LT5135B - Device and method for detecting trace amounts of organic components - Google Patents

Abstract

A device for detecting the trace amounts of organic components, which is a device for detecting an organic halide concentration in a gas, and which comprises a capillary column (54) as a sample introducing a collected sample (51) continuously into avacuum chamber (52) as a leaking molecular beam (53), a laser irradiating means (56) for irradiating the leaking molecular beam (53) with a laser beam (55) for laser - ionising, a converging unit (56) consisting of a plurality of ion electrodes for converging laser - ionised molecules, an ion trap (57) for selectively concentrating the converged molecules, and a time-of-flight mass spectrometer (60) that reflects emitted ions at a specified cycle by means of a reflectron (58) and is provided with an ion detector (59) for detecting reflected ions.

Description

Technical field

The present invention relates to a device and method for detecting traces of organic components such as PCBs and dioxins in processing equipment or in the environment.

Prior art

PCBs (polychlorinated biphenyls; common name for chlorinated biphenyl isomers) have been banned in recent years due to their high toxicity. In Japan, PCB production began around 1954. However, the Kanemi Yush case showed the harmful effects of PCBs on living organisms and the environment. The Japanese government has issued an order stopping the production of PCB products and disposing of PCB products (the obligation of safe storage).

PCB is a compound obtained by replacing 1-10 biphenyl hydrogen atoms with chlorine atoms. In theory, PBCs have 209 isomers that differ in the number and positions of substituted chlorine atoms. Currently, about 100 or more PCB isomers are marketed as PCB products. PCB isomers have different physicochemical properties, different stability in living organisms and different environmental behaviors. Therefore, chemical analysis of PCBs is difficult. In addition, PCBs cause various types of environmental contamination. PCBs are resistant to organic pollutants and are not readily degradable in the environment. PCBs are fat soluble and have a high degree of bioconcentration. In addition, PCBs can spread through the air because they are semi-volatile. PCBs are also known to persist in the environment, e.g. in water or in living organisms.

Because PCBs are highly stable in living organisms, they accumulate in them and these accumulated PCBs cause chronic intoxication (eg skin diseases and liver disease), and are carcinogenic and reproductive and developing toxic.

PCBs have generally been widely used as insulating oils, for example for transformers and capacitors. In order to detoxify the PCBs contained therein, the present inventors have previously proposed a hydrothermal digester for detoxifying PCBs (see, for example, Japanese Patent Application Nos. 11-253796 and 2000-7588). Figure 32 schematically shows the construction of such a hydrothermal splitting device.

As shown in Figure 32, the hydrothermal splitting unit 1 has a cylindrical primary reactor 2; high pressure pumps 3a-3d for pumping oil 4a, PCBiii 4b, NaOH 4c and water 4d; a heater 5 for preheating the liquid mixture of NaOH 6c and water 6d; a secondary reactor 7 having a helical tube; refrigerator 8; and a pressure relief valve 9. The gas-liquid separator device 10 and the activated carbon bath 11 are located downstream of the pressure relief valve 9. The flue gas (CO ₂ ) is discharged from the stack 12 into the environment and the working fluid (H ₂ O, NaCl) 13. , if desired, is submitted to treatment. The oxygen supply tube 14 is connected directly to the primary reactor 2.

In the above-mentioned device 1, the high pressure pumps 15 increase the pressure inside the primary reactor 2 to 26 MPa. The liquid mixture of PCBs, H ₂ O and NaOH 4 is initially heated to about 300 ° C by means of a heater 5. oxygen is fed to reactor reactor 2 and the temperature inside reactor reactor 2 is raised to 380-400 ° C using the reaction temperature that began in the reactor. The reactor 2 undergoes a dechlorination reaction and an oxidative decomposition reaction and decomposes to NaCl, CO _2, and H ₂ O. The effluent from the secondary reactor 7 is then cooled to about 100 ° C in a refrigerator 8 and the fluid pressure is reduced to atmospheric pressure by a pressure relief valve 9 then the liquid is distributed to CO ₂ , steam and treated water using a gas-liquid separator 10. The resulting CO ₂ and vapor are passed through an activated carbon bath 11 and released into the environment.

When treating containers containing PCBs (eg transformers and capacitors) with the device described above, complete decontamination of these containers is achieved. The key to this process is the rapid monitoring of PCB concentration in this equipment. Typically, gaseous PCBs are sampled and concentrated to a liquid, and this PCB-containing liquid is then analyzed. However, the measurement of PCBo concentration by such a method requires several to several tens of hours; thus, rapid monitoring of PCB concentrations is not possible.

In this regard, a mass spectrometer equipped with a multiphoton ionisation detector and a run-time mass spectrometer (TOFMAS) have been proposed to control the trace amounts of PCBs typically present in gas.

A typical analysis device with reference to config.33 will now be described.

As shown in FIG. 33, sample gas 16 is fed in the form of ultrasonic free current through a vibrating nozzle 17 to a vacuum chamber 18. Due to adiabatic expansion, the free current is cooled. In this way, the vibration and rotation levels of the cooled gas are lowered, thereby increasing the wavelength selectivity of the gas. As a result, the gas effectively absorbs the laser beam 19 (multiphoton resonance) and increases the ionization efficiency of the gas. In this way, the molecules in the ionized gas are accelerated by an accelerating electrode 20, and the molecules receive acceleration inversely proportional to their mass. These accelerated molecules run through the flow tube 21. The molecules are reflected by the reflectors 22 and enter the detector 23. When the flow time of the molecules is measured in the flow tube, the masses of the particles formed by the molecules are calculated. The concentration of PCBs (i.e., the measurement target) can be obtained by comparing the intensities of the signals output from the detector 23.

Although the above analysis method can detect traces of material, the detection sensitivity of the device is low because the device employs a laser having a pulse width of nanoseconds.

Based on these facts, it is an object of the present invention to provide an apparatus and method for detecting traces of an organic component that enables rapid and highly sensitive analysis to monitor the concentration of PCBs in gas.

In the above-mentioned hydrothermal cleavage device 1, various reaction parameters are controlled, including feed rates of various chemicals and PCBs (cleavage target) so that the PCBs completely decompose.

Typically, the digestion treatment was controlled on the basis of data obtained by measuring, for example, the amount of PCBs remaining in the digestion fluid and the properties of the degradation products obtained during digestion. However, such measurements take from a few hours to a day or two.

Therefore, there is a need for effective back control of the hydrothermal splitting device 1 during the fracturing treatment.

this. It is another object of the present invention to provide a method for controlling the digestion of a toxic substance that provides rapid feedback control in a digestion unit for toxic substances such as PCBs.

When using the above mentioned device for the decomposition of organic halogenated substances, the concentration of PCBs in the working environment must always be at or below predetermined levels. Therefore, the instrument to measure the traces of PCBs must be calibrated at specified intervals for it to work accurately.

In this regard, another object of the present invention is to provide a device for adjusting the concentration of an organic halogenated substance that enables rapid and highly sensitive analysis when monitoring traces of a component such as PCBs.

DESCRIPTION OF THE INVENTION The present invention encompasses a group of inventions, namely, objects of the invention for detecting traces of an organic component:

The first object of the invention is a device for detecting traces of an organic component, comprising:

a sample delivery device for continuously injecting the collected sample into a vacuum chamber by laser irradiation of the sample thus introduced with the ionizing radiation of said sample;

convergence sections for the approximation of molecules which have been ionized by laser irradiation; and a run-time mass spectrometer that includes an ion detector for detecting ions that are released at predetermined intervals.

The second object of the invention is a device for detecting traces of organic matter according to a first object in which the sample delivery device is a capillary column and the tip of this capillary column intervenes in the convergence section.

A third object of the invention is a device for detecting traces of organic matter according to a first object wherein the capillary column is made of quartz or stainless steel.

A fourth object of the invention is a device for detecting traces of organic material according to a first object, wherein the laser beam emitted from the laser irradiation device has a wavelength of 300 nm or less.

A fifth object of the invention is a device for detecting traces of organic matter according to a first object, wherein the laser beam emitting from the laser irradiation device has a pulse width in the order of picoseconds.

A sixth object of the invention is a device for detecting traces of organic matter according to a first object, wherein the laser beam emitted from the laser irradiation device has a pulse frequency of at least 1 MHz.

A seventh object of the invention is a device for detecting traces of organic material according to a first object, wherein the traces of the organic component are traces of PCBo in a gas treatment unit where PCBo is decomposed.

The eighth object of the invention is a device for detecting traces of organic matter according to a first object, wherein the traces of the organic component are traces of PCBo contained in the pipeline gas or in the spent fluid discharged from the PCBo processing unit.

The ninth object of the invention is a device for detecting traces of organic matter according to a first object, wherein the laser beam emitting from the laser irradiation device has a wavelength of 300 nm or less, a pulse width of 1000 picoseconds or less and an energy density of 1 GW / cm ² ; traces of the organic component are detected while the decomposition of the organic component is stopped.

The tenth object of the present invention is a device for detecting traces of organic matter according to a ninth object wherein the laser beam has a density of energy of 1 to 0.01 GW / cm ² .

The eleventh object of the invention is a device for detecting traces of organic matter according to a ninth object, wherein the traces of the organic component are traces of PCBo having a low chlorine atom number (hereinafter referred to as "low chlorine PCBu"), laser wavelength 250-280 nm, a pulse width of 500 to 100 picoseconds and an energy density of 1 to 0.01 GW / cm ² .

The twelfth object of the invention is a device for detecting traces of organic matter according to a ninth object, wherein the traces of the organic component are traces of PCBo having a high number of chlorine atoms (hereinafter referred to as high chlorine PCBu ''). nm, pulse width from 500 to 1 picosecond, and energy density from 1 to 0.01 GW / cm ² .

The thirteenth object of the invention is a device for detecting traces of organic matter according to a first object in which a laser beam passes through a Raman cell.

The fourteenth object of the invention is a device for detecting traces of organic matter according to a thirteenth object containing hydrogen in a Raman cell.

The fifteenth object of the invention is a device for detecting traces of organic matter according to a first object, wherein the ion trap consists of a first electrode with a cap at its end having a small hole through ionized molecules, a second electrode with a cap at its end having a small hole through which (the first and second electrodes are opposite each other) and a high-frequency electrode for supplying the ion trap with a high-frequency voltage at the end of the first electrode with a cap is lower than that of the convergent ionization molecules and with the second electrode at the end of the cap the voltage at the back of the electrode with a cap; and the ionized molecules are trapped at high frequency voltage while the molecules in the ion trap are selectively retarded.

