JP2003139743A - Instrument and method for laser measurement - Google Patents

Abstract

PROBLEM TO BE SOLVED: To detect an organic halide such as PCB and polychlorinated-dibenzo- p-dioxins in a treating facility or environment. SOLUTION: This instrument is provided with a laser irradiating means 54 for irradiating with a laser beam 55 a leaked molecular beam 53 to be laser- ionized, a convergence part 56 comprising a plurality of ion electrodes, an ion trap 57 for selection-concentrating converged molecules, and a time-of-flight mass spectrograph 60 provided with an ion detector 59 for detecting a ions, and the laser beam is emitted to a sample introduced to be multiply reflected in prism means 71, 72 opposed each other and to preclude the laser beams from being overlapped in an ion area 73.

Description

Detailed Description of the Invention

[0001]

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

[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 decomposition apparatus for detoxifying CB has been proposed (JP-A-11-253796 and JP-A-2000-12658).
No. 8, etc.). An example of the outline of this hydrothermal decomposition apparatus is shown in FIG.

As shown in FIG. 6, the hydrothermal decomposition apparatus 120
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 piping. The secondary reactor 126 having a wound configuration, the cooler 127, and the pressure reducing valve 128 are provided. Further, 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 the chimney 132 to the outside, and wastewater (H ₂ O, NaCl) 133 is separately treated as wastewater. Also, the PCB that becomes the processing liquid 123
H ₂ O and NaOH are introduced into the pipe 134 of FIG. The oxygen pipe 135 is connected to the primary reactor 12
It is directly connected to 5.

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 treatment liquid 123 of PCB, H ₂ O and NaOH to about 300 ° C. In addition, oxygen is jetting out into the primary reactor 122, and the reaction heat inside raises the temperature to 380 ° C to 400 ° C. The cyclone separator 121 is the primary reactor 122.
Larger Na ₂ CO ₃ crystal particles precipitated inside are separated, and 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, PCB
Causes dechlorination reaction and oxidative decomposition reaction, and NaC
1, decomposed into CO ₂ and H ₂ O. Next, in the cooler 127, the fluid from the secondary reactor 126 is cooled to 100 ° C.
The pressure is reduced to a certain degree 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 treated water, and the CO ₂ and steam pass through the activated carbon tank 130 and are discharged into the environment.

By treating a PCB-containing container (for example, a transformer or a condenser) with such a treatment device, it has been made completely harmless. However, it is important to quickly monitor the PCB concentration in the facility. . Conventionally, a method of performing gas sampling, concentrating PCB into a liquid, and analyzing the concentrated liquid has been adopted, but this measurement requires several hours to several tens of hours, and thus rapid monitoring cannot be performed.

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

As shown in FIG. 7, the sample gas 1 is supplied from the pulse nozzle 2 into the vacuum chamber 3 as a supersonic free jet, and the free jet is cooled by adiabatic expansion. Due to such cooling, the vibration / rotational level is biased to the low energy side and the wavelength selectivity is increased, so that the ionization efficiency of the laser 4, which efficiently absorbs resonant multiphotons, is increased. Molecules in the ionized gas are accelerated by the acceleration electrode 5, are given an acceleration inversely proportional to the mass, fly in the flight tube 6, are reflected by the reflectons 7, and enter the detector 8. By measuring the time of flight in the flight tube 6, the mass of the particle, which is the molecule or atom, can be calculated, and the PCB concentration of the measurement object can be calculated by comparing the signal intensities of the detector 8.

Although such an apparatus is excellent in principle in that it can detect a trace amount of substance, it has a problem of low detection sensitivity because it uses a nanosecond laser with a laser pulse width. .

Further, when the ionization of the organic halide is efficiently generated by the laser light, the pulse width may be shortened. However, if the pulse width is too short, the sensitivity decreases. Further, in the case of a high molecular compound such as PCB in which a plurality of Cl groups are bonded, a laser beam having a long pulse width of 100 ps has a good ionization efficiency in the case of a low chlorinated PCB, while a high chlorinated PCB has a high ionization efficiency. It is said that laser light having a short pulse width of 10 ps is preferable. Therefore, in the case of measuring all PCB compounds, it is necessary to prepare a laser device having a plurality of pulse widths, and there is a problem that the device becomes large-scale.

In view of the above problems, it is an object of the present invention to provide an apparatus and method for detecting an organic halide, which enables rapid and highly sensitive analysis when monitoring trace components such as PCB concentration in gas. And

[0013]

A first aspect of the present invention for solving the above-mentioned problems is a sample introducing means for continuously introducing a sample to be collected into a vacuum chamber, and irradiating the introduced sample with a laser. 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. Type mass spectroscope, wherein the laser light from the laser irradiation means is multiple-reflected so that the laser light does not overlap in the ionization region. It is in.

