or their decomposition products in the wastewater discharged from the treatment facility for decomposing substances, and when the concentration of the indicator substances in the wastewater exceeds a prescribed value Since the amount of harmful substances supplied to the decomposition treatment facility is adjusted or stopped, efficient treatment can be performed.

According to a fourth aspect of the present invention, there is provided an operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing an organic halide or a harmful substance containing the organic halide, which is the above harmful substance. If the concentration of the indicator substance exceeds the specified value, it is equipped with a reaction solution monitoring means for measuring the concentration of the indicator substance such as an organic halide or its decomposition product in the decomposition reaction liquid of the substance. Is optimized so that efficient processing can be performed.

According to a fifth aspect of the present invention, there is provided an operation control system for a harmful substance treatment facility for controlling the operation of a treatment facility for decomposing an organic halide or a harmful substance containing the organic halide, the system comprising: Decomposition equipment equipped with reaction solution monitoring means for measuring the concentration of the indicator substance such as the concentration of organic halide in the decomposition reaction solution of the substance or the concentration of its decomposed product, and the indicator substance in the reaction solution exceeds a predetermined value. Since the supply amount of the harmful substance to be supplied to or adjusted to is stopped, efficient processing can be performed.

According to a sixth aspect of the present invention, there is provided an operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing and treating an organic halide or a harmful substance containing the organic halide. When the concentration of the indicator substance in the exhaust gas exceeds the specified value, equipped with wastewater monitoring means that measures the concentration of the indicator substance such as organic halides or its decomposition products in the exhaust gas discharged from the treatment facility that decomposes the substance In addition, since the decomposition conditions of the decomposition treatment equipment are optimized, efficient treatment can be performed.

According to a seventh aspect of the present invention, there is provided an operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing and treating an organic halide or a harmful substance containing the organic halide. When the concentration of the indicator substance in the exhaust gas exceeds the specified value, equipped with wastewater monitoring means that measures the concentration of the indicator substance such as organic halides or its decomposition products in the exhaust gas discharged from the treatment facility that decomposes the substance In addition, since the supply amount of the harmful substance to be supplied to the decomposition treatment facility is adjusted or stopped, efficient treatment can be performed.

According to an eighth aspect of the present invention, in any one of the first to seventh aspects of the present invention, the treatment facility for decomposing and treating harmful substances has sodium carbonate (Na ₂ CO _{3) in the} heated and pressurized reaction tower. ), The hydrothermal oxidative decomposition apparatus decomposes the organic halide into sodium chloride (NaCl), carbon dioxide (CO ₂ ) and the like by a dehalogenation reaction and an oxidative decomposition reaction.
B can be efficiently decomposed.

According to a ninth invention, in the eighth invention, the hydrothermal oxidative decomposition apparatus comprises a cylindrical primary reaction tower provided with a cyclone separator, an oil or an organic solvent, an organic halide, water (H ₂ O) and sodium hydroxide (N
aOH) a pressurizing pump for pressurizing each processing liquid, a preheater for preheating the water, a secondary reaction tower having a spirally wound pipe, and a cooling for cooling the processing liquid from the secondary reaction tower. A vessel,
Since a gas-liquid separation means for separating the treatment liquid into gas and liquid and a pressure reducing valve are provided, it is possible to efficiently decompose, for example, PCB as a harmful substance.

According to the tenth invention, in the ninth invention, the reaction solution is monitored during the reaction process in the reaction solution between the primary reaction column and the secondary reaction column in the hydrothermal oxidative decomposition apparatus, or in the gas. Since it is performed either in the waste water after separation by the liquid separation means, for example, PCB as a harmful substance can be efficiently decomposed.

According to the eleventh invention, in the tenth invention, the above-mentioned operation controls include heating control of the organic halide decomposition treatment equipment, pressurization control, control of the amount of the organic halide treatment liquid added, and addition of the oxidant. Since it is at least one of the control of the amount and the control of the input amount of sodium hydroxide (NaOH), for example, PCB as a harmful substance can be efficiently decomposed.

According to the twelfth invention, in the first invention, the exhaust gas monitoring means is a laser ionization time-of-flight mass spectrometer, so that the organic halide in the exhaust gas can be accurately monitored.