The sixteenth object of the present invention is a device for detecting traces of organic matter according to a fifteenth object wherein the ion trap is an inert gas.

Seventeen object of the invention is a device for detecting trace amounts of organic material in accordance with a fifteenth object of the ionization zone 1x10 ^'3 torr vacuum, the ion convergence section and the ion trap is 1x10 ^"5 torr vacuum and a time-mass spectrometer is 1x10' ⁷ torr vacuum.

The eighteenth object of the invention is a device for detecting traces of organic matter according to a first object, wherein the laser beam emitted from the laser irradiation device is reflected several times so that the reflected laser beams in the ionization zone do not overlap with one another.

The nineteenth object of the present invention is a device for detecting traces of organic matter according to an eighteenth object in which the laser beam emitted from the laser irradiation device is reflected several times using opposing prisms so that the reflected laser beams do not follow the same path.

the present invention also includes objects relating to a method for detecting traces of organic components.

The twentieth object of the invention is a method for detecting traces of an organic component in a gas, comprising: continuously injecting a collected sample into a vacuum chamber; laser irradiating said introduced sample, thereby ionizing said sample by selectively trapping ionized molecules by laser irradiation in an ion trap, bringing the molecules closer together; and detecting the ions emitted from the ion trap at specified intervals using a trap pass time mass spectrometer.

The twenty-first object of the invention is a method for detecting an organic component in a gas according to the twentieth object, wherein the gas is present in a gas treatment plant in which the PCBo is decomposed.

The twenty-second object of the invention is a method for detecting an organic component in a trace gas according to the twentieth object, wherein the ion trap comprises a first electrode with a cap at its end having a small hole through which a second electrode with a cap at its end having a small hole at its end. trapped molecules (first and second electrodes facing each other) and high-frequency electrode to provide high-frequency voltage to the ion trap; the voltage at the end of the first electrode having a cap is lower than the voltage at the ion convergence section to bring the ionized molecules closer together, and the voltage at the end of the second electrode having a cap is higher than the voltage at the end of the first electrode; and the ionized molecules are trapped at high frequency voltage while the molecules in the ion trap are selectively retarded.

The twenty-third invention is the organic component of trace gas detection method according to the twenty-second object, wherein the ion scavenger is permitted inert gas ionization zone 1x10 ^'3 torr vacuum, the convergence section and the ion trap is 1x10 ^"5 torr vacuum and a time-mass spectrometer is a 1 x10 ' ⁷ torus vacuum.

The twenty-fourth object of the present invention is a method for detecting an organic component in a gas according to the twenty-first object, wherein the gas is present in a gas treatment plant in which the PCB is cleaved.

The twenty-fifth object of the present invention is a method for detecting an organic component in a trace gas according to the twenty-first object, wherein the laser beam emitted from the laser irradiation device is reflected multiple times so that the reflected laser beams in the ionization zone do not overlap.

The twenty-sixth object of the present invention is a method for detecting an organic component in a trace gas according to a twenty-fifth object wherein the laser beam emitted from the laser irradiation device is reflected multiple times using opposed prisms so that the reflected laser beams do not follow the same path.

The present invention also relates to objects relating to a method for controlling the decomposition of a toxic substance using a trace detection device for organic components.

The twenty-seventh object of the invention is a method for controlling the degradation treatment of a toxic substance comprising measuring the concentration parameters of the toxic substance and / or the product obtained by cleavage of the toxic substance in the working fluid by a run-time mass spectrometer detailed in the first invention. a material digestion apparatus comprising a reactor for digesting toxic material; and optimizing the digestion conditions of the toxicant based on the concentration of the toxicant and / or toxicant degradation product so measured.

The twenty-eighth object of the invention is a method for controlling the degradation treatment of a toxic substance according to a twenty-seventh object, wherein the degradation products of the toxic substance are, for example, dichlorobenzene, phthalate, volatile organic compound, phenol, biphenyl, benzene derivative or biphenyl, aldehyde, organic acid or aromatic.

. . ,,. ..,. LT 5135 B

The present invention also encompasses objects relating to a digestion system for a toxic substance, which includes a trace detection device for an organic component.

The twenty-ninth object of the present invention is a digestion system for a toxic substance consisting of a hydrothermal oxidation-decomposition device comprising a heated and uniform pressure reactor in which the organic halogenated material is decomposed into, for example, sodium chloride (NaCl) and carbon dioxide (CO ₂ ). through dechlorination and oxidation-cleavage in the presence of sodium carbonate (Na ₂ CC>3); an organic component trace detecting device for measuring the concentration of a toxic substance and / or a product obtained by cleavage of the toxic substance in the digestion fluid discharged from the hydrothermal oxidation-cleavage device, further described in the first invention; and an operation control device for controlling the operation of the hydrothermal oxidation-decomposition unit based on the measurement results obtained by the organic component trace detection device.

The thirtieth object of the invention is a toxic material decomposition system according to a twenty-ninth object, wherein the hydrothermal oxidation-decomposition unit comprises a cylindrical primary reactor; a constant pressure pump for maintaining the pressure of the oil or organic solvent, the toxic substance, water (H ₂ O) and sodium hydroxide (NaOH); a preheater for preheating the water; a secondary reactor having a coiled tube for cooling the treated liquid discharged from the secondary reactor; a gas-liquid separator for separating the treated liquid from the gas; and a pressure relief valve.

The thirty-first object of the present invention is a toxic substance digestion system according to a twenty-ninth object, wherein the action control means controlling at least one of the operations selected from heating a toxic digestion system, maintaining a constant pressure system, a fluid feed rate, and sodium hydroxide (NaOH) feed.

the present invention also includes objects relating to simultaneous measurement of gas samples taken from a plurality of sampling points. This measuring device contains an organic component trace detector.

The thirty-second object of the present invention is an organic component trace measuring device comprising an organic component trace detecting device as further described in the first object; a plurality of sampling tubes for gas sampling from gas sampling points along the gas path; a valve located in each sampling tube; a connecting tube for connecting the sampling tubes to the laser irradiation device of the detection device; a gas suction device for ensuring gas circulation, which is connected to a connecting pipe; a purge device for discharging residual gas bound between the valve disposed in each of the sampling tubes and the detection device; this purge device is connected to the connecting pipe.

The thirty-third object of the present invention is an organic component trace measuring device according to the thirty-second object, further comprising a return tube disposed between the valve and the location to which the sampling tubes are connected and connected to the gas path; and a gas circulation device for providing gas circulation which is mounted on the return pipe.

The thirty-fourth object of the invention is an organic component trace measuring device according to the thirty-second object, wherein the suction device comprises a diaphragm pump connected to the connecting pipe and a valve arranged between the connecting pipe and the diaphragm pump.

The thirty-fifth object of the invention is an organic component trace measuring device according to a thirty-second object, wherein the purifying device comprises a centrifugal helical pump connected to a connecting tube and a valve disposed between the connecting tube and the centrifugal helical pump.

The thirty-sixth object of the invention is an organ component trace measuring device according to the thirty-second object, wherein the valve is any valve selected from a vacuum solenoid valve, an electric ball valve, and a bellows valve.

The present invention also encompasses objects relating to a device for calibrating an organic component trace measuring device.

The thirty-seventh object of the invention is a device for adjusting the concentration of an organic halogenated substance for calibrating an organic component trace detection device described in the first object, which comprises a container containing a defined concentration of an organic halogenated substance; and feeding a standard gas inlet tube purge gas into a standard container for purifying the organic halogenated material, thereby introducing into the mass spectrometer an organic halogenated material accompanied by the purifying gas.

π

The thirty-eighth object of the present invention is a device for adjusting the concentration of an organic halogenated substance according to the thirty-seventh object, further comprising a temperature maintaining device for maintaining the temperature of a standard container such that it is 5-100 degrees above ambient temperature.

The thirty-ninth object of the present invention is a device for adjusting the concentration of an organic halogenated substance according to the thirty-seventh object, further comprising a temperature maintaining device for maintaining a standard gas inlet pipe temperature of 150 ° C or higher.

The fortieth object of the invention is a device for adjusting the concentration of an organic halogenated substance according to the thirty-seventh object, wherein the standard container is provided with a disc having a plurality of holes.

The forty-first object of the invention is a device for adjusting the concentration of an organic halogenated substance according to the thirty-seventh object, wherein the standard container is filled with fiberglass or granules.

The forty-second object of the invention is a device for adjusting the concentration of the organic halogenated substance according to the forty object, wherein the feed pipe for purging gas is arranged at the bottom of a standard container so that the outlet of the feed pipe is downwards and the feed gas is discharged from the upper part.

The forty-third object of the present invention is a device for adjusting the concentration of an organic halogenated substance according to the thirty-seventh object, wherein the inner walls of a standard container are coated with a layer consisting of polytetrafluoroethylene or silica.

The forty-fourth object of the present invention is a device for adjusting the concentration of an organic halogenated substance according to the thirty-seventh object, wherein the standard container is arranged to be removable.

The forty-fifth object of the invention is a device for adjusting the concentration of an organic halogenated substance according to the forty-fourth object, wherein the removable standard container is contained in an airtight container.

The forty-sixth object of the invention is a device for adjusting the concentration of an organic halogenated substance according to a forty-fifth object, wherein the detectable substance is fed to a standard container and the sensor for detecting the detectable substance is arranged in an airtight container.

The forty-seventh object of the invention is a device for adjusting the concentration of an organic halogenated substance according to a forty-sixth object, wherein the detectable material is hydrogen.

The forty-eighth object of the invention is a device for adjusting the concentration of an organic halogenated substance according to the thirty-seventh object comprising PCBo in the sample.

The forty-ninth object of the invention is a method for determining trace amounts of an organic component, comprising detecting the halogenated organic material by adjusting the concentration of the organic halogenated substance over time in a device for adjusting the concentration of the organohalogenated substance described in the thirty-seventh object.

The fiftieth object of the invention is a method for detecting traces of an organic component according to a forty-ninth object, wherein the sample contains PCBs and the organic halogenated substance is PCB.

Brief description of the drawings

Fig. 1 is a schematic view showing a device for detecting organic halogen according to a first embodiment.

Figure 2 shows the measurement results for low chlorine PCBs.

Figure 3 is a schematic representation showing a PCB concentration measurement system according to a second embodiment.

Figure 4 illustrates the relationship between the wavelength, the pulse width and the energy density of the laser beam used in the third embodiment.

Figure 5 shows the measurement results for low chlorine PCBs using a laser beam having an energy density of 0.05 GW / cm ² .

