JP2002181787A - Apparatus and method for detection of organic halogenide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an apparatus and a method for the detection of an organic halogenide such as e.g. PCB and dioxins in a treatment facility or an environment. SOLUTION: The detection apparatus is provided with a capillary column 54 as a sample introduction means by which a sampled sample 51 is continuously introduced into a vacuum chamber 52 as a leakage molecular beam 53, a laser irradiation means 56 by which the leakage molecular beam 53 is irradiated with a laser beam 55 so as to be laser-ionized, a convergence part 56 which is composed of a plurality of ion electrodes used to converge laser-ionized molecules, an ion trap 57 which selects and concentrates the converged molecules and a time-of-flight mass spectrometer 60 in which ions emitted at a definite cycle are reflected by a reflection 58 and which is equipped with an ion detector 59 used to detect the reflected ions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus and a method for detecting organic halides such as PCBs and dioxins in a processing facility or environment.

[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 decomposition apparatus for detoxifying CB has been proposed (JP-A-11-253796, JP-A-2000-12658).
No. 8, etc.). FIG. 5 shows an example of the outline of this hydrothermal decomposition apparatus.

[0005] As shown in FIG.
Is a cylindrical primary reactor 122 provided with a cyclone separator 121, a pressurizing pump 124 for pressurizing a treatment liquid 123 of PCB, H ₂ O and NaOH, a preheater 125 for preheating the mixed liquid, and a pipe. It comprises a wound secondary reactor 126, a cooler 127 and a pressure reducing valve 128. Further, downstream of the pressure reducing valve 127,
The gas-liquid separator 129 and the activated carbon tank 130 are arranged,
The exhaust gas (CO ₂ ) 131 is discharged from the chimney 132 to the outside, and the waste water (H ₂ O, NaCl) 133 is separately subjected to waste water treatment as needed. Also, a PCB that becomes the processing liquid 123
H ₂ O and NaOH are respectively introduced into the pipe 134. The oxygen pipe 135 is connected to the primary reactor 12.
5 is directly connected.

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 steam and the treated water are separated by the gas-liquid separator 129, and the CO ₂ and steam pass through the activated carbon tank 130 and are discharged into the environment.

[0007] By treating PCB-containing containers (for example, transformers and condensers) and the like using such a processing apparatus, complete harmlessness is achieved, but it is also important to quickly monitor the PCB concentration in the facility. . Conventionally, a method has been adopted in which the PCB is concentrated into a liquid by gas sampling, and the concentrated liquid is analyzed. However, since this measurement requires several hours to several tens of hours, rapid monitoring was not possible.

However, as a method of measuring a trace amount of PCB in a gas for monitoring, a multiphoton ionization detector and a time-of-flight mass spectrometer (Time of Flight Mass Spectrosc
opy: TOFMAS) has been proposed. The outline of this conventional analyzer will be described with reference to FIG.

As shown in FIG. 6, a sample gas 1 is supplied from a pulse nozzle 2 into a vacuum chamber 3 as a supersonic free jet, and the free jet is cooled by adiabatic expansion. Due to such cooling, a gas whose vibration / rotation level is biased toward the low energy side and whose wavelength selectivity is increased, the ionization efficiency of efficiently absorbing resonant multiphotons such as the laser 4 is increased. The molecules in the ionized gas are accelerated by the accelerating electrode 5, are given an acceleration inversely proportional to the mass, fly in the flight tube 6, are reflected by the reflectron 7, and enter the detector 8. By measuring the time of flight in the flight tube 6, the mass of the molecule or atom particle is obtained by calculation, and the concentration of the PCB to be measured can be obtained from the comparison of the signal intensity of the detector 8.

Such an apparatus is excellent in principle in that a trace substance can be detected, but has a problem that the detection sensitivity is low because the laser pulse width uses a nanosecond laser. .

The present invention has been made in consideration of the above problems, and has been developed in view of the above problem.
An object of the present invention is to provide an organic halide detection device and method capable of performing quick and highly sensitive analysis when monitoring the B concentration.

[0012]

Means for Solving the Problems A first invention of the present invention for solving the above-mentioned problems is a detecting device for detecting the concentration of an organic halide in a gas, wherein a sample is continuously introduced into a vacuum chamber. A sample introducing means for introducing, a laser irradiating means for irradiating the introduced sample with laser and laser ionizing, and a converging unit for converging the laser ionized molecules
It is characterized by comprising 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.

