JP2003247984A - Organic halide concentration calibrating device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic halide concentration calibrating device for accurately measuring the concentration of the organic halide in a PCB treatment installation, for example. <P>SOLUTION: This device is equipped with a standard container 12 with the organic halide 11 of a fixed concentration sealed within, a purge gas supply pipe 14 for supplying the container 12 with a purge gas 13 for purging the halide 11 sealed within, and a standard gas introducing pipe 16 for introducing a standard gas 15 accompanied by the halide 11 of the fixed concentration into a mass spectroscope 50 by the supplied gas 13. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic halide concentration calibrating device for accurately measuring the concentration of organic halides in, for example, PCB processing equipment.

[0002]

BACKGROUND ART In recent years, PCB (Polychlorinated biph)
Since enyl, polychlorinated biphenyl: a generic term for chlorinated isomers of biphenyl) is highly toxic, its production and import are prohibited. Although this PCB was first manufactured in Japan around 1954, its adverse effects on the living body and environment became clear as a result of the Kanemi Yusho incident.
In the past year, there was a history of instructions to discontinue production and collection (duty of storage) due to administrative guidance.

PCB 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. 8, the hydrothermal decomposition apparatus 120
Is a cylindrical primary reactor 122, oil 123a, PCB
123b, NaOH 123c, water 123d
It is provided with pressurizing pumps 124a to 124d for pressurizing, a preheater 125 for preheating the liquid mixture, a secondary reactor 126 having a pipe wound structure, a cooler 127 and a pressure reducing valve 128. . Further, a gas-liquid separator 129 and an activated carbon tank 130 are arranged downstream of the pressure reducing valve 127, and exhaust gas (CO ₂ ) 131 is discharged from a chimney 132 to the outside.
Waste water (H ₂ O, NaCl) 133 is separately treated as necessary. The oxygen pipe 135 is directly connected to the primary reactor 125.

In the above apparatus, the pressure inside the primary reactor 122 is increased to 26 MPa by pressurization by the pressurizing pump 124. Further, the preheater 125 preheats the mixed 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. 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 secondary reactor 1
The fluid from 26 is cooled to about 100 ° C. and is depressurized to atmospheric pressure by the depressurization 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. 9, 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 a device 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 time width. is there.

Further, in the above-mentioned organic halide decomposing apparatus, it is necessary to confirm that the PCB concentration in the working environment or the like is always below a predetermined value. In addition, calibration is required to confirm that the measuring device is normal.

In view of the above problems, the present invention is directed to, for example, a PCB.
An object of the present invention is to provide an organic halide concentration calibrating device capable of performing a quick and highly sensitive analysis when monitoring the concentrations of trace components such as.

[0013]

A first aspect of the present invention for solving the above-mentioned problems is to provide a standard container in which an organic halide having a predetermined concentration is sealed, and a purging gas for expelling the organic halide in the standard container. And a standard gas introduction pipe for introducing an organic halide of a predetermined concentration and introducing the same into the mass spectrometer, the organic halide concentration calibrating device.

A second aspect of the present invention is the organic halide concentration calibrating apparatus according to the first aspect of the present invention, which is equipped with a heat retaining means for holding the standard container at an ambient temperature of +5 to 10 ° C.

A third aspect of the present invention is the organic halide concentration calibrating apparatus according to the first aspect of the present invention, further comprising a heat retaining means for holding the standard gas introducing pipe at 150 ° C. ± 20 ° C.

A fourth invention is the organic halide concentration calibrating apparatus according to the first invention, characterized in that the standard container is internally provided with a disk having a plurality of pores.

A fifth invention is the organic halide concentration calibrating apparatus according to the first invention, characterized in that the standard container is filled with glass fiber or beads.