Figure 6 shows the measurement results for low chlorine PCBs using a laser beam having an energy density of 0.5 GW / cm ² .

Fig. 7 is a schematic view showing a trace detection device for an organic component according to a fourth embodiment.

Figure 8 shows the Raman effects of a laser beam that has passed through a Raman cell.

Figure 9 shows the relationship between the wavelength of a laser beam and the effect of energy on Raman effects.

Figure 10 shows the relationship between the wavelengths and the ionization efficiencies of PCBs containing 1-6 chlorine atoms.

Figure 11 shows the measurement results of PCBs using a laser beam passing through a Raman cell.

FIG. 12 is a schematic representation showing an organic component trace detecting device according to a fifth embodiment.

Fig. 13 is a schematic representation showing an ion trap.

FIG. 14 shows the relationship between the electric potential and the ion approximation to the central part of the ion trap.

FIG. 15 is a schematic representation showing an organic component trace detecting device according to a sixth embodiment.

FIG. 16 shows a PCB analysis of a device according to a sixth embodiment containing a vacuum of 1x10 ⁵ torus.

FIG. Figure 17 shows a comparative analysis of PCBs using a device according to a sixth embodiment containing a 1x10 ⁴ torus vacuum.

Fig. 18 is a schematic view showing a device for detecting an organic halogenated substance according to a seventh embodiment.

Figure 19 is a schematic representation showing multiple reflections of a laser beam.

Fig. 20 is a schematic view showing an optical device for laser beam input.

Figure 21 (A) is a side view of the device shown in Figure 20; and Figure 21 (B) is a perspective view of the device shown in Figure 20.

Figure 22 is a schematic representation showing a system for detoxifying PCBs according to an eighth embodiment.

Fig. 23 is a schematic representation showing a digestion system for an organic halogenated material according to a ninth embodiment.

Fig. 24 shows the measurement results of the cleavage products.

Fig. 25 is a schematic representation showing a configuration of a multi-site measuring system according to a tenth embodiment.

Figure 26 is a schematic representation showing a device for adjusting the concentration of organic halogenated material according to an eleventh embodiment.

Figure 27 is a schematic representation showing the main part of the device for adjusting the concentration of organic halogenated material.

Figure 28 is a schematic representation showing a standard container.

Fig. 29 is a schematic representation showing another container

Fig. 30 is a schematic representation showing another standard container

Figure 31 is a graph showing the PCB measurement results after a standard calibration.

Fig.32 is a schematic representation showing a hydrothermal splitting device.

Fig.33 is a schematic view showing a conventional measuring device in which a laser beam is used.

Best embodiments of the present invention

To further illustrate the present invention, best practices for its implementation will be described below with reference to the accompanying drawings. However, the present invention is not limited to the following embodiments.

The first embodiment

Fig. 1 is a schematic view showing a device for detecting an organic halogenated substance according to a first embodiment. In this embodiment, the organic halogenated substance detection device 24 is used to detect the organic halogen in the gas. As shown in FIG. 1, this detection device 24 has a capillary column 25 (sample delivery device) for continuous delivery of a sampled sample 26 having the shape of a passing molecular beam 27 into a vacuum chamber 52; a laser irradiation device 66 for irradiating the incident molecular beam 27 with a laser beam 28 thereby ionizing the molecules; a convergence section for converging 29 ionizing molecules of laser irradiation containing a plurality of ionic electrodes; an ion trap for selectively trapping 30 molecules so fused; and a run-time mass spectrometer 31 having an ion detector 32 for detecting ions that are emitted at certain time intervals and reflected by reflector 33.

Concentrations of PCBs (i.e., measurement target) can be obtained by comparing the intensities of the signals output from detector 32.

The concentration of PCBs thus obtained can be sent, for example, to and from the monitor-control chamber using, for example, a monitoring device (not shown) mounted outside the detection device 24.

Preferably, the capillary column 25 is arranged such that the tip of the column is submerged in the ion convergence section 29. More particularly, the cap of the capillary column is flush with the electrode adjacent the capillary column in the convergence section or the capillary column is mounted the tip is intervened in the convergence section toward the ion trap at some distance, measured from this electrode.

Preferably the capillary column is made of quartz or stainless steel. When the capillary column is made of stainless steel, the passing molecular beam can be regulated by applying a voltage to the ion convergence section 29.

Preferably, the capillary column has a diameter of 1 mm or less. Preferably, the capillary column is positioned such that its tip is approximately 3 mm away from the laser beam. Preferably, the capillary column outlet is located near the point where the molecular beam is irradiated with a laser beam. However, when the distance between the outlet and the irradiation site is very small, the laser beam destroys the tip of the capillary column. Therefore, it is desirable to reduce the distance so as to avoid disruption of the capillary column, for example by reducing the distance to about 12 mm, thereby increasing the ionization efficiency.

The laser beam 28 emitted from the laser irradiation device 34 has a pulse wavelength of 300 nm or less, preferably 234 ± 10 nm. If the pulse wavelength exceeds 300 nm, the ionization of the organic halogenated material (i.e., the measurement target) is no longer efficient.

Preferably, the laser beam 28 emanating from the laser irradiation device 34 has a pulse width in the order of picoseconds. If a laser beam with a nano (10 ' ⁹ ) - second pulse width is used, the detection sensitivity is reduced.

Thus, when using a laser beam having a peak (10 ^'12 ) -second pulse width, the laser beam-induced cleavage of the PCBo can be reduced and the detection sensitivity increased.

Table 2 shows sensitivity results for PCB detection when lasers with different pulse widths are used.

For this measurement, a sample of PCBs containing PCBs containing 1 to 4 chlorine atoms (hereinafter referred to as PCBs containing chlorine atoms can generally be referred to as "n-CI PCB") and mainly 2-CI PCBs and 3-CI PCBs was used.

Signal intensities were measured using a laser beam having a 100 picosecond pulse width and a laser beam having a 24 nanosecond pulse width.

In this embodiment, a picosecond laser (fixed wavelength: 234 nm) was used for measurements.

(Table 1) PCB detection sensitivities at different laser pulse widths

Measuring molecule Signal intensity (mV) when a laser beam was used, having 100 picosecond pulse width Signal intensity (mV), when laser was used a beam having a pulse width of 100 picoseconds 1-CI PCB 26.5 6.8 2-CI PCB 87.5 12.8 3-CI PCB 31.8 6.4 4-CI PCB 1.7 0.4 PCB decay product 24.4 4.4

Figures 2 (a) and 2 (b) are diagrams showing the signals emitted by the PCB ion detector. In each of the graphs, the horizontal axis represents the passage time (in seconds) and the vertical axis represents the ionic signal intensity (V). The signal corresponding to the 4-CI PCB is also shown in Fig. 2 (b), which is an enlarged view of Fig. 2 (a).

Using the aforementioned measuring device, the concentration of PCBs remaining, for example, in the gas PCB digester or in the liquid discharged from the device, can be measured quickly and accurately. Based on the results of these measurements, for example, the process can be monitored.

If the concentration of PCBs remaining in the working fluid is measured, the working fluid is injected into the device or the working fluid is vaporized and the resulting vapor is injected into the device.

Second embodiment

Figure 3 is a schematic representation showing a device for measuring the concentration of PCBs in gas.

As shown in Figure 3, the PCB concentration measurement system 35 includes a gas sampling line 36 that is connected to the vacuum chamber 37 of the detection device 24. As shown in Figure 1, the sample is introduced into the vacuum chamber 37 via a flow line 36 and is ionized with a laser beam 28 emitted from the laser irradiation device 34, and the resulting ions are detected by a pass-through mass spectrometer 31. The number 38 denotes a vacuum device for evacuating the vacuum chamber 37, and the number 39 denotes control devices for the above devices.

Using a measuring system 35, rapid, highly sensitive PCB analysis can be performed; more specifically, PCBs can be determined to the nearest 0.01 mg / Nm ³ in 1 minute.

Third embodiment

In this embodiment, the laser irradiation conditions used in the first embodiment are further specified.

The measuring device of this embodiment has a structure similar to that of the first embodiment. Therefore, the device of this embodiment will be described with reference to FIG.

In a first embodiment, the laser beam 28 emitted from the laser irradiation device 34 has a wavelength of 300 nm or less, preferably 234 ± 10 nm. In this embodiment, when the organic halogenated material (i.e., the assay target) is a low chlorine PCB, i.e. PCBs containing 1-3 chlorine atoms are preferably at a wavelength of 224-280 nm.

Then, when the organic halogenated material (i.e. the target of the assay) is a high chlorine PCB, i.e. PCBs having at least 4 chlorine atoms are preferably at a laser wavelength of 270-300 nm for the following reason: As the number of chlorine atoms in PCBo increases, the PCBo absorption wavelength shifts toward 300 nm.

In this embodiment, it is desirable that the laser beam 28 emitted from the laser irradiation device 34 has a pulse width (laser pulse width) of 240 peak (10 ^'12 ) -sec (ps) or less. When a laser beam with a nano (10 ' ⁹ ) - second pulse width is used, the accuracy of the determination is reduced.

In this embodiment, it is desirable that the laser beam 28 emitting from the laser irradiation device 34 has an energy density of 1 to 0.01 GW / cm ² , more preferably 0.05 to 0.01 GW / cm ² . When the laser energy density (GW / cm ² ) exceeds 1 GW / cm ² , the amount of PCB degradation products increases.

As described above, in this embodiment, the laser beam wavelength is set at 240 picoseconds or less and the laser energy density is set at 1 GW / cm ² or less. Thus, laser-induced decay can be suppressed and detection sensitivity can be greatly increased.

A particularly suitable energy density is 0.1 GW / cm ² or close to it.

Fig. 4 shows the relationship between the aforementioned wavelength, pulse width and energy density.

The mass spectra of the PCBo standard sample and the N2 gas sample were measured using a run-time mass spectrometer. The results are shown in Fig.5 and Fig.6. A laser beam having a pulse width of 100 picoseconds was used for this measurement. Figure 5 shows the measurement results at a laser beam energy density of 0.05 GW / cm ² , and Figure 6 shows the measurement results at a laser beam energy density of 0.5 GW / cm ²

A PCBo sample containing 1- to 4-CI PCBs, mainly 2-CI PCBo and 3-CI PCBo was used in this measurement.

As shown in Fig. 5, for a laser beam energy density of 0.05 GW / cm ² , clear peaks corresponding to PCBs are obtained. In contrast, as shown in FIG. 6, at a laser beam energy of 0.5 GW / cm ² , many PCB degradation products are generated and no clear peak corresponding to PCBs is obtained.