According to the thirteenth invention, in the tenth invention, the exhaust gas monitoring means continuously introduces the sample into the vacuum chamber, and the sample introduction means irradiates the sample with a laser beam. Time-of-flight provided with laser irradiation means for laser ionization, a converging unit for converging laser-ionized molecules, an ion trap for selectively concentrating the converged molecules, and an ion detector for detecting ions emitted at a constant period. Since it is provided with a type mass spectrometer, the detection accuracy is improved.

According to the fourteenth invention, in any one of the first to seventh inventions, since the wastewater monitoring means is a solid-phase extraction gas chromatograph device, the organic halide in the wastewater can be accurately monitored. .

According to a fifteenth invention, in any one of the first to seventh inventions, the above-mentioned wastewater monitoring means introduces the sample to be collected, and the solid phase / adsorption means for holding the organic halide by the solid phase adsorbent. And the detection means for qualitatively and quantitatively analyzing the organic halide eluted from the solid phase / adsorption means with the eluent, the monitoring of the organic halide in the waste water becomes accurate.

According to a sixteenth invention, in any one of the first to seventh inventions, the organic halide is PCB.
Also, since it is a PCB contaminant, PCB treatment can be performed efficiently.

[Brief description of drawings]

FIG. 1 is a schematic diagram of an operation control system of a hazardous substance treatment facility according to a first embodiment.

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

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

FIG. 4 is a flow chart of a wastewater monitoring system.

FIG. 5 is a schematic diagram of an operation control system for a hazardous substance treatment facility according to a second embodiment.

FIG. 6 is a schematic diagram of an operation control system for a hazardous substance treatment facility according to a third embodiment.

FIG. 7 is a schematic view of an activated carbon tank.

FIG. 8 is a schematic diagram of a wastewater monitoring system.

FIG. 9 is a schematic diagram of a wastewater monitoring system. P
It is a schematic diagram of a CB concentration measurement system.

FIG. 10 is an example of a measurement chart from an ion detector that detects PCB.

FIG. 11 is an equipment diagram of a harmful substance decomposition processing system.

FIG. 12 is a schematic diagram of a hydrothermal oxidative decomposition apparatus.

[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 code FI theme code (reference) C07B 37/06 C07B 37/06 G01N 27/62 G01N 27/62 V 27/64 27/64 B (72) Inventor Akihiro Nozaki 5-717-1, Fukahori-cho, Nagasaki-shi, Nagasaki Sanryo Heavy Industry Co., Ltd. Nagasaki Research Institute (72) Inventor Keigo Baba 1-717, Fukahori-cho, Nagasaki-shi, Nagasaki Nagata Engineering Co., Ltd. F-term (Reference) 2E191 BA13 BC01 BD11 4D050 AA12 AB19 BB01 BC01 BC02 BD08 4H006 AA04 AA05 AC13 AC26

Claims (16)