A sixth aspect of the invention is the fuel cell system according to the fourth or fifth aspect of the invention, in which the standard gas is inserted into the bottom of the standard container so as to face the supply port of the supply pipe for supplying the purge gas, and the supplied gas is discharged from the upper part of the container. The organic halide concentration calibrating device is characterized in that

A seventh invention is the organic halide concentration calibrating apparatus according to the first invention, characterized in that the inner surface of the standard container is formed with a coating layer of polytetrafluoroethylene or silicon oxide.

An eighth aspect of the present invention is the organic halide concentration calibrating device according to the first aspect, wherein the standard container is detachable.

A ninth aspect of the invention is the organic halide concentration calibrating device according to the eighth aspect of the invention, in which the detachable standard container is housed in a closed container.

A tenth aspect of the present invention is the organic halide according to the ninth aspect, characterized in that a detection substance is supplied to the standard container and a sensor for detecting the detection substance is provided in the closed container. It is in the concentration calibration device.

An eleventh invention is the tenth invention, wherein
The organic halide concentration calibrating device is characterized in that the detection substance is hydrogen.

A twelfth invention is the organic halide concentration calibrating apparatus according to the first invention, wherein the measurement sample is PCB.

A thirteenth aspect of the present invention introduces the organic halide concentration calibrating device according to any one of the first to twelfth aspects, and sample introducing means for continuously introducing the sample from the measurement line into the vacuum chamber. Laser irradiation means for irradiating a sample with laser to perform laser ionization, a converging unit for converging laser ionized molecules, an ion trap for selectively concentrating the converged molecules, and an ion for detecting ions emitted at a constant period. A time-of-flight mass spectrometer equipped with a detector is provided, which is a detector for organic trace components.

A fourteenth invention is the organic trace component detection apparatus of the thirteenth invention, wherein the sample introducing means is a capillary column, and the tip of the capillary column faces the ion converging portion. In the detection device.

A fifteenth invention is the invention of the thirteenth invention for detecting an organic trace component, wherein the pulse wavelength of the laser is 2
An organic trace component detection device is characterized by having a thickness of 80 nm or less.

[0028] A sixteenth invention is the organic trace element detector of the thirteenth invention, wherein the pulse time width of the laser is 500 picoseconds or less.

A seventeenth aspect of the invention is to measure the organic halide while calibrating the concentration of the organic halide with an organic halide concentration calibrating device at a predetermined number of times of measurement, using the thirteenth organic trace component detecting device. It is in the method of detecting a characteristic organic trace component.

The eighteenth invention is the seventeenth invention, wherein
The above-mentioned measurement sample is PCB, which is a method for detecting organic trace components.

[0031]

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 an organic halide concentration calibrating apparatus according to the present embodiment. As shown in FIG. 1, an organic halide concentration calibrating device 10 according to the present embodiment includes a standard container 12 in which an organic halide 11 having a predetermined concentration is enclosed, and the standard container 1
2 is a mass spectroscope which includes a purge gas supply pipe 14 for supplying a purge gas 13 for purging the enclosed organic halide 11 and a standard gas 15 accompanied by the supplied gas 13 with an organic halide 11 having a predetermined concentration. And a standard gas introduction pipe 16 to be introduced into 50.

Further, valves 23 and 24 are provided on the supply line 21 and the gas discharge line 22 which are branched from the purge gas supply pipe 14 and which supply gas to the standard container. Also, the purge gas supply pipe 14 and the standard gas introduction pipe 1
A valve 25 that opens and closes the flow path with 6 is interposed.

The ambient temperature of the standard container 12 is +5 to +5 than that of the outside of the container by a constant temperature holding means (not shown).
It is kept at 30 ° C. This is to keep the saturation concentration of the organic halide 11 sealed inside constant.

Here, the organic halide 11 is PC
The relationship between the saturated vapor pressure and the concentration of PCB in the case of B is shown in "Table 1" below. When the number of chlorine in the PCB is 2 to 4, it is preferable that the temperature control by the constant temperature bath is 35 ° C. (room temperature (= 25 ° C.) + 10 ° C.). Also,
When the number of chlorine in the PCB is 5 to 7, it is preferable that the temperature control by the constant temperature bath is 50 ° C. (room temperature (= 25 ° C.) + 25 ° C.).