Using the aforementioned measuring device, the concentration of PCBs ^: residual, for example, in a gas PCB digester or in liquid discharged from the device, can be measured quickly and accurately at very high sensitivity. Based on the results of these measurements, the treatment process can be monitored

Fourth embodiment

This embodiment further specifies the laser irradiation conditions used in the first embodiment; more specifically, a laser beam that passes through a Raman cell is used.

Figure 7 is a schematic view showing a trace detection device for an organic component according to this embodiment. In this embodiment, the organic component trace detection device 24 is used to detect the organic component trace in the recovered fluid or in the pipeline gas. As shown in FIG. 7, the detection device 24 has a capillary column 25 (sample delivery device) for continuous delivery of a sampled sample 26 having the form of a passing molecular fiber 27 into a vacuum chamber 37; a laser irradiation device 34 for irradiating the incident molecular beam 27 through the laser beam 28, which has passed through Raman cell 40, thereby ionizing the molecules; a convergence section for converging 29 ionizing molecules of laser irradiation containing a plurality of ionic electrodes; an ion trap for selectively trapping 30 molecules so fused; and a run-time mass spectrometer 31 having an ion detector 32 for detecting ions that are emitted at certain time intervals and reflected by reflector 33.

When a Raman cell 40 is fitted, as shown in FIG. 8, the laser beam 28 (its wavelength λ-ι) emitting from the laser irradiation device 34 is distributed to the Stokes light beams (wavelengths: λι + Μι, λι + Μ _2). ...) and anti-Stokes light rays (wavelengths: λι-Μι, λ _ν Μ ₂ ...). In this way, a laser beam 28 having a single wavelength produces a large number of light beams having different wavelengths. Therefore, PCBs having different numbers of chlorine atoms may be simultaneously excited by light rays of different wavelengths thus obtained.

Examples of the above Raman cell include a Raman cell containing a gas such as N ₂ , H _2, or CH 4 under high pressure (e.g., about 24 atm). When a 234 nm laser beam is injected into such a Raman cell, the interaction between the gas molecules in the cell results in a beam having a specific wavelength; for example, a 283 nm light beam is emitted when the cell contains N ₂ , a 301 nm light beam is emitted when the cell contains H _2, or a 288 nm light beam is emitted when the cell contains CH 4.

Figure 9 shows the relationship between the wavelengths and energies of the light beams transmitted through the laser beam 28 through the Raman cell 40.

As shown in FIG. 10, as the number of chlorine atoms in PCBs increases, the PCBo absorption wavelength shifts from a lower level to a higher level. Therefore, the concentration of PCBs can be efficiently measured using a large number of light rays of different wavelengths obtained from a laser beam passing through a Raman cell 40.

FIG. Figure 11 shows the PCB measurement results using the device shown in Figure 7, in which the laser beam is scattered into light beams of different wavelengths using a Raman cell. In Figure 11, the horizontal axis represents the passage time (in seconds) and the vertical axis represents the signal intensity (V).

The results show that an efficient measurement can be made using the device shown in Fig. 7.

Using the aforementioned measuring device, the concentration of PCBs remaining, for example, in the effluent from the PCB digester, can be measured quickly and accurately. Based on the results of these measurements, the treatment process can be monitored

Fifth embodiment

In this embodiment, the ionized capture of laser irradiated molecules is further specified.

FIG. 12 is a schematic representation showing an organic component trace detecting device according to this embodiment. In this embodiment, the organic component trace detection device 24 is used to detect the organic component trace in the recovered liquid or in the effluent gas. As shown in FIG. 12, the detecting device 24 comprises a capillary column 25 (sample delivery device) for continuous introduction of a sampled sample 26 having the shape of a passing molecular beam 27 into a vacuum chamber 37; a laser irradiation device 34 for irradiating the incident molecular beam 27 with a laser beam 28, thereby ionizing the molecules; a convergence section for aligning 29 laser irradiated ionized molecules comprising a plurality of ionic electrodes from 29-1 to 29-3; an ion trap for selectively trapping 30 molecules so fused; and a run-time mass spectrometer 31 having an ion detector 32 for detecting ions that are emitted at certain time intervals and reflected by reflector 33.

FIG. 13 is a schematic representation showing the ionization zone and ion trap. · .. ····

As shown in Fig. 13, the trap 30 has a first electrode with a cap 41 and a small hole 41a through which ionized molecules enter, a second electrode with a cap 42 and a small hole 42a through which the captured molecules are released (first and second electrodes). is located opposite each other) and a high frequency electrode 43 to apply high frequency voltage to the ion trap zone 44.

At the end of the first electrode with a cap 41, the voltage is adjusted so that it is lower (e.g. 6 V) than the voltage of the ion convergence section 29 to approximate the ionized molecules, for example, the voltage of the electrode 41 is adjusted to 0 V. at the end 42, the voltage is adjusted to be higher than that of the first electrode with a cap 41 (e.g., 0V), for example, the voltage of the electrode 42 is adjusted to be 12V.

Since the voltage at the end of the first electrode with a cap 41 is fed below the voltage of the ion convergence section 29 (e.g. 6 V) to bring the ionized molecules together, for example the voltage of the electrode 41 is adjusted to be OV, the ionized molecules are accelerated towards the first electrode with the cap At the end 41, the molecules pass through a small hole 41a in the first electrode with a cap 41 and effectively enter the ion trap 30. In the ion trap 30, the molecules are rapidly decelerated because the voltage at the second electrode at the end 42 is adjusted to be higher than the first electrode. voltage at the end of the cover 41 (eg 0 V); for example, the voltage of the electrode 42 is adjusted to 12 V. When the ion trap 30 is supplied with a high frequency voltage using the high frequency electrode 43, the molecules are rotated about an axis and trapped about the center of the ion trap 30.

When the high-frequency voltage supply is stopped by the high-frequency electrode 43, a high voltage (e.g., 400 V) is applied to the first electrode with a cap 41 and a low voltage (e.g., 400 V) to the second electrode 42. The ions are discharged through the small hole 42a and are detected by an ion detector 32 mounted on a run-time mass spectrometer 31.

The concentration of the measured substance (eg PCBs) can be obtained by comparing the intensities of the signals output from the detector 32.

In the present invention, the high frequency electrode voltage and frequency are preferably 1000-1240 V and at least 1 MHz, respectively. In the case of measurements on PCBs, where the voltage and frequency have the above values, the ions are effectively trapped in the ion trap zone.

There are no specific limits to the voltage and frequency of the high frequency electrode since both the voltage and frequency can be varied as required to the shape of the ion trap and the type of material being measured, thereby optimizing ion trapping.

FIG. 14 illustrates the relationship between electric potential and ion proximity to the central portion of the ion trap when the voltages of the first electrode 29-1, the second electrode 29-2, and the third electrode 29-3 are 6 V, 6 V, and 5 V, respectively; the voltage at the end of the first electrode with the cap 41 is 0 V and the voltage at the end of the second electrode with the cap 42 is 12 V.

As shown in FIG. 14, the ionized molecules are accelerated by the lens-type effect of the convergence section 29, the molecules having the highest velocity near the first electrode with a cap 41 and the accelerated molecules passing through the hole 41a of the first electrode with the cap 41. In the ion trap, the molecules are rapidly decelerated because the voltage at the end of the second electrode with a cap 42 is 12 V; i.e. the voltage of the electrode 42 is higher than that of the electrode 41. As a result, the movement of the molecules stops near the center of the ion trap 30.

The motion of the trapped molecules stops near the position where the electrical potential is almost equal to the potential of the position at which the ionization of the molecules was initiated. Therefore, the voltage at the end of the second electrode with the cap 42 can be adjusted to adjust the location of the trapped molecules.

Preferably, the voltage at the end of the second electrode with the cap 42 is adjusted to be approximately twice that of the first electrode 29-1. In this embodiment, the voltage of the first electrode 29-1 is 6 V and the voltage of the second electrode with the cap 42 is 12 V.

It is not necessary for the voltage of the second electrode shell 42 to be twice the voltage of the first electrode 29-1 and, if necessary, the voltage of the second electrode shell can be selected depending on the shape of the ion trap and the mass of molecules to be trapped.

As described above, the voltage of the second electrode with a cap 42 must be greater than that of the first electrode with a cap 41 to stop movement of the ionized sample in the ion trap.

There are no specific restrictions on sample ionization devices. For example, the ionization device may be a laser irradiation device for irradiating the sample with a laser beam, thereby ionizing the sample. Alternatively, the sample may be ionized using, for example, electron bombardment or plasma bombardment.

Sixth embodiment

FIG. 15 is a schematic view showing an organic component trace detecting device according to this embodiment. In this embodiment, the organic component trace detection device 24 is used to detect the organic component trace in the recovered fluid or in the pipeline gas. As shown in Figure 15, the detection device 24 has an ionization zone45 for ionizing the sample; an area 46 comprising an ion convergence section for approximating 29 ionizing molecules by laser irradiation and accelerating the path of the molecules toward an ion trap for trapping 30 ions; and a run-time mass spectrometer 31. The ionization zone 45, the zone 46, and the spectrometer 31 are separated from each other by partitions. The vacuum in the ionization zone is adjusted to 1 x ^{10 3} tor, the vacuum in zone 46 including the ion convergence section and ion trap is adjusted to 1 x ^{10 5} tor, and the vacuum in the mass spectrometer is adjusted to 1 x ^{10 7} tor.

The components of the device described above are similar to those of the device shown in FIGS.

In this embodiment, the ionization zone 45 and the zone 46 comprising the ion convergence section and the ion trap are separated from each other. Therefore, the unwanted gas does not fall within zone 46, which includes an ion convergence section and an ion trap, and is thus effectively analyzed.

Because the vacuum in zone 46, which includes the ion convergence section and the ion trap, is as much as 1 x 10 < ⁵ > tor, the amount of inert gas can be reduced and the degradation of the readily degraded target compound can be avoided.

FIG. 16 shows the measurement results for PCBs with the vacuum in the region 46 comprising the ion convergence section and the ion trap adjusted to 1 x 10 < ⁵ > tor. As shown in FIG. 16, clear peaks corresponding to 1 -Cl PCB, 2-CI PCB and 3-CI PCB were obtained.

Fig. 17 shows the PCB measurement results when the vacuum in zone 46, which includes the ion convergence section and the ion trap, is adjusted to 1x1 (T ⁴ torr).