A second invention is characterized in that, in the first invention, the sample introduction means is a capillary column, and the tip of the capillary column faces the ion focusing section.

According to a third aspect, in the first aspect, the capillary column is made of quartz or stainless steel.

According to a fourth aspect, in the first aspect, the pulse wavelength of the laser irradiated from the laser irradiation means is 3
It is characterized in that it is not more than 00 nm.

According to a fifth aspect based on the first aspect, the pulse width of the laser beam emitted from the laser irradiation means is picosecond.

In a sixth aspect based on the first aspect, the pulse frequency of the laser beam emitted from the laser irradiation means is 1 MHz or more.

A seventh invention is characterized in that, in the first invention, the gas is a gas in a processing facility which has undergone PCB decomposition processing.

An eighth invention is a detection method for detecting the concentration of an organic halide in a gas, wherein a sample is continuously introduced into a vacuum chamber, and the introduced sample is irradiated with a laser. The method is characterized in that ions are ionized, and the laser ionized molecules are converged and selectively concentrated by an ion trap, and ions emitted from the ion trap at a constant period are detected by a time-of-flight mass spectrometer.

A ninth invention is characterized in that, in the eighth invention, the gas is a gas in a processing facility which has undergone PCB decomposition processing.

[0021]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described, but the present invention is not limited thereto.

[First Embodiment] FIG. 1 is a schematic diagram of an apparatus for detecting an organic halide according to the present embodiment.
As shown in FIG. 1, an organic halide detection device 50 according to the present embodiment is a detection device that detects the concentration of an organic halide in a gas, and continuously collects a sample 51 into a vacuum chamber 52. A capillary column 54, which is a sample introduction means for introducing the leaked molecular beam 53 into the laser beam 55; a laser irradiation means 54 for irradiating the leaked molecular beam 53 with a laser beam 55 to be laser-ionized; A converging section 56 composed of an ion electrode, an ion trap 57 for selectively concentrating the converged molecules, and an ion detector 59 for reflecting ions emitted at a constant period by a reflectron 58 and detecting the reflected ions. And a time-of-flight mass spectrometer 60 having Then, from the comparison of the signal intensities detected by the detector 59, the PCB concentration of the measurement target can be obtained. The measured PCB concentration may be sent to the monitoring command room, and may be disclosed to the outside by, for example, a monitor device (not shown).

The capillary column 54 preferably has a tip facing the ion converging section 56. Specifically, among the electrodes constituting the ion converging section 56, the electrode is closest to the electrode closest to the capillary column. It is preferable to protrude toward the ion trap side from the electrode.

The material of the capillary column is preferably quartz or stainless steel. In the case of stainless steel, control can be performed by applying an electric field by the ion focusing section 56.

The capillary column has a hole diameter of 1 mm or less, preferably about 3 mm for a laser. Also,
The shorter the distance from the outlet of the capillary column to the laser irradiation position, the better. However, even if it is too close, the tip will be damaged by the laser beam. Preferably, it is improved.

The pulse wavelength of the laser light 55 irradiated from the laser irradiation means 56 is 300 nm or less, preferably 266 ± 10 nm. This is because if it exceeds 300 nm, ionization of the organic halide to be measured is not performed well.

The pulse width of the laser beam 56 emitted from the laser irradiating means 56 is preferably a picosecond pulse laser. This is because a laser having a pulse width of nanoseconds (10 ^-9 ) has a low detection sensitivity and is not preferable.

The pulse frequency of the laser light emitted from the laser irradiating means 56 is 1 MHz or more, particularly preferably 7 MHz.
Preferably, it is 6 MHz. This is because if the frequency is less than 1 MHz, continuous ionization cannot be performed, and the ionization efficiency decreases, which is not preferable.

As described above, by reducing the pulse width of the laser light to picoseconds (10 ^-12 ), the pulse width of the laser light is reduced.
Decomposition of CB can be suppressed, and detection sensitivity can be improved.

The following Table 1 shows P based on the pulse width of the laser beam.
The measurement result of CB detection sensitivity is shown. In the measurement,
Using a PCB sample mainly containing 3 chlorine, a PCB of 1 to 4 chlorine was measured.

In this measurement, the signal intensity was measured when using a laser beam of 100 picoseconds and when using a 5 nanosecond laser beam. Note that a mode-locked picosecond laser (76 MH) having a fixed wavelength (266 nm) was used for the measurement in this embodiment.
z) was used.