[0036]

[Table 1]

Kanechlor KC300 (trade name: manufactured by Kanega Fuchi Chemical Co., Ltd.), which is a commercially available substance of the above PCB, contains 2 chlorine P
CB, 3 chlorine PCB, and 4 chlorine PCB are mixed. Kanechlor KC400 (trade name: Kanega Fuchi Chemical Co., Ltd.) contains 3 chlorine PCBs, 4 chlorine PCBs, and 5 chlorine PCBs. Kanechlor K60 (trade name: manufactured by Kanega Fuchi Kagaku) has 5 chlorine PCB, 6 chlorine PCB, 7 chlorine PCB
Are mixed.

To bring the PCB into a predetermined saturation state,
A PCB solution dissolved in a standard solution (for example, n-hexane) was supplied into the standard container, degassed in a vacuum for 1 hour, n-hexane was removed, and then sealed at 100 ° C. for 1 hour, It is made uniform and saturated.

The inside of the standard gas introducing pipe 16 is 15
Insulating means (for example, heater) 26 for keeping at 0 ° C ± 20 ° C
Is provided to prevent the organic halide from adhering to the inside of the tube.

Further, it is preferable that the distance D from the standard gas introducing pipe 16 to the standard container 12 is about 10 times the pipe diameter (φ) of the standard gas introducing pipe 16. This is to prevent the heated gas from entering the standard container when the valve 24 is opened when the distance is short.

Since the regulated value of exhaust gas in the above-mentioned PCB treatment equipment is 0.15 mg / Nm ³ (= 15 ppb / V) at present, 1/5 of that amount should be used as a calibration gas in a mass spectrometer as a PCB standard. . Therefore, as shown in FIG. 2, a dilution gas supply pipe 28 for supplying a dilution gas (air or nitrogen etc.) 27 is connected to the standard gas introduction pipe 16 and diluted to a predetermined concentration to form the standard gas 15.

Further, as shown in FIG. 3, the standard container 1 described above is used.
A plurality of discs 31 having a plurality of pores are laminated and installed in the interior of the chamber 2, and the supply port 21a of the supply pipe for supplying the purge gas 13 is inserted so as to face the bottom of the standard container 12. ing. And the drive gas 13
Gas is introduced into the bottom once, and then the gas is passed through the innumerable pores of the plurality of stacked discs 31 to obtain saturated PC.
B is accompanied outside. As a result, a standard PCB product having a uniform concentration can be introduced into the mass spectrometer. Reference numeral 32 in FIG. 3 indicates a thermometer.

Further, as shown in FIG.
Instead of 1, glass fibers or beads 33 may be filled in a standard container.

A coating layer of, for example, polytetrafluoroethylene or silicon oxide may be formed on the inner surface of the standard container 12. This is to prevent the PCB from penetrating into the wall of the container.

Further, as shown in FIG. 5, the standard container 1 described above is used.
2 may be a cartridge type which is detachable via the detachable member 41. As a result, the standard container 12 can be easily mounted, and a plurality of types of standard products can be mounted.

Further, as shown in FIG. 5, the standard container 12 may be covered in the closed container 42 when this detachable container is used. By covering with such an airtight container 42, it is possible to prevent leakage of the PCB to the outside when there is leakage of the PCB during attachment / detachment.

Further, by supplying a detection substance into the standard container 12 and providing a sensor for detecting the detection substance inside the closed container 42, it is possible to detect the mounting failure early.

As the above-mentioned detection substance, for example, hydrogen or the like is preferable, and by mixing about several% of the supply gas 13 to be supplied and mounting a known detection means on the inner wall of the hermetically sealed container 42 covering the cartridge, a rapid leak is obtained. Can be detected.
As a result, the mounting failure can be detected by detecting the detection substance. The hydrogen to be mixed may be 100%, but considering the problem at the time of leakage, it is preferably 4% or less of the explosion limit of hydrogen.