As shown in FIG. 17, no clear peaks corresponding to PCBs were obtained; peaks correspond to PCB degradation products.

Seventh embodiment

FIG. 18 is a schematic view showing a laser measuring device according to this embodiment. As shown in FIG. 18, the laser device 24 of this embodiment has a capillary column 25 (sample delivery device) for continuous delivery of a sampled sample 26 having a shape of a passing molecular beam 27 into a vacuum chamber 37; a laser irradiation device 34 for irradiating the incident molecular beam 27 with a laser beam 28, thereby ionizing the molecules; a convergence section for converging 29 ionizing molecules of laser irradiation containing a plurality of ionic electrodes; an ion trap for selectively trapping 30 molecules so fused; and a run-time mass spectrometer 31 having an ion detector 32 for detecting ions that are emitted at certain time intervals and reflected by reflector 33. The concentration of the measured substance can be obtained by comparing the intensities of the signals exiting the detector 32.

FIG. The numbers 47 and 48 in Figure 18 represent the lens type boxes and the figure 49 represent the reflecting mirror.

As shown in FIG. 19, the laser beam 28 emitted from the laser irradiation device 34 is repeatedly reflected by prismatic units 50 and 51 positioned opposite each other such that the reflected laser beams do not overlap with each other in the ionization zone 52 and the laser beam introduced into the zone 52. the sample is irradiated by the following laser beams. The prismatic device 50 has many prisms, but the prismatic device has no particular limitations.

Because many pulsed laser beams do not collide with the same portion of the sample at a time, fragmentation of the sample is avoided. In addition, the laser ionization efficiency of the sample is increased.

Figures 20 and 21 schematically show an optical device for laser beam input, avoiding laser beam overlap. Fig. 20 is a perspective view of this optical device; Figure 21 (A) is a side view of this device; 21 (A) is a projection image of this device.

As shown in FIGS. 20 and 21, this optical device has prisms 53 and 54 that face each other. By adjusting the incident angle of the laser beam 28, the reflected laser beams do not overlap with one another. In this embodiment, since a reflective mirror 55 is provided, the sample is repeatedly excited by reflected laser beams.

In the case of laser irradiation within the ionization zone of 6 mm, if the above prisms reflect a laser beam of 1 mJ 10 times, the same effect is obtained as when a laser beam of 10 mJ is used. This can reduce the cost of the meter.

In the case where the re-reflected laser beam produces overlapping rays, the molecules of the substance that have been ionized by the laser beam are again irradiated with another laser beam and this causes the decomposition of these molecules.

In the present invention, the laser beam is repeatedly reflected so that the reflected laser beams do not overlap with one another.

To re-reflect the laser beam so that the reflected laser beams do not overlap with one another, for example, FIG. 19 shows the method; i.e. a technique using multiple prisms and a reflective mirror. Alternatively, a method may be used in which the incident laser beam is controlled by a pair of superimposed prisms. The present invention may employ any method in which the laser beam can be repeatedly reflected so that the laser beams thus reflected do not overlap with one another.

If organic halogenated materials (e.g. PCBs) are analyzed, the incident laser beam pulse width is increased to increase the ionization efficiency of low chlorine PCBs (i.e. PCBs having 2 to 4 chlorine atoms). However, in order to increase the ionization efficiency of PCBs with high chlorine content (i.e. PCBs having 5-7 chlorine atoms), the pulse width of the incident laser beam is reduced.

Using two types of laser beams with different pulse widths, it is possible to measure both low-chlorine PCBs and high-chlorine PCBs simultaneously.

. In the above embodiment, the measured material is selected PCBs. However, the present invention is not limited to the measurement of PCBs; the present invention may also be adapted to measure the concentrations of dioxin or of the environmental hormones in the effluent emitted from waste incinerators such as refuse incinerators or from an incinerator such as a boiler.

Eighth embodiment

A gas monitoring system for a PCB detoxification treatment device comprising the device of the present invention will now be described.

According to this embodiment, the toxic materials treatment system is used for a treated product (hereinafter referred to as a "treated product") to which a toxic organic halogenated substance (e.g., PCBas) is attached, a treated product containing such substance, or a treated product containing material to be decontaminated. As shown in Figure 22, this treatment system includes pretreatment devices 56, which are either removal devices 57 for removing toxic substance 58 from container 60 (i.e., treated product 59) containing toxic substance 58 (e.g., PCBs), and / or breaking means 61 for breaking the treated article 59 into components 60a, 60b, etc .; core separating means 62 for distributing the core 60a, which is an integral part of the product to be passed through the pre-processing means, into a roll 60b and an iron core 60c; roll separation means 63 for dividing the previously separated roll 60b into copper wire 60d and paper / wood 60e; washing means 62 for washing the iron core 60c, which was separated by the core separator 62, the metal container 59 (including the main container body and lid), which was broken in the breaker 61, and the copper wire 60d, which was separated by the coil separator 63; 64; toxic substance digestion means 65 for digestion of recovered fluid 66 discharged from washer 67 and / or toxic material 58 removed in pretreatment devices; a working fluid monitoring device 68 for measuring the concentration of PCBs in the spent fluid 13 released from the toxic material digestion means 65 (i.e., a PCB processing unit); and a pipeline gas monitoring device 69 for measuring the concentrations of PCBs in the pretreatment unit 56 for breaking the product to be treated and the pipeline gas 70 discharged from the toxic material digestion unit 65.

When the aforementioned toxic agent is in liquid form, the toxic agent is directly fed to the toxic agent digestion means 65 and the material is decontaminated. The components of the container in which the toxic substance was stored are also decontaminated.

The flue gas discharged from the treatment plant is passed through an activated carbon filter and the concentration of PCBs contained in the resulting flue gas is measured by a flue gas monitoring device 69, thereby confirming that the PCBs are present at or below the PCB discharge standard

The concentration of PCBs in the environment outside the treatment plant, as well as in the treatment plant, can be controlled by a gas-gas monitoring device 69.

The above-mentioned Toxic Material Handling Devices 65 may be shown in FIG. 32 as hydrothermal oxidation-decomposition units, supercritical water oxidation units, or periodic oxidation-decomposition units.

Toxic substances that pollute the environment are decontaminated using the treatment system of the present invention. Examples of such toxic substances include, but are not limited to, PCBs, vinyl chloride sheets, toxic waste, inadequate fuels, toxic chemicals, end-of-life resins and untreated explosives.

Examples of processed products that are treated by the system of the present invention include, but are not limited to, transformers and capacitors containing PCBs as insulating oils and containers containing toxic materials such as paint.

PCBs have generally been used in ballasts for fluorescent lamps and therefore have to be decontaminated. Because of the small volume of such ballast, such ballast can be decontaminated by placing the ballast directly into the separator 62 without any pre-treatment.

When the above-mentioned toxic substance is in liquid form, such toxic substance is fed directly to the toxic substance digester 65 and the substance is decontaminated. The components of the container in which this toxic substance was stored shall also be decontaminated. The concentration of PCBs in the liquid thus decontaminated must be confirmed to be less than or equal to 3 ppb (PCB emission standard).

The components of the toxic material treatment device 65, which are similar to the components of the device shown in FIG. 32, are denoted by the same numerals and therefore are not repeated.

The gas monitoring device 69 of this embodiment utilizes the same measuring system 35, which includes the measuring device 24 shown in Figure 3, and controls the gas in the gas 70 discharged from the treatment device 65 and purified by the concentration of activated carbon PCBs.

In this embodiment, the working fluid monitoring device 68 utilizes the same measuring system 35, which includes the measuring device 24 shown in Figure 3, and is controlled by the working fluid 13, which is discharged from the processing device 65 and is purified using a concentration of activated carbon PCBs.

Once the aforementioned measuring system is installed, the concentration of PCBs can be controlled quickly and efficiently. As a result, digestion may be carried out, controlling the proper implementation of the treatment process and thus complying with environmental regulations.

With the aforementioned measuring device, PCB analysis can be performed at certain scheduled intervals to control PCB concentrations at or below the PCB discharge standard. Therefore, when necessary, for example when PCB concentrations above the exhaust standard are scrubbed with gas, for example, activated carbon and operational procedures are checked to prevent environmental contamination outside the treatment system.

Ninth embodiment

Figure 23 is a schematic representation showing a system for the decomposition of an organic halogenated material.

The breaking system for the organic halogenated material of the present invention will be described as an example of a PCB breaking treatment

As shown in FIG. 23, the decomposition system of the organic halogenated material of this embodiment comprises a hydrothermal oxidation decomposition unit 1 having a heated constant pressure reactor in which PCBs are decomposed into, for example, sodium chloride (NaCl) and carbon dioxide (CO ₂ ) through dechlorination and oxidation. decomposition in the presence of sodium carbonate (Na ₂ CO ₃ ); and a measuring system 35 for measuring the concentration parameters of the PCBs and / or PCB degradation product remaining in the working fluid 13 discharged from the gas-liquid separator 10; measurement system 35 uses laser time-of-flight mass spectroscopy.

The measuring system 35 may be any of the measuring devices according to the first to seventh embodiments.

As shown in Figure 23, the hydrothermal oxidation-decomposition unit 1 of the organic halogenated fission system comprises a fission zone 1A and a feed zone 1B. The hydrothermal oxidation-decomposition unit 1 may show a hydrothermal oxidation-decomposition treatment unit 1 in FIG. However, hydrothermal oxidation-splitting device does not raise any special restrictions as long as the device can divide PCBus the presence of sodium carbonate (Na2CO ₃₎

As shown in FIG. 23, the organic halogenated material (PCB) digestion system includes an analysis-operation control area 1C. In the Analytical Operations Control Area 1C, the measurement system 35 measures the concentration parameters of PCBs and / or PCB degradation products remaining in the working fluid 13 and thus measures the concentration parameters fed to a calculator 71, thereby optimizing the hydrothermal oxidation-digester processing unit) conditions 1 through feedback control.

Examples of PCBs that can be detected using the device described above are low chlorine PCBs such as 1-CI PCB (monochlorobiphenyl) 2-CI PCB (dichlorobiphenyl) and 3-CI PCB (trichlorobiphenyl), and high chlorine PCBs such as 4-CI PCB (tetrachlorobiphenyl) and 5-CI PCB (pentachlorobiphenyl). Such PCBs are detected and data is transmitted for processing.

Examples of processing products that are treated using the system of the present invention include, but are not limited to, PCB-containing insulating oils (various oils containing high or low concentrations of PCBs) that have been used, for example, in transformers and capacitors; and PCB-containing paints.