[0032]

[Table 1]

FIGS. 2A and 2B show signals from the ion detector which detected PCB. Here, the horizontal axis is the flight time (second), and the vertical axis is the ion signal intensity (V). FIG. 2B is an enlarged view of FIG. 2A for the 4-chlorine PCB.

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

[Second Embodiment] FIG. 3 shows a PC in a gas.
The outline of the B concentration measurement system is shown. As shown in FIG.
In the PCB concentration measurement system 62, the gas sampling line 63 branched from the PCB discharge line is connected to the vacuum chamber 5
2 and the vacuum chamber 5
The sample is introduced into the sample 2 as a leaked molecular beam, 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, P
High sensitivity quick analysis with a CB concentration of 0.01 mg / Nm ³ and a detection time of less than 1 minute is possible.

[Third Embodiment] Next, a gas monitoring system in a PCB detoxification processing facility using the apparatus of the present invention will be described.

As shown in FIG. 4, the PCB detoxification processing system is a harmful substance processing system for detoxifying an object to which PCB, which is a harmful substance, is attached, contained, or stored. Harmful substances (eg PC
B) Separation means 1004 for separating the harmful substance 1002 from the container 1003 for storing 1002, and the constituent material 1001 constituting the object 1001
a, b,... disassembling means 1005 for disassembling one or both of them, and a core 1001 which is a constituent material constituting an object processed in the pre-processing means 1006
a into a coil 1001b and an iron core 1001c, and the separated coil 1001b into a copper wire 1001d and paper
Coil separating means 1008 for separating into tree 1001e, iron core 1001c separated by core separating means 1008 and metal container (container body and lid etc.) 1003 separated by disassembling means 1005 and coil separating means 1008 Cleaning solution 10
Washing means 1011 for washing in 10, and harmful substance decomposition treatment means 1013 for decomposing one or both of the washing waste liquid 1012 after washing and the harmful substance 1002 separated by the pretreatment means,
It is provided.

The harmful substances to be detoxified in the present invention include, in addition to PCBs, for example, vinyl chloride sheets, hazardous waste paints, waste fuels, hazardous chemicals, waste resins, untreated explosives and the like. However, as long as it is a harmful substance caused by environmental pollution, it is not limited thereto.

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. It is not limited.

Also, in the ballast for fluorescent lamps, PCB has been used conventionally, so that it is necessary to perform detoxification treatment. In this case, since the capacity is small, it is not necessary to perform pretreatment and directly to the separation means 1009. Detoxification treatment can be performed by charging.

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. It is necessary to confirm that the liquid after the treatment is 3 ppb or less, which is the PCB discharge standard. Since the configuration of the harmful substance processing means 1013 is the same as that shown in FIG. 5, the same components are denoted by the same reference numerals and description thereof will be omitted.

The measuring system 60 of the present invention monitors the concentration of PCB in the exhaust gas 131 purified by passing through the activation tank from the processing means 1013. By providing this measurement system, the PCB concentration can be monitored quickly and efficiently. As a result, it is possible to disassemble while constantly monitoring whether the work process is being performed properly,
Environmentally friendly measures can be taken.

Therefore, the present measuring device can be used to analyze at predetermined time intervals to constantly monitor whether the gas standard is satisfied. If an emergency occurs, the PCB concentration exceeds the emission standard. For example, the exhaust gas can be further purified through, for example, an activation tank, and only the operation procedure and the like can be adjusted to prevent external environmental pollution.

[0044]

As described above, according to the first aspect of the present invention, there is provided a detector for detecting the concentration of an organic halide in a gas, wherein a sample is introduced continuously into a vacuum chamber. Means, a laser irradiating means for irradiating the introduced sample with laser and laser ionizing, a converging unit for converging the laser-ionized molecules, and an ion trap for selectively concentrating the converged molecules, and emitted at a constant period. And a time-of-flight mass spectrometer provided with an ion detector for detecting the ions. For example, simple analysis of organic halides such as PCBs and dioxins can be performed.

According to a second aspect of the present invention, in the first aspect, the sample introduction means is a capillary column, and the tip of the capillary column faces the ion focusing portion, so that the ionization efficiency is improved.

According to a third aspect of the present invention, in the first aspect, since the capillary column is made of quartz or stainless steel, a good leakage molecular beam can be ejected.

In a fourth aspect based on the first aspect, the pulse wavelength of the laser irradiated from the laser irradiation means is 3
Since it is not more than 00 nm, ionization of the organic halide is performed favorably.