A mass spectrometer 60, which will be described later, is provided by separately providing a sampling port for the organic halide measuring line 100 in a closed container that covers the cartridge type standard container 12.
It is also possible to measure online at.

[Second Embodiment] FIG. 1 is a schematic view of an organic trace component detection apparatus according to the present embodiment. Figure 4
As shown in FIG. 1, the organic trace component detection device 50 according to the present embodiment is a detection device that detects the concentration of organic trace components, and is the organic halide concentration calibration device 1 shown in FIG.
0 and a capillary column 54 which is a sample introduction means for continuously leaking a measurement sample 100 from a normal sample introduction tube 51 into the vacuum chamber 52 and introducing it as a molecular beam 53.
Then, the leaking molecular beam 53 is irradiated with a laser beam 55,
Laser irradiation means 54 for laser ionization, a converging part 56 composed of a plurality of ion electrodes for converging laser ionized molecules, an ion trap 57 for selectively concentrating the converged molecules, and a reflection of ions emitted at a constant period. Time-of-flight mass spectrometer 60 equipped with an ion detector 59 that reflects the ions reflected by the Ron 58 and detects the reflected ions.
And is provided. A vacuum pump 61 is provided in the sample introduction tube, and only a part of the sample is introduced into the capillary column 54. Then, the PCB concentration of the measurement object can be obtained by comparing the signal intensities detected by the detector 59. PCB measured
The concentration may be sent to the monitoring command room and may be disclosed to the outside by, for example, a monitor device (not shown).

By providing the above-mentioned halide concentration calibrating device 10, the time-of-flight mass spectrometer 60 is used for continuously measuring the PCB concentration in the PCB processing facility.
It is possible to calibrate quickly even if there is a measurement fluctuation.

Further, an internal standard gas (for example, monochlorobenzene) 35 having a predetermined concentration for monitoring is supplied to each of the sample introducing pipe 51 and the expelling gas supply pipe 14, and the monitoring gas is monitored to measure. Fluctuations can be detected.

That is, in normal measurement, the concentration of PCB is almost zero, so it is determined whether it is actually zero or whether it is zero due to an abnormality in the device or clogging of the piping. I can't do it. However, by supplying the above-mentioned monitoring gas, it is always detected as a peak with a constant concentration, and therefore the abnormality in the device, piping, etc. can be promptly detected due to the fluctuation.

Also, in the case of calibrating as the standard gas 15, by supplying the monitoring gas 35, if the ratio between the peak and the standard gas is always constant, the standard gas is appropriate. You can check. An example of the measurement chart of the standard calibration measured by both is shown in FIG.

The outline of the measuring device will be described below, but the measuring device applicable to the calibration device of the present invention is not limited to the following device.

It is preferable that the tip of the capillary column 54 into which the gas-exchanged sample 51 is introduced faces the ion converging portion 56. Specifically, among the electrodes forming the ion converging portion 56. It is preferable that the electrode is flush with the electrode closest to the capillary column or protrudes 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 irradiating means 56 is 300 nm or less, preferably 280 nm or less, more preferably 266 ± 10 nm, as will be described later in Examples. . This is because if the thickness exceeds 300 nm, the ionization of the organic trace component, which is the object of measurement, will not be performed well.

The pulse time width of the laser beam 56 emitted from the laser irradiating means 56 is preferably 500 pico (10 ^-12 ) seconds or less, more preferably 200 pico seconds or less. This is because a laser having a pulse time width of nanosecond (10 ⁻⁹ ) has low detection sensitivity and is not preferable.

The pulse repetition frequency of the laser light emitted from the laser irradiating means 56 is preferably 10 MHz or higher, and particularly preferably 76 MHz. This is because the ionization efficiency is continuously improved by improving the pulse repetition frequency.