PCBs are broken down into various products. Examples of such PCB degradation products are dichlorobenzenes, phthalates, volatile organic compounds, phenol, biphenyl, benzene or biphenyl derivatives, aldehydes, organic acids and aromatic hydrocarbons. Specific examples of such PCB cleavage products are given below, but the cleavage products are not limited to these examples.

Examples of dichlorobenzenes include o-dichlorobenzene and p-dichlorobenzene.

Examples of phthalates include dimethyl phthalate, diethyl phthalate, dibutyl phthalate and di-2-ethylhexyl phthalate.

Examples of volatile organic compounds (VOCs) include 1,1-dichloroethylene, dichloromethane, trans-1,2-dichloroethylene, cis-1,2-dichloroethylene, chloroform,

1,1,1-trichloroethane, carbon tetrachloride, benzene, 1,2-dichloroethane, trichloroethylene, 1,2-dichloropropane, dichlorobromomethane, cis-1,3-dichloropropene, toluene, trans-1,3-dichloropropene, 1,1,2 -trichloroethane, tetrachloroethylene, dibromochloromethane, p-xylene, m-xylene, o-xylene, bromoform and p-dichlorobenzene.

Examples of alkylbenzenes include ethylbenzene, 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, sec-butylbenzene, iso-butylbenzene and n-butylbenzene.

Examples of phenolic products include phenol, 2-methylphenol, 4-methylphenol, 2,6-dimethylphenol, 2-ethylphenol, 2,5-dimethylphenol, 3-ethylphenol, 2,3-dimethylphenol, 3,4-dimethylphenol, 2,4, 6-trimethylphenol, 2,3,6-trimethylphenol, 2,3,5-trimethylphenol and 4nonylphenol.

Examples of benzene derivatives and biphenyls include styrene monomer, amethyl styrene, benzyl alcohol, acetophenone, 4'-ethylacetophenone, 2-methylnaphthalene, biphenyl, 1,3-diacetylbenzene, dibenzofuran, fluorene, benzophenone and xanthone.

Examples of aldehydes include formaldehyde, acetaldehyde and benzaldehyde.

Examples of organic acids are formic acid, acetic acid and lactic acid.

Of the above-mentioned dichlorobenzenes, o-dichlorobenzene is a particularly suitable detection object; i.e. the concentration parameters of one of these substances are obtained.

Of the phthalates mentioned above, dimethyl phthalate is a particularly suitable detection object; i.e. the phthalate concentration parameters are obtained.

Of the above-mentioned volatile organic substances (VOCs), benzene or toluene is a particularly suitable target; i.e. the concentration parameters of one of these substances are obtained.

Of the alkylbenzenes mentioned above, a particularly suitable target is ethylbenzene, 1,3,5-trimethylbenzene or 1,2,4-trimethylbenzene; i.e. the concentration parameters of one of these substances are obtained.

Of the above-mentioned phenolic products, phenol, 2-methylphenol, 4-methylphenol or 4-nonylphenol are particularly suitable for detection; i.e. the concentration parameters of one of these substances are obtained.

Of biphenyl products, a particularly suitable target for detection is monochlorobiphenyl, dichlorobiphenyl or trichlorobiphenyl; i.e. the concentration parameters of one of these substances are obtained.

Of benzene derivatives and biphenyls, benzyl alcohol, acetophenone, dibenzofuran or benzophenone are particularly suitable detection agents; i.e. the concentration parameters of one of these substances are obtained.

Of aldehydes, a particularly suitable detection object is formaldehyde, acetaldehyde or benzaldehyde; i.e. the concentration parameters of one of these substances are obtained.

PCBs and / or PCB degradation products are detected using the detector 32 of the aforementioned device.

Fig. 24 shows the concentration parameters of PCB degradation products thus determined.

Fig. 24 shows the concentration parameters of the PCB cleavage products contained in the processed liquid 13 obtained by cleaving the PCBs in the above-mentioned hydrothermal cleavage unit 1. The cleavage products include biphenyl, aromatic hydrocarbons, monochlorobiphenyl, dichlorobiphenyl, trichlorobiphenyl, and hydrocarbons such as Cl ₂ H ₂ 4, C ₁₅ H ₂ 8 and C ₁₅ H 30.

As shown in Figure 24, no PCBs were detected.

Tenth embodiment

Where the above monitoring system is in operation, samples may be taken from many sampling points for analysis. An exemplary multipoint measurement of the present invention will now be described.

Fig. 25 is a schematic view showing the overall construction of an organic component trace measuring apparatus according to the present invention.

As shown in Figure 25, the first ends of the pipeline gas sampling tubes 72a72e are connected to five sampling locations 73a-73e located in the pipeline gas path 73 through which the pipeline gas passes. The other ends of these sampling tubes 72a-72e are connected to the first end of the connecting tube 74. The other end 74 of this connecting tube is connected to the sample delivery device 24 of the detection device 24 shown in FIG. The first end of the suction pipe 75 and the first end of the outlet pipe 76 are connected to this connecting pipe 74.

The second end of the suction pipe 75 and the second end of the drain pipe 76 are connected to a drain pipe 76 connected to the gas path 73 of the pipeline.

Sampling tubes 72a-72e are connected to discharge tube 77 via branching tubes 78a-78e. The vacuum chamber 37 of the above-mentioned detection device 24 is connected to the discharge tube 77 via the discharge tube 79. A run-time mass spectrometer 31 of the detection device 24 is connected to the discharge tube 77 via the discharge tube 80.

Sampling tubes 72a-72e are fitted with vacuum solenoid valves 81a-81e, respectively. Vacuum solenoid valve 82 and diaphragm pump 83 are provided in suction pipe 75. Vacuum solenoid valve 84 and centrifugal helical pump 85 are provided in outlet tube 76. Flowmeters 86a-86e and diaphragm pumps 87 are provided in diverting tubes 78a-78e. The outlet tube 79 is provided with a centrifugal helical pump 88. The outlet tube 80 is provided with a deep vacuum pump 89.

As shown in FIG. 1, the detection device 24 used in this embodiment has a vacuum chamber 37 which is connected to a discharge tube 79 and generates a vacuum of approximately 10 '¹; a capillary column 25 (sample delivery device) for continuous introduction of the conduit gas 88 taken from the connecting tube 74 in the form of a passing molecular beam 89 into a vacuum chamber 37; a laser irradiation device 34 for irradiating the incident molecular beam 89 with a laser beam 90 thereby ionizing the molecules; a convergence section for the convergence of 29 ionized molecules of laser irradiation containing a plurality of ionic electrodes; an ion trap for selectively trapping 30 molecules so fused; and a run-time mass spectrometer 31 coupled to a vacuum chamber 37 and a discharge tube 80, which generates a very deep vacuum of approximately 10 ' ^{7 to} 10 ⁸ ' torus and which has a reflector to reflect the ions trapped at certain intervals in the ion trap, and ion detector for detecting 32 ions.

The ion detector 32 of the run-time mass spectrometer 31 of the detecting device 24 is electrically coupled to the control-control device 90 embedded in the control chamber (not shown). Electrically connected vacuum solenoid valves 81a-81e, 82 and 84, diaphragm pump 83, centrifugal helical pumps 85 and 88, deep vacuum pump 89, and laser irradiation device 34 of detection device 24 are connected to control-control device 90. an inlet device 91a and a display 91b are connected.

In this embodiment, the suction tube 75, the vacuum solenoid valve 82 and the diaphragm pump 83 comprise a gas suction device outlet pipe 76, a vacuum solenoid valve 84, and a centrifugal helical pump 85 form a cleaning device outlet pipe 77 and branch pipes 78a-78e form a return pipe 86 and diaphragm pumps 87a-87e provide gas circulation equipment.

An organic component trace measuring device 92 having the above design functions as follows:

In particular, diaphragm pumps 87a-87e are actuated; at sampling points 73a-73e, sampling the gas 88 passing through the gas path 73 and injecting it into the sample tubes 72a-72e, at which time the flow rates of the gas 72a-72e are checked by flow meters 86a86e; and the pipeline gas 88 is discharged by the branching pipes 78a-78e and returned to the pipeline gas path 73 by the discharge pipe 77. During the above procedure, the vacuum solenoid valves 81a-81e, 82 and 84 are closed.

After actuation of the control-control device 90, the vacuum solenoid valves 81a and 82 are opened and the diaphragm pump 83, the centrifugal helical pumps 85 and 88 and the deep vacuum pump 89 are actuated.

When the laser irradiation device 34 of the detector device 24 is actuated, a pipeline gas 88 is sampled into the vacuum chamber 37 through the connecting tube 74 and the capillary column 25 of the detector device 24 and sampled at the sampling points 73a-73e. taking tube 72a. This molecular beam 89 is irradiated with a laser beam 90 so that, upon ionization of the molecules, the ions of interest are trapped in the ion trap 30 and these trapped ions are detected by the ion detector 32 of the mass spectrometer 31. The control unit 90 calculates organic components. concentrations of traces, such as toxic substances (such as PCBs), in the pipeline gas 88 sampled at the gas pipeline 73 sampling site.

After measuring the concentrations of toxic substances in the gas 88 of the pipeline, sampled at the sampling point 73a of the gas path 73, vacuum vacuum solenoid valves 81a and 82 are closed, vacuum control valve 84 is opened by the control device 90 and into the gas path. The discharge pipe 77 is used to discharge the pipeline gas 88, which has been taken up in the pipeline gas passage 73a and remains in the connecting pipe 74, thereby cleaning the inside of the connecting pipe 74.

After cleaning the inside of the connecting pipe 74 in the manner described above, the vacuum solenoid valve 84 is closed and the control-control device 90 opens the vacuum solenoid valves 81b and 82, and then the pipeline gas 88, sampled at the pipeline 73 the pick-up tube 72b through the connecting tube 74 introduced into the laser irradiation-ionization zone of the detection device 24. Thereafter, concentrations of the toxic substances present in the pipeline gas 88, sampled at the sampling line 93b of the gas pipeline 73, are then measured in a similar manner. The vacuum solenoid valves 81b and 82 are then closed, the vacuum solenoid valve 84 is opened, and the gas line 88 is discharged into the pipeline 73 by the outlet pipe 77, which has been taken in the pipeline outlet 73a and remains in the connecting pipe 74. 74 inside.

Each of the vacuum solenoid valves 81c-81e is then operated in a similar manner to that described above, thereby performing an analysis of the pipeline gas 88 sampled at the respective pipeline 73 sampling points 73c-73e. Subsequently, the pipeline gas 88 is vented from the connecting pipe 74, thereby purifying the inside of the pipe 74.