A second aspect of the invention is the invention of claim 1
The laser measuring device is characterized in that the prisms in which the multiple reflections face each other are used and the multiple reflections are performed so as not to pass through the same path.

A third invention is the laser measuring apparatus according to the first invention, wherein the sample introducing means is a capillary column, and the tip of the capillary column faces the ion converging portion.

A fourth invention is, in the first invention, a laser measuring apparatus characterized in that the capillary column is made of quartz or stainless steel.

A fifth aspect of the invention is the laser measuring device according to the first aspect of the invention, in which the pulse width of the laser emitted from the laser irradiating means is in the range of picoseconds to tens of picoseconds.

A sixth aspect of the invention is the laser measuring device according to the first aspect of the invention, in which the pulse frequency of the laser beam emitted from the laser irradiation means is 1 MHz or higher.

A seventh aspect of the present invention is the laser measuring device according to the sixth aspect, wherein the pulse frequency of the laser emitted from the laser irradiating means is 10 to 200 MHz.

An eighth aspect of the present invention is the laser measuring device according to the first aspect, wherein the sample is a gas in a processing facility that has undergone a PCB decomposition process.

A ninth aspect of the present invention continuously introduces a sample to be collected into a vacuum chamber, irradiates the sample with a laser to cause laser ionization, and selectively concentrates the laser-ionized molecules with an ion trap. Then, a detection method for detecting the concentration of the organic halide in the gas by detecting the ions emitted from the ion trap at a constant period with a time-of-flight mass spectrometer, wherein the laser light from the laser irradiation means is A laser measuring method is characterized in that laser beams are irradiated in multiple reflections so that they do not overlap in the ionized region.

A tenth aspect of the present invention is the laser measuring method according to the ninth aspect, characterized in that the prisms in which the multiple reflections face each other are used, and the multiple reflections are performed so as not to pass through the same path.

An eleventh aspect of the present invention is the method for detecting an organic halide according to the ninth aspect, wherein the sample to be collected is a gas in a treatment facility where the PCB is decomposed.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below, but the present invention is not limited thereto.

[First Embodiment] FIG. 1 is a schematic view of a laser measuring apparatus according to the present embodiment. As shown in FIG. 1, the laser measuring apparatus 50 according to the present embodiment includes a capillary column 54 which is a sample introducing means for continuously leaking a sample 51 into a vacuum chamber 52 and introducing the sample 51 as a molecular beam 53. Laser beam 5 on the leaking molecular beam 53
Laser irradiation means 54 for irradiating 5 to perform laser ionization
A converging unit 56 composed of a plurality of ion electrodes for converging the laser-ionized molecules, an ion trap 57 for selectively concentrating the converged molecules, and an ion emitted at a constant period is reflected by a reflectron 58 to be reflected. And a time-of-flight mass spectrometer 60 having an ion detector 59 for detecting the generated ions. Then, the concentration of the measurement target can be obtained by comparing the signal intensities detected by the detector 59. In FIG. 1, reference numeral 61,
62 is a lens window and 70 is a reflecting mirror.

Laser light 5 from the laser irradiation means 56
Reference numeral 5 denotes prism means 7 facing each other, as shown in FIG.
The sample is introduced so that the laser beams are multiply reflected at 1, 72 and do not overlap with each other in the ion region 73. The prism means 7
1 uses a plurality of prisms, but is not limited to this. As a result, the pulsed laser light does not hit the sample, so that the sample is not decomposed and the laser ionization efficiency for the sample is improved.

FIGS. 3 and 4 show an outline of the optical device for introducing the laser beams so that they do not overlap each other. 3 is a perspective view, FIG. 4 (A) is a side view thereof, and FIG. 4 (B) is a plan view thereof. As shown in FIGS. 3 and 4, the optical device is composed of single prisms 74 and 75 facing each other.
By adjusting the incidence of the laser light 55 to be introduced, it is possible to make reflections that never overlap. In the present embodiment, the reflection mirror 76 is provided so that the sample is reflected back to further excite the sample a plurality of times.

Assuming, for example, an ionization area of 6 mm using the above-mentioned prism, 10 m for one incident laser beam.
What requires J output can be reflected by a laser with an output of 1 mJ 10 times, and the device configuration can be made inexpensive. There is also a method of simply multiple-reflecting laser light, but if the laser light paths overlap during multiple reflection, the ionized molecules will be irradiated again with laser light, which will accelerate the decomposition of the molecules to be measured. Defect occurs. Therefore, in the present invention, when multiple reflection is performed,
It is essential that the laser optical paths never overlap. Examples of the method in which the laser light paths do not overlap each other include a method of using a plurality of prisms and mirrors as shown in FIG. 2, a method of adjusting incident laser light to a pair of prisms facing each other, and the like. However, the present invention is not limited to these, and any other method may be used as long as the laser light does not overlap.