In this way, the pulse time width of the laser light is set to 5
By shortening it to 00 picoseconds (10 ⁻¹² ) or less, it is possible to suppress the decomposition of PCB by the laser beam and improve the detection sensitivity.

Using the above measuring device, the organic halide concentration calibrating device 1 is used when a predetermined number of times of measurement or time has elapsed.
By calibrating the device with the standard gas 15 from 0, for example, the PCB concentration in the PCB decomposition treatment facility can be measured quickly and accurately over a long period of time.

[Third Embodiment] FIG. 7 shows a monitoring system for gas in a PCB detoxification treatment facility using the above-mentioned measuring device. As shown in FIG. 1, the system according to the present embodiment is a harmful substance treatment system for detoxifying an object to be treated to which an organic halide (eg, PCB), which is a harmful substance, is attached, contained, or stored. , Hazardous substance (eg PCB) 1002 which is the object to be treated 1001
Means 1004 for extracting the harmful substance 1002 from the container 1003 for storing the object, and the constituent material 1001a constituting the object 1001 to be processed,
b, ... Dismantling means 1005 for dismantling one or both of them, pretreatment means 1006, core 1001a which is a constituent material constituting the object processed in pretreatment means 1006, coil 1001b and iron core 1001c Core separation means 10 for separating into
07, separated coil 1001b, copper wire 1001d and paper / wood 10
Coil separating means 1008 for separating into 01e, iron core 1001c separated by the above core separating means 1008, metal container (container body and lid etc.) 1003 separated by disassembling means 1005 and coil separating means 1008 The cleaning means 1011 for cleaning the copper wire 1001d with the cleaning liquid 1010, and the harmful substance decomposition treatment means 1013 for decomposing either one or both of the cleaning waste liquid 1012 after the cleaning and the harmful substance 1002 separated by the pretreatment means, PCB
From the wastewater monitoring means 1100 that measures the PCB concentration in the wastewater 133 discharged from the hazardous substance decomposition processing means 1013 that is the treatment facility, and the PCB concentration and harmful substance decomposition processing means 1013 in the pretreatment means 1006 that disassembles the PCB-treated material. The exhaust gas monitoring means 1200 for measuring the PCB concentration of the exhaust gas 131 or the like to be discharged is provided.

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.

Regarding the exhaust gas discharged from the treatment equipment, it is confirmed that the concentration of PCB in the exhaust gas after passing through the activated carbon filter is below the emission standard of PCB using the exhaust gas monitoring means 1200. I am trying to do it. Furthermore, the exhaust gas monitoring means 1200 may be used to monitor the PCB concentration in the environment outside the facility as well as inside the facility.

The harmful substance processing means 1013 is shown in FIG.
In addition to the hydrothermal oxidative decomposition treatment means for hydrothermal oxidative decomposition treatment shown in (1), for example, a supercritical water oxidation treatment means for supercritical water oxidization treatment or a batch type hydrothermal oxidative decomposition treatment may be used.

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

PCBs have been conventionally used in ballasts for fluorescent lamps, so it is necessary to detoxify them. In this case, since the capacity is small, there is no need for pretreatment, and the separation means 1009 can be directly treated. It can be detoxified by throwing it in.

Therefore, when the presence / absence of PCB concentration is analyzed at every predetermined time using this measuring device, the calibration gas is supplied from the calibration device every time a predetermined time elapses (for example, one week or 10 days). It is possible to always prove that the measuring device is sound by inputting.

[0071]

As described above, according to the present invention,
By using the above-mentioned measuring device and calibrating with a standard product from an organic halide concentration calibrating device when a predetermined number of measurements or time has elapsed, for example, a PC in a PCB decomposition treatment facility
The B concentration can be measured quickly and accurately over a long period of time.

[Brief description of drawings]

FIG. 1 is a schematic diagram of an organic halide concentration calibrating apparatus according to a first embodiment.