In this embodiment, the concentrations of toxic substances in the pipeline gas 88 sampled at the pipeline 73 sampling points 73a-73e can be measured using a detection device 24 alone. Therefore, the cost of such a measurement can be reduced.

Because a centrifugal helical pump 85 is used to clean the inside of the connecting pipe 74 by taking a sample of the pipeline gas 88 from each sampling point 73a-73e, the concentrations of the toxicants in the pipeline gas 88 sampled at the sampling points 73a-73e can be accurately measured. .

Vacuum solenoid valves are used in this embodiment. However, for example, an electric ball valve or a bellows valve may be used in place of such a vacuum solenoid valve.

In this embodiment, the vacuum solenoid valve 82 and the diaphragm pump 83 form a gas intake device, while the vacuum solenoid valve 84 and the centrifugal helical pump form a purge device. However, when a valve with a slightly adjustable orifice is used, the gas inlet device and the purge device may be combined together with a centrifugal helical pump.

The detection device used in this embodiment may be any of the devices according to the second to eighth embodiments.

Eleventh embodiment

When component traces are continuously measured over the long term by the above monitoring system, a correction device must be used. An example of a correction device associated with this embodiment will now be described.

Fig. 26 is a schematic view showing a device for adjusting the concentration of organic halogenated material according to this embodiment. As shown in FIG. 26, the organic halogenated concentration adjusting device 93 of this embodiment includes a standard container 94 containing a certain predetermined concentration of the organic halogenated substance 95; a purge gas feed tube 96 for supplying purge gas 97 to remove organic halogenated material 95 in standard container 94; and a standard gas inlet tube 98 for introducing a standard gas 99 containing a predetermined concentration of organic halogenated material 95, accompanied by the scrubbing gas 97, into a mass spectrometer 24.

The purge gas feed tube 96 has a branched feed line 100 for supplying the purge gas to a standard container. Valves 101 and 102 are located in supply line 100 and gas outlet line 103. respectively. Valve 104 is located in the path between the purge gas supply tube 96 and the standard gas inlet tube 98 so as to open and close this path.

The internal temperature of the standard container 94 is maintained at 5 to 30 degrees higher than the ambient temperature of the container by means of a temperature maintaining device (not shown), thereby maintaining the saturation concentration of the organic halogenated substance 95 in the container.

Table 1 shows the relationship between saturated vapor pressure and PCB concentration in the case of the above-mentioned organohalogenated substance 95 PCB.

If the aforementioned halogenated material is from 2 to 4-CI PCB, it is desirable that the standard container bot be stored at 35 ° C (i.e., room temperature (25 ° C) + 10 degrees) using a thermostated bath.

If the above halogenated material is 5- to 7-CI PCB, it is desirable to keep the standard container at 24 ° C (i.e., room temperature (25 ° C) + 25 degrees) using a thermostated bath.

table

saturated vapor pressure PCBo concentration 10 mg / Nm ³ 2-CI PCBas ........... .0.2 mg / Nm ³ 3 mg / Nm ³ 3-CI PCBas ........... .0.5 mg / Nm ³ 0.5 mg / Nm ³ 3-CI PCBas ............. .05 mg / Nm ³

Kanechlor KC300 (a product of Kanegafuchi Chemical Industry Co., Ltd.) is a commercially available PCB product containing 2-CI PCBo, 3-CI-PCBo and 4-CI PCBo. Kanechlor KC400 (product of Kanegafuchi Chemical Industry Co., Ltd.) contains 3-CI PCBo, 4-CI-PCBo and 5-CI PCBo. Kanechlor K31 (product of Kanegafuchi Chemical Industry Co., Ltd.) contains 5-CI PCBo, 6-CI-PCBo and 7-CI PCBo.

To maintain the saturation concentration of PCBo at a defined level, a standard container is provided with a PCBo solution prepared by dissolving PCBs in a standard liquid (e.g., n-hexane); this container is degassed under vacuum for one hour to remove n-hexane; the container is sealed and the container is maintained at 100 ° C for 1 hour, thereby creating a uniform concentration of PCBs inside the container.

A standard gas inlet pipe 98 (e.g., a heater) is fitted to the standard gas inlet pipe 98 to maintain the temperature inside the pipe 98 at 150 ± 20 ° C, thereby preventing organic halogenated material from adhering to the inner wall of the pipe.

Preferably, the distance D between the standard gas inlet pipe 98 and the standard container 94 is such that this distance D is about 10 times the internal diameter (Φ) of the standard gas inlet pipe 98.

In the case where the distance D is short, when the valve 102 is opened, the heated gas enters the standard container. Therefore, to avoid this problem, the distance D is set as described above.

The current emission limit for pipeline gas from the PCB treatment plant described above is 0.15 mg / Nm ³ (ie 15 ppb / V). Therefore, a standard gas containing 1/5 of the above amount of PCBs is used to adjust the concentration in the mass spectrometer. As shown in Figure 27, a standard gas inlet pipe 98 is provided with a dilution gas supply pipe 106 for supplying the dilution gas 107 (air or nitrogen). The reference gas 99 is diluted with the dilution gas 107 so as to obtain a predetermined concentration.

As shown in Fig. 30, the standard container 94 has a plurality of discs 108 having a plurality of holes; and a feed line 100 for supplying purification gas 97 to the bottom of container 94. The cleaning gas 97 is fed to the bottom of the container 94 and is forced to pass through the holes 108 of the disks 108 to thereby carry the saturated PCBais gas out of the container.

In this way, a standard sample of PCBo of uniform concentration can be introduced into the mass spectrometer.

Fig. 28 Number 109 denotes a thermometer.

As shown in Fig. 29, instead of using the disks 108, the standard container may be filled with fiberglass or bead 110.

The inner wall of standard container 94 is coated with a coating layer consisting of, for example, polytetrafluoroethylene or silica. Such a coating layer is required to prevent the PCBs from penetrating the inner wall of the container.

As shown in Fig. 30, the standard container 94 may be of the retractable cartridge type having a removable part 111.

Thus, standard container 94 is readily available and any type of standard container may be provided.

As shown in FIG. 30, the removable standard container 94 may be in an airtight container 112. When the container 94 is in an airtight container 112, it is possible to prevent the PCBs from escaping outward during connection / disconnection of the container 94.

When the detectable substance is fed into a standard container 94 and the sensor for detecting the detectable substance is in an airtight container

112, improper connection of the container 94 may be discovered at an early stage.

Preferably, the above-mentioned detectable material is, among other materials, hydrogen. If purge gas 97 containing about a few percent hydrogen is fed into container 94 and known detection devices are provided on the inner wall of airtight container 112, hydrogen leakage can be detected rapidly. As a result, when the hydrogen is detected (the detectable substance), an improper connection of the container 94 may be found. The hydrogen content of the scrubbing gas may be 100%. However, in terms of hydrogen leakage, it is desirable to have a hydrogen content in the purification gas of 4% (i.e., a lower explosion limit of hydrogen) or less.

When an organic halogenated sampling line is inserted in an airtight container containing a standard cartridge type 94 container

113, direct measurement of the concentration of the organic halogenated substance can be made using a measuring system 35 comprising a measuring device 24 according to any one of the first to seventh embodiments.

In the case of the above-mentioned halogenated concentration adjusting device 93, when the concentration of PCBs in the PCB processing unit is continuously measured, even if the measuring conditions in the run-time mass spectrometer 31 are changed, such changes can be quickly corrected.

Sample feed pipe 88 and purge gas feed pipe 96 are fed with a predetermined concentration of internal standard gas 35 (e.g., monochlorobenzene) for control purposes. Changes in measurement conditions can be confirmed by controlling the concentration of these gases 35.

In general, the concentration of PCBs measured by the above-mentioned device is almost zero. Therefore, it is difficult to determine whether the concentration of PCBs measured in this way is really zero, or if the concentration of PCBs is inaccurately determined due to abnormal operation of the measuring device or clogging of pipes. However, when the aforementioned control gas is supplied, if the intensity of the peak of the control gas thus supplied changes (usually the intensity of this peak must be constant), abnormal operation of the measuring device or blockage of the pipes can be detected very quickly.

The concentration of the reference gas may be corrected by confirming that the relationship between the peak intensity of the control gas 35 and the peak intensity of the standard gas 99 is constant.

Figure 31 is a graph showing the results of standard gas and control gas measurements.

The measuring device that may be used in the correction device of the present invention is not limited to the aforementioned measuring device.

In the case where the concentration of PCBs is measured by the aforementioned measuring device at certain scheduled intervals, if, after a predetermined period of time (eg one week or 10 days), the measuring device is supplied with a gas for concentration adjustment, the measuring device may: work properly.

Industrial applications

As described above, the present invention provides a device for detecting organic halogenated gas in a gas. This detection device includes a sample delivery device for continuous injection of a sampled sample into a vacuum chamber; a laser irradiation device for irradiating a sample so introduced with a laser beam, thereby ionizing the sample by converging a section to approximate molecules that have been ionized by laser irradiation; an ion trap for the selective capture of such fused molecules; and a run-time mass spectrometer having a detector for detecting ions which are emitted at specified intervals. The detection device shall permit rapid analysis of organic halogens such as PCBs and dioxins.