Here, for example, P that is an organic halide is used.
When analyzing CB, low chlorine (chlorine number 2 to
4) In order to improve the ionization efficiency of PCB, the pulse width may be increased.
7) To improve the ionization efficiency of the PCB, the pulse width of the incident laser light may be narrowed.

Therefore, as shown in FIG. 5, reflection lens groups 71A, 71B, 72A and 72B having different L are provided,
Two types of pulsed laser light are used, and a plurality of types of PCB concentrations from low chlorine to high chlorine can be simultaneously measured.

Here, it is preferable that the tip of the capillary column 54 faces the ion converging portion 56,
Specifically, among the electrodes forming the ion converging unit 56, it may be flush with the electrode closest to the capillary column, or may protrude toward the ion trap side with respect to the electrode.

The material of the capillary column is preferably quartz or stainless steel. Further, when it is made of stainless steel, control can be performed by applying an electric field by the ion converging unit 56.

The hole diameter of the capillary column is 1 mm or less, preferably about 3 mm for the laser. Also,
The closer the distance from the outlet of the capillary column to the laser irradiation position is, the better. However, if the distance is too close, the tip will be damaged by the laser light, so the ionization efficiency should be close enough to avoid damage (for example, about 1 to 2 mm). It is preferable to improve.

The pulse wavelength of the laser beam 55 emitted from the laser irradiation means 56 is 300 nm or less, preferably 266 ± 10 nm. This is because if it exceeds 300 nm, the ionization of the organic halide, which is the object of measurement, will not be performed well.

The laser irradiated from the laser irradiation means 56 is
The pulse width of the laser light 56 is in the range of picoseconds to tens of picoseconds.
It is preferable that it is a user. This has a pulse width of nanoseconds
(10 ^-9) Laser has low detection sensitivity and is not preferable?
It is.

The pulse frequency of the laser light emitted from the laser irradiating means 56 is 1 MHz or more, and particularly preferably 1
It is preferably 0 to 200 MHz. This is 1MH
This is because if it is less than z, ionization cannot be performed continuously and the ionization efficiency decreases, which is not preferable.

By using the above measuring device, for example, the gas in the PCB decomposition treatment facility can be measured quickly and accurately,
Based on this measurement result, the processing steps can be monitored.

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

As shown in FIG. 5, the PCB detoxification treatment system is a harmful substance treatment system for detoxifying an object to be treated on which PCB, which is a harmful substance, is attached, contained, or stored, and the object to be treated 1001 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 to be treated 1001.
Pretreatment means 1006 having one or both of disassembly means 1005 for disassembling a, b, ...
core separating means 1007 for separating a into a coil 1001b and an iron core 1001c, and the separated coil 1001b with a copper wire 1001d and paper.
A coil separating means 1008 for separating into a tree 1001e, an iron core 1001c separated by the core separating means 1008, a metal container (a container body and a lid, etc.) 1003 separated by a disassembling means 1005, and a coil separating means 1008. Washed copper wire 1001d with cleaning liquid 10
Cleaning means 1011 for cleaning at 10, and cleaning waste liquid 1012 after cleaning and harmful substance decomposition treatment means 1013 for decomposing either or both of the harmful substances 1002 separated by the pretreatment means,
It is equipped with.

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

Examples of the object to be treated in the present invention include transformers and capacitors using PCB as insulating oil, storage containers storing paints which are harmful substances, and the like. It is not limited.

In the ballast for fluorescent lamps, PCB has been used in the past, so it is necessary to detoxify it. In this case, since the capacity is small, pretreatment is not necessary and the separation means 1009 can be directly used. It can be detoxified by throwing it in.

When the harmful substance is a liquid or the like,
The harmful substance is decomposed by directly putting it into the harmful substance decomposition treatment means 1013, and the stored container can be treated by the detoxification treatment of the constituent materials. It is necessary to confirm that the treated liquid is 3 ppb or less, which is the emission standard of PCB. The structure of the harmful substance treating means 1013 is the same as that shown in FIG. 6, and thus the same components are designated by the same reference numerals and the description thereof will be omitted.