According to a fifth aspect, in the first aspect, the detection sensitivity is improved because the pulse width of the laser irradiated from the laser irradiation means is picosecond.

According to a sixth aspect, in the first aspect, since the pulse frequency of the laser irradiated from the laser irradiating means is 1 MHz or more, ionization can be continuously performed, and the ionization efficiency is improved.

According to a seventh aspect of the present invention, in the first aspect, since the above-mentioned gas is a gas in a processing facility which has undergone PCB decomposition processing, a quick and accurate analysis of the PCB concentration in the gas becomes possible.

An eighth invention is a detection method for detecting the concentration of an organic halide in a gas, wherein a sample is continuously introduced into a vacuum chamber, and the introduced sample is irradiated with a laser. It is ionized and selectively concentrated by an ion trap while converging the laser ionized molecules, and ions emitted from the ion trap at regular intervals are detected by a time-of-flight mass spectrometer. For example, organic substances such as PCBs and dioxins are used. Simple analysis of halides becomes possible.

According to a ninth aspect, in the eighth aspect, since the gas is a gas in a processing facility which has undergone PCB decomposition processing, a quick and accurate analysis of the PCB concentration in the gas becomes possible.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an organic halide detection device according to an embodiment.

FIG. 2 is a measurement result diagram of low chlorine PCB.

FIG. 3 is a schematic diagram of a PCBPCB concentration measurement system according to the present embodiment.

FIG. 4 is a schematic diagram of a PCB detoxification processing system according to the embodiment;

FIG. 5 is a schematic diagram of a hydrothermal decomposition apparatus.

FIG. 6 is a schematic diagram of a laser measurement device according to the related art.

[Explanation of symbols]

 Reference Signs List 50 Organic halide detection device 51 Sampling sample 52 Vacuum chamber 53 Leaked molecular beam 54 Capillary column 55 Laser light 56 Converging section 57 Ion trap 58 Reflectron 59 Ion detector 60 Time-of-flight mass spectrometer 61 Measurement system 62 Gas sampling Line 63 Evacuation device 64 Controller

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) G01N 30/72 G01N 30/72 A 30/88 30/88 C H01J 49/04 H01J 49/04 49/10 49/10 49/40 49/40 (72) Inventor Shinsaku Dobashi 5-717-1, Fukabori-cho, Nagasaki-shi, Nagasaki F-term (reference) in Nagasaki Research Laboratories, Mitsubishi Heavy Industries, Ltd. 4G075 AA03 AA37 AA65 BA01 BA08 BD11 CA14 CA36 CA65 DA02 DA18 EA02 EB01 EB33 EC01 EC21 FA01 FB02 FB06 5C038 EE01 EF03 GG07 GH04 GH10 GH11 GH13

Claims (9)

[Claims] 1. A detecting device for detecting the concentration of an organic halide in a gas, comprising: a sample introducing means for continuously introducing a collected sample into a vacuum chamber; and a laser irradiating the introduced sample with a laser. A laser irradiation means for ionizing, a converging section for converging the laser ionized molecules, an ion trap for selectively concentrating the converged molecules, and a time-of-flight type including an ion detector for detecting ions emitted at a constant period An apparatus for detecting an organic halide, comprising: a mass spectrometer. 2. The organic halide detector according to claim 1, wherein the sample introduction means is a capillary column, and the tip of the sample introduction means faces an ion focusing portion. 3. The organic halide detector according to claim 1, wherein the capillary column is made of quartz or stainless steel. 4. The organic halide detecting device according to claim 1, wherein a pulse wavelength of the laser irradiated from the laser irradiating means is 300 nm or less. 5. The organic halide detecting device according to claim 1, wherein a pulse width of the laser irradiated from the laser irradiation means is picosecond. 6. The organic halide detector according to claim 1, wherein a pulse frequency of the laser irradiated from the laser irradiation means is 1 MHz or more. 7. The organic halide detecting device according to claim 1, wherein the gas is a gas in a processing facility that has undergone PCB decomposition processing. 8. A detection method for detecting the concentration of an organic halide in a gas, wherein a sample to be collected is continuously introduced into a vacuum chamber, and the introduced sample is irradiated with a laser to be ionized by laser. A method for detecting an organic halide, comprising selectively concentrating a laser ionized molecule by an ion trap while converging the ionized molecule, and detecting ions emitted from the ion trap at a constant period by a time-of-flight mass spectrometer. 9. The method for detecting an organic halide according to claim 8, wherein the gas is a gas in a processing facility subjected to a PCB decomposition treatment.