[Claims] 1. An operation control system of a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing an organic halide or a harmful substance containing the organic halide, which is a treatment for decomposing the harmful substance. Equipped with monitoring means for measuring the concentration of indicator substances such as organic halides or their decomposition products in the wastewater discharged from the facility, and if the concentration of the above-mentioned indicator substances exceeds a specified value, the wastewater will not be discharged temporarily. An operation control system for an organic halide treatment facility, characterized in that it is stored in or retreated in the treatment facility. 2. An operation control system of a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing an organic halide or a harmful substance containing the organic halide, the treatment system decomposing the hazardous substance. Equipped with wastewater monitoring means to measure the concentration of indicator substances such as organic halides or their decomposition products in the wastewater discharged from the facility, and if the concentration of the indicator substance in the wastewater exceeds a prescribed value, the decomposition equipment will be decomposed. An operation control system for an organic halide treatment facility characterized by optimizing conditions. 3. An operation control system of a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing an organic halide or a harmful substance containing the organic halide, the treatment system decomposing the harmful substance. Equipped with wastewater monitoring means to measure the concentration of indicator substances such as organic halides or their decomposition products in the wastewater discharged from the facility.If the concentration of the index substance in the wastewater exceeds a specified value, supply it to the decomposition treatment facility. An operation control system for an organic halide treatment facility, characterized by adjusting or stopping the supply of harmful substances. 4. An operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing an organic halide or a harmful substance containing the organic halide, which comprises: It is equipped with a reaction solution monitoring means for measuring the concentration of the indicator substance such as the organic halide or its decomposition product, and when the concentration of the above-mentioned indicator substance exceeds a predetermined value, the decomposition conditions of the decomposition treatment equipment should be optimized. A characteristic operation control system for organic halide treatment equipment. 5. An operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing an organic halide or a harmful substance containing the organic halide, the system comprising: If the indicator substance in the reaction solution exceeds the specified value, it is provided with a reaction solution monitoring means for measuring the concentration of the indicator substance such as the concentration of organic halide or its decomposed product concentration in the reaction solution. An operation control system for an organic halide treatment facility, characterized by adjusting or stopping the supply of harmful substances. 6. An operation control system of a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing an organic halide or a harmful substance containing the organic halide, the treatment system decomposing the hazardous substance. Equipped with wastewater monitoring means to measure the concentration of indicator substances such as organic halides or their decomposition products in the exhaust gas discharged from the facility, and if the concentration of the indicator substance in the exhaust gas exceeds a specified value, decomposition treatment equipment An operation control system for an organic halide treatment facility, characterized by optimizing the decomposition conditions of. 7. An operation control system for a hazardous substance treatment facility for controlling the operation of a treatment facility for decomposing an organic halide or a harmful substance containing the organic halide, the treatment system decomposing the hazardous substance. Equipped with wastewater monitoring means to measure the concentration of indicator substances such as organic halides or their decomposition products in the exhaust gas discharged from the facility, and if the concentration of the indicator substance in the exhaust gas exceeds a specified value, decomposition treatment equipment An operation control system for an organic halide treatment facility, characterized by adjusting or stopping the supply of harmful substances to be supplied to. 8. The organic halogen according to claim 1, wherein the treatment facility for decomposing the harmful substance is in the presence of sodium carbonate (Na ₂ CO ₃ ) in the heated and pressurized reaction tower. An organic halide treatment facility monitoring system, which is a hydrothermal oxidative decomposition apparatus for decomposing sodium chloride (NaCl), carbon dioxide (CO ₂ ) or the like through a dehalogenation reaction and an oxidative decomposition reaction of a halide. 9. The hydrothermal oxidative decomposition apparatus according to claim 8, wherein the hydrothermal oxidative decomposition apparatus is a cylindrical primary reaction tower provided with a cyclone separator, oil or an organic solvent, an organic halide, water (H ₂ O) and sodium hydroxide. (NaO
H) a pressurizing pump that pressurizes each treatment liquid, a preheater that preheats the water, a secondary reaction tower in which pipes are spirally wound, and a cooling that cools the treatment liquid from the secondary reaction tower. An organic halide treatment facility monitoring system comprising a container, a gas-liquid separating means for separating a processing liquid into a gas and a liquid, and a pressure reducing valve. 10. The method for monitoring the reaction liquid during the reaction process according to claim 9, wherein the reaction liquid is monitored in the reaction liquid between the primary reaction tower and the secondary reaction tower in the hydrothermal oxidative decomposition apparatus, or after separation by the gas-liquid separation means. An organic halide treatment facility monitoring system characterized by being performed either in the wastewater. 11. The operation control according to claim 10, wherein the operation control is heating control of an organic halide decomposition treatment facility, pressurization control, control of an input amount of an organic halide treatment liquid, control of an input amount of an oxidizer, or hydroxylation. Sodium (N
An organic halide treatment facility monitoring system, characterized in that it is at least one of the control of the input amount of aOH). 12. The organic halide treatment facility monitoring system according to claim 1, wherein the exhaust gas monitoring means is a laser ionization time-of-flight mass spectrometer. 13. The sample introduction means according to claim 10, wherein the exhaust gas monitoring means continuously introduces the sample to be collected into the vacuum chamber; and a laser irradiation means for irradiating the introduced sample with laser to perform laser ionization. A time-of-flight mass spectrometer equipped with a converging unit for converging laser-ionized molecules, an ion trap for selectively concentrating the converging molecules, and an ion detector for detecting ions emitted at a constant period. An organic halide treatment facility monitoring system characterized by the following. 14. The organic halide treatment facility monitoring system according to claim 1, wherein the wastewater monitoring means is a solid-phase extraction gas chromatograph. 15. The solid phase / adsorption means according to claim 1, wherein the wastewater monitoring means introduces a sample to be collected and holds an organic halide with a solid phase adsorbent,
An organic halide treatment facility monitoring system, comprising: a detection means for performing qualitative and quantitative analysis of an organic halide eluted from the solid phase / adsorption means by an eluent. 16. The PCB processing facility monitoring system according to claim 1, wherein the organic halide is PCB and a PCB contaminant.