Claims (50)

DEFINITION OF INVENTION 1. An instrument for the detection of traces of an organic component, having: a sample delivery device for continuous injection of the sampled sample into a vacuum chamber; a laser irradiation device for irradiating the sample thus introduced with ionizing radiation, characterized in that it still has; a convergence section for approximating molecules that have been ionized by laser irradiation; an ion trap for the selective capture of molecules thus converged; and a run-time mass spectrometer incorporating an ion detector for detecting ions that are released at predetermined intervals. 2. An apparatus for detecting traces of an organic component according to claim 1, characterized in that the sample delivery device is a capillary column and the tip of said capillary column intervenes in the convergence section. 3. An apparatus for detecting traces of an organic component according to claim 1, characterized in that the capillary column is made of quartz or stainless steel. 4. An apparatus for detecting traces of an organic component according to claim 1, wherein the laser beam emitting from the laser irradiation device has a wavelength of 300 nm or less. 5. An apparatus for detecting traces of an organic component according to claim 1, wherein the laser beam emitting from the laser irradiation device has a pulse width in the order of picoseconds. 6. An apparatus for detecting traces of an organic component according to claim 1, wherein the laser beam emitting from the laser irradiation device has a pulse rate of at least 1 MHz. 7. An organic component trace detection device according to claim 1, wherein the organic component traces are traces of polychlorinated biphenyl (PCBo) contained in the gas of the processing unit in which the PCBo is decomposed. 8. An organic component trace detection device according to claim 1, wherein the organic component trace material is a trace amount of PCBo contained in the pipeline gas or in the spent fluid discharged from the processing unit in which the PCBo was decomposed. 9. An organic component trace detection device according to claim 1, wherein the laser beam emitting from the laser irradiation device has a wavelength of 300 nm or less, a pulse width of 1000 picoseconds or less, and an energy density of 1 GW / cm ² or less. , and traces of the organic component are detected while stopping the organic component. 10. The device for detecting traces of an organic component according to claim 9, wherein the laser beam has an energy density of from 1 to 0.01 GW / cm ² . 11. An organic component trace detection device according to claim 9, wherein the organic component trace is a trace PCBo with a low chlorine atom, a laser wavelength of 250 to 280 nm, a pulse width of 500 to 100 picoseconds, and energy density is 1 to 0.01 GW / cm ² . 12. An organic component trace detection device according to claim 9, wherein the organic component trace is a trace PCBo containing a high number of chlorine atoms, the laser beam has a wavelength of 270 to 300 nm, a pulse width of 500 to 1 picosecond, and density is between 1 and 0.01 GW / cm ² . 13. A device for detecting traces of an organic component according to claim 1, wherein said laser beam passes through a Raman cell. 14. An apparatus for detecting traces of an organic component according to claim 13, wherein the Raman cell contains hydrogen. 15. The device for detecting traces of an organic component according to claim 1, characterized in that the ion trap consists of a first electrode with a cap at the end having a small hole passing through ionized molecules, a second electrode with a cap at the end having a small hole at which the trapped molecules (the first and second electrodes with caps at each end are opposite each other), and a high-frequency electrode to supply the ion trap with a high-frequency voltage at the end of the first electrode with a cap to approximate the ionized molecules of the ion convergence section the voltage at the end of the cap is higher than that of the first electrode with the cap; and the ionized molecules are trapped at high frequency voltage while the molecules in the ion trap are selectively retarded. 16. An apparatus for detecting traces of an organic component according to claim 15, wherein an inert gas is passed through an ion trap. 17. A device for detecting an organic trace component according to claim 15 characterized in that the ionization zone is 1 x 10 ^"3 torr vacuum, the ion convergence section and the ion trap is 1x10" ⁵ torr vacuum and a time-mass spectrometer is 1x10 ^'7 torr vacuum. 18. An apparatus for detecting traces of an organic component according to claim 1, wherein the laser beam emitted from the laser irradiation device is reflected multiple times so that the reflected laser beams do not overlap with one another in the ionization zone. 19. The device for detecting traces of an organic component according to claim 18, wherein the laser beam emitted from the laser irradiation device is reflected multiple times using opposing prisms so that the reflected laser beams do not follow the same path. A method for detecting traces of an organic gas component, comprising continuously introducing a collected sample into a vacuum chamber; laser irradiation of said entrained sample, thereby ionizing said sample, characterized by selectively trapping ionized laser radiation molecules in an ion trap by converging ionized laser radiation molecules; and detecting the ions emitted from the ion trap at specified time intervals on a run-time mass spectrometer. 21. The method of detecting traces of an organic component according to claim 20, wherein the trace gas is present in the treatment plant in which the PCB digestion was performed. 22. The method of detecting traces of an organic component according to claim 20, comprising the use of an ion trap consisting of a first electrode with a cap at the end having a small hole through which ionized molecules enter, a second electrode with a cap at the end having a small hole at the captured molecules are released, the first and second electrodes with caps at each other and a high-frequency electrode to supply the ion trap with a high-frequency voltage at the end of the first electrode with a cap below the converging section to approximate the ionized molecules and the second electrode with the cap the voltage at the rear is higher than the voltage at the end of the first electrode with a cap; and trap the ionized molecules under high frequency voltage while the molecules in the ion trap are selectively retarded. 23. The organic trace component detection method according to claim 22, characterized in that in the ion trap allows inert gas ionization zone supports 1x10 ^'3 torr vacuum convergence section and the ion trap maintains 1x10 ^"5 torr vacuum and a time-mass spectrometer supports 1x10" ⁷ Torr vacuum. 24. The method of detecting traces of an organic component according to claim 21, wherein the gas is present in the gas in the treatment plant in which the PCBo is decomposed. 25. The method of detecting traces of an organic component according to claim 21, wherein the laser beam emitted from the laser irradiation device is reflected several times so that the reflected laser beams do not overlap with one another in the ionization zone. 26. The method of detecting traces of an organic component according to claim 25, wherein the laser beam emitted from the laser irradiation device is repeatedly reflected using opposing prisms so that the reflected laser beams do not follow the same path. 27. A method of controlling the decomposition of a toxic substance, comprising measuring the decomposition products, wherein using a run-time mass spectrometer according to claim 1, measuring the concentration parameters of the toxic substance and / or the product obtained by cleaving the toxic substance in the treated liquid. digestion in a toxic material digestion unit including a reactor for digesting the toxic material; and optimizes the digestion conditions of the toxicant based on the concentration of the toxicant and / or toxicant degradation product so measured. 28. A method for controlling the decomposition of a toxic substance according to claim 27, wherein the toxic substance produces a product which is, for example, dichlorobenzene, phthalate, volatile organic compound, phenol, biphenyl, benzene or biphenyl derivative, aldehyde, organic acid or aromatic hydrocarbon. 29. An organic material decomposition system comprising a hydrothermal oxidation-decomposition unit, characterized in that the unit comprises a heated and uniform pressure reactor in which the organic halogenated material is decomposed, for example, into sodium chloride (NaCl) and carbon dioxide (CO _2). ) through dechlorination and oxidation-cleavage in the presence of sodium carbonate (Na 2 CO 3); an organic component trace detection device according to claim 1, for measuring the concentration of a toxic substance and / or a product obtained by cleaving the toxic substance in the treated liquid discharged from the hydrothermal oxidation-cleavage device; and a performance control device for controlling the operation of the hydrothermal oxidation-decomposition device by measuring the results obtained with the organic component trace detection device. 30. The organic material decomposition system of claim 29, wherein the hydrothermal oxidation-decomposition unit comprises a cylindrical reactor with a cyclone separator; a constant pressure pump to maintain the pressure of the oil or organic solvent, the toxic substance, water (H ₂ O) and sodium hydroxide (NaOH); heater for initial water heating; a secondary reactor having a helical tube; refrigerating the treated liquid discharged from the secondary reactor in the refrigerator; a gas-liquid separator for separating the treated liquid from the gas; and a pressure-reducing valve. 31. An organic material digestion system according to claim 29, comprising an operating control device controlling at least one of the parameters selected from heating the toxic material digestion system, maintaining a constant pressure in the system, the amount of liquid to be treated, and the amount of oxidizing agent. and sodium hydroxide (NaOH). 32. An organic component footprint measuring device, characterized in that it has: an organic component trace detection device according to claim 1; a plurality of sampling tubes for gas sampling from gas sampling points located on the gas path; a valve installed in each sampling tube; a connecting tube for connecting the sampling tubes to the laser irradiation device of the detection device; a gas suction device for securing gas circulation, which is connected to a connecting pipe; and a purge device for venting the residual gas between the valve in each of the sampling tubes and the detection device; said cleaning device being connected to a connecting pipe. 33. The organic component trace measuring device of claim 32, further comprising a return tube disposed between the valve and a location to which each of the sampling tubes is connected and connected to the gas path; and a gas circulation device for providing gas circulation, which is mounted in the return pipe. 34. An organic component trace measuring device according to claim 32, wherein the gas suction device comprises a diaphragm pump connected to the connecting pipe and a valve arranged between the connecting pipe and the diaphragm pump. 35. An organic component trace measuring device according to claim 32, wherein the cleaning device comprises a centrifugal helical pump connected to the connecting pipe and a valve disposed between the connecting pipe and the centrifugal spiral pump. 36. An organic component trace measuring device according to claim 32, wherein the valve is any valve selected from a vacuum solenoid valve, an electric ball valve, and a bellows valve. 37. An organic halogenated substance concentration adjustment device for adjusting an organic component trace detection device according to claim 1, characterized in that it consists of a standard container containing a defined concentration of the organic halogenated substance; and introducing a standard gas inlet tube for purifying gas into a standard container for removing organic halogenated material, thereby introducing into the mass spectrometer organic halogenated material accompanied by the cleaning gas. 38. The device for adjusting the concentration of an organic halogenated substance according to claim 37, further comprising a temperature maintaining device for maintaining the temperature of a standard container such that it is 5 to 100 degrees above ambient temperature of the container. 39. A device for adjusting the concentration of an organic halogenated substance according to claim 37, further comprising a temperature maintaining device for maintaining a standard gas inlet temperature of 150 ° C or higher. 40. The device for adjusting the concentration of an organic halogenated substance according to claim 37, wherein the standard container is provided with a disc having a plurality of holes. 41. A device for adjusting the concentration of an organic halogenated substance according to claim 37, wherein the standard container is filled with fiberglass or granules. 42. The device for adjusting the concentration of an organic halogenated substance according to claim 40, wherein the feed pipe for supplying the scrubbing gas is located at the bottom of a standard container so that the outlet of the feed pipe is downward and the feed scrubbing gas is discharged from the upper portion of the container. 43. The device for adjusting the concentration of an organic halogenated substance according to claim 37, wherein the standard container is provided with a coating consisting of polytetrafluoroethylene or silica. 44. The device for adjusting the concentration of an organic halogenated substance according to claim 37, wherein the standard container is removable. 45. The device for adjusting the concentration of an organic halogenated substance according to claim 44, characterized in that the removable standard container is contained in an airtight container. 46. The device for adjusting the concentration of an organic halogenated substance according to claim 45, wherein the detectable substance is fed into a standard container and the sensor for detecting the detectable substance is incorporated in an airtight container. 47. A device for adjusting the concentration of an organic halogenated substance according to claim 46, wherein the detectable substance is hydrogen. 48. The device for adjusting the concentration of an organic halogenated substance according to claim 37, wherein the sample contains PCBo. 49. A method for determining trace amounts of an organic component, comprising the step of detecting the organohalogenated material by adjusting the concentration of the organohalogenated material at appropriate time intervals using an organic halogenated material concentration adjusting device according to claim 37. 50. A method for determining trace amounts of an organic component according to claim 49, wherein the sample comprises PCBs and the organic halogenated substance is PCB.