FIG. 2 is a schematic view of a main part of an organic halide concentration calibrating device.

FIG. 3 is a schematic view of a standard container.

FIG. 4 is a schematic view of another standard container.

FIG. 5 is a schematic view of another standard container.

FIG. 6 is a measurement chart of standard calibration.

FIG. 7 is a schematic diagram of a PCB detoxification processing system.

FIG. 8 is a schematic diagram of a hydrothermal decomposition apparatus.

FIG. 9 is a schematic diagram of a laser measuring device according to a conventional technique.

[Explanation of symbols]

10 Organic Halide Concentration Calibration Device 11 Predetermined concentration of organic halide 12 standard containers 13 Expulsion gas 14 Drive-out gas supply pipe 15 standard gas 16 Standard gas inlet pipe 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

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinsaku Dobashi             3-5-1, 717-1, Fukahori-cho, Nagasaki-shi, Nagasaki             Hishi Heavy Industries Ltd. Nagasaki Research Center

Claims (18)

[Claims] 1. A standard container in which an organic halide having a predetermined concentration is enclosed, and a purging gas for expelling the organic halide is supplied to the standard container to accompany the organic halide having a predetermined concentration,
An apparatus for calibrating an organic halide concentration, comprising: a standard gas introduction pipe introduced into a mass spectrometer. 2. The organic halide concentration calibrating device according to claim 1, further comprising a heat retaining unit that keeps the standard container at an ambient temperature of +5 to 100 ° C. 3. The organic halide concentration calibrating device according to claim 1, further comprising a heat retaining means for holding the standard gas introducing pipe at 150 ° C. or higher. 4. The organic halide concentration calibrating device according to claim 1, wherein a disk having a plurality of pores is provided inside the standard container. 5. The organic halide concentration calibrating device according to claim 1, wherein the standard container is filled with glass fiber or beads. 6. The method according to claim 4, wherein the supply port of the supply pipe for supplying the purge gas is inserted into the bottom of the standard container so as to face it, and the supplied gas is discharged from the upper part of the container. Organic halide concentration calibration device. 7. The organic halide concentration calibrating device according to claim 1, wherein the inner surface of the standard container is provided with a coating layer of polytetrafluoroethylene or silicon oxide. 8. The organic halide concentration calibrating device according to claim 1, wherein the standard container is removable. 9. The organic halide concentration calibrating device according to claim 8, wherein the removable standard container is housed in a closed container. 10. The organic halide concentration calibrating device according to claim 9, further comprising a sensor for supplying the detection substance into the standard container and a sensor for detecting the detection substance in the closed container. 11. The organic halide concentration calibrating device according to claim 10, wherein the detection substance is hydrogen. 12. The organic halide concentration calibrating device according to claim 1, wherein the measurement sample is PCB. 13. The organic halide concentration calibrating device according to claim 1, sample introducing means for continuously introducing a sample from a measurement line into a vacuum chamber, and a laser for introducing the sample. A laser irradiation means for irradiating the laser beam for laser ionization, a converging unit for converging the laser ionized molecules, an ion trap for selectively concentrating the converged molecules, and an ion detector for detecting the ions emitted at a constant period. A time-of-flight mass spectrometer provided with the detection apparatus for organic trace components. 14. The organic trace component detection device according to claim 13, wherein the sample introduction means is a capillary column, and the tip of the capillary column faces the ion converging portion. 15. The organic trace component detection apparatus according to claim 13, wherein the laser has a pulse wavelength of 280 nm or less. 16. The organic trace component detection device according to claim 13, wherein the pulse time width of the laser is 500 picoseconds or less. 17. The organic trace component detecting device according to claim 13, wherein the organic halide concentration is calibrated by an organic halide concentration calibrating device every predetermined number of measurements, and the organic halide is measured. Method for detecting organic trace components. 18. The method for detecting an organic trace component according to claim 17, wherein the measurement sample is PCB.