The measuring system 100 of the present invention is the exhaust gas 131 purified by passing through the active tank from the processing means 1013.
It is intended to monitor the PCB concentration inside. By providing this measuring system, the PCB concentration can be monitored quickly and efficiently. As a result, it is possible to carry out the disassembling process while constantly monitoring whether or not the work process is appropriately performed, and it is possible to take environmentally friendly measures.

Therefore, by using this measuring device, it is possible to constantly analyze whether or not the gas standard is satisfied by performing analysis every predetermined time, and when there is an emergency, when the PCB concentration exceeds the emission standard. For example, the exhaust gas can be further purified through, for example, an active tank, and the work procedure and the like can be corrected to prevent external environmental pollution.

[0046]

As described above, according to the present invention,
Sample introduction means for continuously introducing the sample to be collected into the vacuum chamber, laser irradiation means for irradiating the introduced sample with a laser to cause laser ionization, and a converging unit for converging the laser ionized molecules, and the converged A laser measuring device comprising an ion trap for selectively concentrating molecules, and a time-of-flight mass spectrometer equipped with an ion detector for detecting ions emitted at a constant cycle, comprising: Since multiple reflection irradiation of the laser light is performed so that the laser light does not overlap in the ionization region, the sample is not decomposed, the laser ionization efficiency with respect to the sample is improved, and, for example, analysis of a trace amount of PCB in gas becomes possible. Become.

[Brief description of drawings]

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

FIG. 2 is a schematic diagram of laser light multiple reflection.

FIG. 3 is a schematic diagram of an optical device that introduces laser light.

4 (A) is a side view of FIG. 3 and FIG. 4 (B) is a plan view of FIG.

FIG. 5 is a schematic diagram of a PCB detoxification processing system according to the present embodiment.

FIG. 6 is a schematic diagram of a hydrothermal decomposition apparatus.

FIG. 7 is a schematic diagram of a laser measuring device according to a conventional technique.

[Explanation of symbols]

50 Organic halide detector 51 Collected samples 52 Vacuum chamber 53 Leakage molecular beam 54 capillary columns 55 laser light 56 Converging section 57 Ion trap 58 Reflectron 59 Ion detector 60 time-of-flight mass spectrometer 61,62 lens window 70 Reflector 71,72 Prism means 73 Ion region 74,75 Single prism 76 Reflector

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01J 49/40 H01J 49/40 (72) Inventor Shinsaku Dobashi 5-717-1, Fukahori-cho, Nagasaki-shi, Nagasaki Prefecture Sanryo Heavy Industries Co., Ltd. Nagasaki Research Laboratory F-term (reference) 5C038 GG07 GH10 GH15

Claims (11)

[Claims] 1. A sample introduction means for continuously introducing a sample to be collected into a vacuum chamber, a laser irradiation means for irradiating the introduced sample with a laser to cause laser ionization, and a converging unit for converging laser ionized molecules. A laser measurement device comprising: 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 period, wherein: A laser measuring device, characterized in that the laser beams from the laser irradiating means are subjected to multiple reflection irradiation so that the laser beams do not overlap in the ionized region. 2. The laser measuring device according to claim 1, wherein the multiple reflections are formed by using prisms opposed to each other so that the multiple reflections do not pass through the same path. 3. The laser measuring device according to claim 1, wherein the sample introducing means is a capillary column, and a tip of the capillary column faces an ion converging portion. 4. The laser measuring device according to claim 1, wherein the capillary column is made of quartz or stainless steel. 5. The laser measuring device according to claim 1, wherein the pulse width of the laser emitted from the laser irradiating means is in the range of picoseconds to several tens of picoseconds. 6. The laser measuring device according to claim 1, wherein the pulse frequency of the laser emitted from the laser emitting means is 1 MHz or more. 7. The laser measuring device according to claim 6, wherein the pulse frequency of the laser irradiated from the laser irradiation means is 10 to 200 MHz. 8. The laser measuring device according to claim 1, wherein the sample is a gas in a processing facility that decomposes PCB. 9. A sample is continuously introduced into a vacuum chamber, the sample introduced is irradiated with a laser to be laser-ionized, and the laser-ionized molecules are converged and selectively concentrated by an ion trap. A detection method for detecting the concentration of organic halides in a gas by detecting ions emitted from a trap in a fixed period with a time-of-flight mass spectrometer, wherein the laser light from the laser irradiation means overlaps in the ionization region. A laser measuring method characterized by irradiating multiple reflections of laser light so that there is no such a case. 10. The laser measuring method according to claim 9, wherein prisms in which the multiple reflections face each other are used, and the multiple reflections are performed so as not to pass through the same path. 11. The method for detecting an organic halide according to claim 9, wherein the sample to be collected is a gas in a processing facility that decomposes PCB.